CN110233290A - Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution - Google Patents

Abstract

The issue of the present invention is to provide a kind of nonaqueous electrolytic solution and use the non-aqueous electrolyte secondary battery of the nonaqueous electrolytic solution, the nonaqueous electrolytic solution has capacity retention ratio after excellent circulation, it is exported after circulation, discharge capacity after circulation, the cycle characteristics such as cyclic discharge capacity ratio, output characteristics, High temperature storage characteristic, cryogenic discharging characteristic, it is large current discharge characteristic, High temperature storage characteristic, safety, high capacity, height output, the cycle characteristics of high current density, and the having both property of these performances etc. is also excellent, by the present invention in that with mono-fluor phosphate and/or difluorophosphoric acid salt is contained, and solves the above subject containing the nonaqueous electrolytic solution with specified chemical structure or the compound of specific physical property.

Description

Nonaqueous electrolytic solution and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution

The application be the applying date be on April 18th, 2008, application No. is 201510395046.2, it is entitled " non-aqueous The divisional application of the application of electrolyte and the non-aqueous electrolyte secondary battery for using the nonaqueous electrolytic solution ".

Technical field

The present invention relates to non-aqueous electrolyte for secondary battery and use the secondary electricity of nonaqueous electrolyte of the nonaqueous electrolytic solution Pond, more particularly it relates to the nonaqueous electrolytic solution containing special component and the non-aqueous solution electrolysis using the nonaqueous electrolytic solution Electrolitc secondary cell.

Background technique

In recent years, along with the miniaturization of electronic equipment, the requirement to the high capacity of secondary cell is continuously improved, energy Density is higher than nickel-cadmium cell and the lithium secondary battery of nickel-metal hydride battery attracts attention.

As the electrolyte of lithium secondary battery, adopted is to make LiPF₆、LiBF₄、LiClO₄、LiCF₃SO₃、 LiAsF₆、LiN(CF₃SO₂)₂、LiCF₃(CF₂)₃SO₃Equal electrolyte dissolutions are in cyclic carbonates such as ethylene carbonate, propylene carbonates Ester, the linear carbonates such as dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate；The cyclic esters such as gamma-butyrolacton, gamma-valerolactone Class；Nonaqueous electrolytic solution obtained from the nonaqueous solvents such as the chains esters such as methyl acetate, methyl propionate

<nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>is equivalent to Claims 1 to 4,23~29

Firstly, the non-aqueous electrolyte secondary battery has the advantages that energy density is high and is not likely to produce self discharge.Cause This is widely used in the power supply of the civilian portable equipment such as mobile phone, laptop, PDA in recent years.The secondary electricity of nonaqueous electrolyte The electrolyte that pond is used as the lithium salts of supporting electrolyte and the organic solvent of non-water system by constituting.For the organic solvent of non-water system For, it is desirable that it has for making the high dielectric constant of lithium salts dissociation, showing high ionic conductance in wide temperature region Rate and stable in the battery.Due to being difficult to realize these requirements with a kind of solvent, usually by propylene carbonate, carbonic acid Ethyl etc. is that the low boiling point solvents such as high boiling solvent and dimethyl carbonate, the diethyl carbonate of representative are applied in combination.

In addition, it was recently reported that add various additives in the electrolytic solution largely to improve initial capacity, speed characteristic, circulation The method of characteristic, High temperature storage characteristic, trickle charge characteristic, self-discharge characteristics, overcharge prevention characteristics etc..For example, as suppression The method of the self discharge of system at high temperature, it was recently reported that the method (referring to patent document 1) of addition lithium fluophosphate class.

<nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>is equivalent to claim 5~9,23~29

Secondly, in order to improve the battery behaviors such as the output characteristics of above-mentioned lithium secondary battery, cycle characteristics, preservation characteristics, it is right Nonaqueous solvents and electrolyte have carried out various researchs.For example, being described in patent document 2 by using containing relative to just Gross activity material layer area on electrode current collector is the electrolyte of a certain amount of tetrafluoroborate, excellent to make low temperature output characteristics Different battery.

But in the method, although having the effect of improving output characteristics to a certain extent, and high temperature will not be made Cycle characteristics reduces, but the limitation that its output improves, and cannot cope with the requirement of higher output.

<nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>is equivalent to claim 10~15,23~29

3rd, for batteries such as the load characteristic, cycle characteristics, preservation characteristics, the low-temperature characteristics that improve above-mentioned lithium secondary battery Characteristic has carried out various researchs to nonaqueous solvents and electrolyte.For example, in patent document 3, by using containing vinyl The electrolyte of ethylene carbonate compound, the decomposition of electrolyte can be inhibited in minimum limit, so as to make preservation characteristics, The excellent battery of cycle characteristics；In patent document 4, by using the electrolyte containing propane sultone, after preservation being made Recovery capacity increase.

But when making in electrolyte containing above compound, although achieving raising preservation characteristics to a certain extent And the effect of cycle characteristics, but since the higher epithelium of resistance can be formed in negative side, thus it is particularly present discharge load spy Property reduce the problem of.

<nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>is equivalent to claim 16~29

4th, for batteries such as the load characteristic, cycle characteristics, preservation characteristics, the low-temperature characteristics that improve above-mentioned lithium secondary battery Characteristic has carried out various researchs to nonaqueous solvents and electrolyte.For example, in patent document 3, by using containing vinyl The electrolyte of ethylene carbonate compound, the decomposition of electrolyte can be controlled in bottom line, so as to be made preservation characteristics, The excellent battery of cycle characteristics.In addition, in patent document 4, by using the electrolyte containing propane sultone, can make to protect Recovery capacity after depositing is increased.

But when making in electrolyte containing above compound, although achieving raising preservation characteristics to a certain extent And the effect of cycle characteristics, but since the higher epithelium of resistance can be formed in negative side, thus it is particularly present discharge load spy Property reduce the problem of.

On the other hand, compound represented by the formula (1) by addition patent document 5 is reported in patent document 5, it can So that the technology that cycle characteristics and current characteristics are improved simultaneously.In addition, in patent document 6, it was recently reported that special by addition The technology that fixed compound improves cryogenic discharging characteristic.

But battery behaviors such as load characteristic, cycle characteristics, preservation characteristics, low-temperature characteristics and insufficient, still there is improvement Leeway.

<nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>is equivalent to claim 30~34

5th, from the so-called civilian power supply such as mobile phone, laptop to the extensive of the drivings vehicle power supplies such as automobile Use on the way, the nonaqueous electrolyte batteries such as lithium secondary battery are gradually practical.But in recent years, to non-aqueous solution electrolysis The requirement of the high performance of electrolyte cell is continuously improved, and while improving battery behavior, is also strongly desired changing for battery security It is kind.

It is usually mainly made of electrolyte and nonaqueous solvents for the electrolyte in nonaqueous electrolyte battery.As non-aqueous The cyclic carbonates such as ethylene carbonate, propylene carbonate can be used in the main component of agent；Dimethyl carbonate, diethyl carbonate, The linear carbonates such as methyl ethyl carbonate；Cyclic carboxylic esters such as gamma-butyrolacton, gamma-valerolactone etc..

But above-mentioned organic solvent has volatility, and is easy kindling, therefore, for having used containing a large amount of above-mentioned For the nonaqueous electrolyte battery of the electrolyte of organic solvent, when heated, internal short-circuit of battery when, when external short-circuit of battery, When overcharge perhaps overdischarge when etc. to there is kindling and explosion etc. in the case where misuse, abuse or in accident potential Risk, in particular, risk is high seeking suitable for the large-sized battery of automobile power supply.

From the above point of view, it proposes using the non-aqueous of room temperature fuse salt (also referred to as room temperature molten salt or ionic liquid) Electrolyte.The known room temperature fuse salt is liquid, and its volatility is down to the degree that can not be detected, in addition, due to this Room temperature fuse salt is non-volatile thus non-ignitable.In patent document 7, it discloses secondary as lithium by using the room temperature fuse salt Battery electrolytic solution has obtained the excellent nonaqueous electrolyte battery of safety.

In addition, Patent Document 8 discloses following technologies: in addition to make Reductive stability it is excellent have quaternary ammonium sun from It is also such and above-mentioned normal dissolved with ethylene carbonate or vinylene carbonate in electrolyte other than sub room temperature fuse salt dissolution Warm fuse salt is compared the compound of reduction decomposition under high potential and is so issued compared with room temperature fuse salt in high potential The compound of raw reduction decomposition is electrochemically reacted in charge and discharge process in the early stage, on electrode active material, particularly Electrode protection envelope is formed on negative electrode active material, to improve efficiency for charge-discharge.

Patent document 1: No. 3439085 bulletins of Japanese Patent No.

Patent document 2: Japanese Unexamined Patent Publication 2004-273152 bulletin

Patent document 3: Japanese Unexamined Patent Publication 2001-006729 bulletin

Patent document 4: Japanese Unexamined Patent Publication 10-050342 bulletin

Patent document 5: Japanese Unexamined Patent Publication 08-078053 bulletin

Patent document 6: Japanese Unexamined Patent Publication 11-185804 bulletin

Patent document 7: Japanese Unexamined Patent Publication 4-349365 bulletin

Patent document 8: Japanese Unexamined Patent Publication 2004-146346 bulletin

Summary of the invention

Subject to be solved by the invention

<nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>

But with the continuous improvement required non-aqueous electrolyte secondary battery high performance, it is desirable that with higher level reality Now there are the various characteristics such as high capacity, High temperature storage characteristic, trickle charge characteristic, cycle characteristics simultaneously.It is being only to high temperature The patent document 1 that preservation characteristics tell in the prior art, as shown in subsequent comparative example, exists especially in high voltage Under the conditions of cycle characteristics difference such problems.Therefore, the present invention 1 is exactly to complete in view of the aforementioned technical background, purpose It is to provide cycle characteristics excellent nonaqueous electrolytic solution 1.

<nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>

The present invention 2 is to complete in view of the aforementioned technical background, its purpose is to provide output characteristics excellent, High temperature storage Characteristic and cycle characteristics also excellent non-aqueous electrolyte for secondary battery 2 (nonaqueous electrolytic solution 2).

<nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>

The present invention 3 is to complete in view of the aforementioned technical background, and its purpose is to provide the secondary electricity that cycle characteristics is excellent Pond is with nonaqueous electrolytic solution 3 (nonaqueous electrolytic solution 3).

<nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>

The present invention 4 is completed in view of the above subject.That is, the present invention 4 project be, provide cryogenic discharging characteristic and It is large current discharge excellent, and High temperature storage characteristic and cycle characteristics are also excellent, what also there is no problem in safety is non- Water electrolysis liquid 4.

<nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>

But in recent years to battery high performance require continuous improvement, it is desirable that with higher level realize high capacity, High output, High temperature storage characteristic, cycle characteristics etc. and high security.

It is electric when due to its charge and discharge for having used the nonaqueous electrolyte battery of electrolyte documented by patent document 7 The invertibity of pole reaction is insufficient, therefore battery performance as charge/discharge capacity, efficiency for charge-discharge and cycle characteristics cannot enable People is satisfied (referring to the comparative example 1~3 of the present invention 5).In addition, normal documented by just having used in the embodiment of patent document 8 For the nonaqueous electrolyte battery of the electrolyte formed in warm fuse salt dissolved with ethylene carbonate or vinylene carbonate, When 80 DEG C or more holding rechargeable batteries, the electrode protection envelope that is formed by the decomposition of ethylene carbonate or vinylene carbonate It cannot inhibit the decomposition of room temperature fuse salt, to generate a large amount of decomposition gases in battery.When generating decomposition gas in battery, The internal pressure of battery rises and safety valve is caused to work, in addition, in the battery of not safety valve, due to the pressure of the gas of generation And lead to cell expansion, sometimes resulting in battery itself cannot use.In addition, when the gas generated is imflammable gas, even if The nonaqueous electrolytic solution of room temperature fuse salt has been used not have flammability, but there is also the risk of kindling or explosion.

Therefore, the nonaqueous electrolytic solution for using room temperature fuse salt documented by patent document 7 or patent document 8 is being used In the case of, it is still unsatisfactory in terms of being provided simultaneously with battery behavior and safety.

Therefore, the purpose of the present invention 5 is, can be with using nonaqueous electrolytic solution 5 for using room temperature fuse salt Efficiency for charge-discharge is improved, while keeping high security.

Solution to the problem

<nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>Claims 1 to 4,23~29

The present inventor has made intensive studies in view of the above subject, as a result, it has been found that, by making in nonaqueous electrolytic solution Containing fluorophosphate, and the iron family element containing certain concentration can especially improve while keeping high capacity in high electricity Cycle characteristics under the conditions of pressure, so as to complete the present invention 1.

That is, the present invention 1 is related to nonaqueous electrolytic solution 1, which contains electrolyte and dissolves the non-aqueous of the electrolyte Solvent, the nonaqueous electrolytic solution contain mono-fluor phosphate and/or difluorophosphoric acid salt, also containing relative to nonaqueous electrolytic solution total amount being The iron family element of 1~2000ppm.

In addition, the present invention 1 further relates to non-aqueous electrolyte secondary battery 1, which has used above-mentioned Nonaqueous electrolytic solution 1.

<nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>claim 5~9,23~29

The present inventor has made intensive studies in view of the above subject, as a result, it has been found that, contain certain in nonaqueous electrolytic solution When kind organic compound and specific inorganic compound, output characteristics is excellent, and High temperature storage characteristic and circulation can be made special Property keep good, so as to complete the present invention 2.

That is, the present invention 2 is related to nonaqueous electrolytic solution 2, which mainly by electrolyte and dissolves the non-of the electrolyte Aqueous solvent is constituted, and the nonaqueous electrolytic solution contains selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, with the aromatic series of halogen atom At least one kind of compound in compounds and ethers with fluorine atom also contains mono-fluor phosphate and/or difluorophosphoric acid salt.

In addition, the present invention 2 further relates to non-aqueous electrolyte secondary battery 2, which contains non-water power Solution liquid and the cathode and anode that can occlude and release lithium ion, wherein the nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.

<nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>claim 10~15,23~29

The present inventor has made intensive studies in view of the above subject, as a result, it has been found that, it is added in nonaqueous electrolytic solution When specific compound and " mono-fluor phosphate and/or difluorophosphoric acid salt ", cycle characteristics can be made to keep good, so as to complete The present invention 3.

That is, the present invention 3 is characterized by non-aqueous electrolyte for secondary battery 3, it is used for non-aqueous electrolyte secondary battery, institute Non-aqueous electrolyte secondary battery is stated with nonaqueous electrolytic solution and the cathode and anode that can occlude and release ion, wherein described Nonaqueous electrolytic solution contains electrolyte and nonaqueous solvents, also contains mono-fluor phosphate and/or difluorophosphoric acid salt, and relative to this Nonaqueous electrolytic solution total amount is that the ratio of 0.001 weight of weight %~10 % contains the following general formula (1) and/or the following general formula (2) table The compound shown

[chemical formula 1]

[R¹、R²、R³、R⁴It is respectively independent, it is organic group or halogen atom, R¹、R²、R³、R⁴In at least one group be and X The atom of Direct Bonding is heteroatomic group, R¹、R²、R³、R⁴It is identical or different.X is the atom other than carbon atom.]

[chemical formula 2]

[R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, R⁵、R⁶、R⁷In at least one group be direct with Y The atom of bonding is heteroatomic group, R⁵、R⁶、R⁷It is identical or different.Y is the atom other than carbon atom.]

In addition, the present invention 3 is characterized by non-aqueous electrolyte for secondary battery 3, it is used for non-aqueous electrolyte secondary battery, The non-aqueous electrolyte secondary battery has nonaqueous electrolytic solution and can occlude and release the cathode and anode of ion, wherein institute It states nonaqueous electrolytic solution and contains mono-fluor phosphate and/or difluorophosphoric acid salt, and the nonaqueous electrolytic solution is used to use the following general formula (1) And/or in the non-aqueous electrolyte secondary battery that is handled positive or negative pole of compound represented by the following general formula (2).

[chemical formula 3]

[R¹、R²、R³、R⁴It is respectively independent, it is organic group or halogen atom, R¹、R²、R³、R⁴In at least one group in, with The atom of X Direct Bonding is hetero atom, R¹、R²、R³、R⁴It is identical or different.X is the atom other than carbon atom.]

[chemical formula 4]

[R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, R⁵、R⁶、R⁷In at least one group in, it is direct with Y The atom of bonding is hetero atom, R⁵、R⁶、R⁷It is identical or different.Y is the atom other than carbon atom.]

In addition, the present invention 3 is characterized by non-aqueous electrolyte secondary battery 3, which at least has Having nonaqueous electrolytic solution and can occlude and release the cathode and anode of ion, wherein the nonaqueous electrolytic solution is above-mentioned non-aqueous Electrolyte 3.

<nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>claim 16~29

The present inventor has made intensive studies in view of the above subject, as a result, it has been found that, it is added in nonaqueous electrolytic solution When specific compound, it is possible to produce cryogenic discharging characteristic and heavy-current discharge excellent, and High temperature storage characteristic and circulation Characteristic also excellent battery, so as to complete the present invention 4.

That is, the present invention 4 is related to nonaqueous electrolytic solution 4, the nonaqueous electrolytic solution 4 is containing lithium salts and dissolves the non-aqueous of the lithium salts Agent, the nonaqueous electrolytic solution contains compound represented by the following general formula (3), and contains mono-fluor phosphate and/or difluoro phosphorus Hydrochlorate.Hereinafter, the invention is referred to as " embodiment 4-1 ".

[chemical formula 5]

[in general formula (3), A and B indicate various substituent groups, and wherein at least one is fluorine, and n indicates 3 or more natural number.]

In addition, the present invention 4 is related to nonaqueous electrolytic solution 4, the nonaqueous electrolytic solution 4 is containing lithium salts and dissolves the non-aqueous of the lithium salts Agent, the nonaqueous electrolytic solution are above-mentioned logical to contain relative to the ratio that nonaqueous electrolytic solution total amount is 0.001 weight of weight %~5 % Compound represented by formula (3), also, to contain relative to the ratio that nonaqueous electrolytic solution total amount is 0.001 weight of weight %~5 % There is carbonic ester, the carbonic ester has at least one of unsaturated bond and halogen atom.Hereinafter, the invention is referred to as " implementing Mode 4-2 ".

In addition, the present invention 4 is characterized by non-aqueous electrolyte secondary battery 4, which includes non- Water electrolysis liquid and the cathode and anode that can occlude and release lithium ion, wherein the nonaqueous electrolytic solution is above-mentioned non-water power Solve liquid.

<nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>claim 30~34

To achieve the goals above, further investigation has been repeated in the present inventor etc., as a result, it has been found that, by making With the compound with specific structure is contained in the nonaqueous electrolytic solution of room temperature fuse salt, the above subject can solve, thus complete At the present invention 5.

That is, the present invention 5 is characterized by nonaqueous electrolytic solution 5, which contains lithium salts and room temperature fuse salt, In, mono-fluor phosphate and/or difluorophosphoric acid salt are contained in nonaqueous electrolytic solution.

In addition, the present invention 5 is characterized by nonaqueous electrolyte battery 5, which has nonaqueous electrolytic solution With the cathode and anode that can occlude and release lithium ion, wherein the nonaqueous electrolytic solution is above-mentioned nonaqueous electrolytic solution.

The effect of invention

<nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>

According to the present invention 1, high capacity and the excellent nonaqueous electrolytic solution 1 and nonaqueous electrolyte two of cycle characteristics can be provided Primary cell 1.

<nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>

According to the present invention 2, it can provide that output characteristics is excellent, and High temperature storage characteristic and cycle characteristics are also excellent is used for The nonaqueous electrolytic solution 2 and non-aqueous electrolyte secondary battery 2 of secondary cell.

<nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>

According to the present invention 3, can provide cycle characteristics it is excellent for the nonaqueous electrolytic solution 3 of secondary cell and non-aqueous Electrolyte secondary battery 3.

<nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>

4 nonaqueous electrolytic solution according to the present invention can provide cryogenic discharging characteristic and heavy-current discharge excellent, and High temperature storage characteristic and cycle characteristics are also in excellent non-aqueous electrolyte secondary battery 4 and the non-aqueous electrolyte secondary battery 4 Nonaqueous electrolytic solution 4.

<nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>

According to the present invention 5, the high safety of the great advantage as the nonaqueous electrolytic solution for using room temperature fuse salt can be kept Property, and may be implemented the high charge-discharge capacity to compare favourably with the usually used nonaqueous electrolytic solution using non-water system organic solvent and High charge-discharge efficiencies, and can also realize the enlarged and further high performance of nonaqueous electrolyte battery.

Specific embodiment

In the following, being carried out in detail for the embodiment of the present invention 1 to 5 (they are referred to as " present invention " sometimes) of the invention Illustrate, but the explanation to constituent element of following records be embodiments of the present invention an example (typical example), the present invention not by The limitation of these particular contents can carry out without departing from the gist of the present invention various modifications to implement the present invention.

<nonaqueous electrolytic solution 1, non-aqueous electrolyte secondary battery 1>

[1. nonaqueous electrolytic solution 1]

Nonaqueous electrolytic solution used in the non-aqueous electrolyte secondary battery of the present invention 1 is (hereinafter, be properly termed as " in the present invention 1 Nonaqueous electrolytic solution ") be the nonaqueous electrolytic solution containing electrolyte and the nonaqueous solvents for dissolving the electrolyte, which contains There are mono-fluor phosphate and/or difluorophosphoric acid salt, also containing the iron family element for being 1~2000ppm relative to nonaqueous electrolytic solution total amount.

<1-1. electrolyte>

The electrolyte of nonaqueous electrolytic solution for the present invention 1 is not particularly limited, can be arbitrarily containing in target non-aqueous solution electrolysis The well known electrolyte used in electrolitc secondary cell as electrolyte.The nonaqueous electrolytic solution of the present invention 1 is used for nonaqueous electrolyte When secondary cell, electrolyte is preferably lithium salts.

As the specific example of electrolyte, it can be mentioned, for example:

LiClO₄、LiAsF₆、LiPF₆、Li₂CO₃、LiBF₄Equal inorganic lithium salts；

LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂、LiN(CF₃SO₂)(C₄F₉SO₂)、LiC(CF₃SO₂)₃、LiPF₄ (CF₃)₂、LiPF₄(C₂F₅)₂、LiPF₄(CF₃SO₂)₂、LiPF₄(C₂F₅SO₂)₂、LiBF₃(CF₃)、LiBF₃(C₂F₅)、LiBF₂ (CF₃)₂、LiBF₂(C₂F₅)₂、LiBF₂(CF₃SO₂)₂、LiBF₂(C₂F₅SO₂)₂Etc. fluorine-containing organic lithium salt；

Two (oxalate conjunction) lithium borates, three (oxalate conjunction) lithium phosphates, difluoro oxalate root close the networks containing dicarboxylic acids such as lithium borate Close the lithium salts of object；

KPF₆、NaPF₆、NaBF₄、CF₃SO₃The sodium salts such as Na or sylvite etc..

In above-mentioned electrolyte, preferably LiPF₆、LiBF₄、LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂, two (oxalic acid Root closes) lithium borate, particularly preferred LiPF₆Or LiBF₄。

Lithium salts can be used alone, can also in any combination and ratio use two or more.Wherein, when being applied in combination 2 kinds of specific inorganic lithium salts or when inorganic lithium salt and fluorine-containing organic lithium salt is applied in combination, can inhibit the generation in trickle charge Gas or inhibition deteriorate after High temperature storage, therefore preferably.

LiPF is particularly preferably applied in combination₆And LiBF₄, or by LiPF₆、LiBF₄Equal inorganic lithium salts and LiCF₃SO₃、LiN (CF₃SO₂)₂、LiN(C₂F₅SO₂)₂It is applied in combination etc. fluorine-containing organic lithium salt.

In addition, when LiPF is applied in combination₆And LiBF₄When, contained LiBF₄Shared ratio is usual in electrolyte total amount Preferably 0.01 weight of weight %~20 %.Work as LiBF₄Degree of dissociation it is too low, when ratio is excessively high, may cause nonaqueous electrolytic solution Resistance increase.

On the other hand, by LiPF₆、LiBF₄Equal inorganic lithium salts and LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂Etc. containing When fluorine organic lithium salt is applied in combination, inorganic lithium salt ratio shared in lithium salts total amount is preferably generally 70 weights of weight %~99 Measure the range of %.In general, when fluorine-containing organic lithium salt and inorganic lithium salt compared to molecular weight is excessive, ratio is excessively high when, sometimes result in Nonaqueous solvents ratio shared in nonaqueous electrolytic solution total amount reduces, so that the resistance of nonaqueous electrolytic solution be made to increase.

In addition, it is unobvious destroy the present invention 1 effect in the range of, lithium salts the present invention 1 nonaqueous electrolytic solution most The concentration in composition can be arbitrary eventually, but usually be existed in 0.5mol/L or more, preferably in 0.6mol/L or more, more preferably 0.8mol/L or more, in addition, usually in 3mol/L or less, preferably in 2mol/L or less, more preferably in 1.5mol/L model below It encloses.When the concentration is too low, the conductivity that may cause nonaqueous electrolytic solution is insufficient；When the concentration is too high, it since viscosity increases, leads Electric rate decline, sometimes results in the reduced performance of the non-aqueous electrolyte secondary battery of the nonaqueous electrolytic solution using the present invention 1.

In particular, when the nonaqueous solvents of nonaqueous electrolytic solution is with carbonate compounds such as alkylene carbonates or dialkyl carbonates When object is main, LiPF can be used alone₆, but preferably by LiPF₆With LiBF₄It is applied in combination, because can inhibit in this way because continuous Capacity deterioration caused by charging.When LiPF is applied in combination₆And LiBF₄When, LiBF₄With LiPF₆Molar ratio usually 0.005 Above, preferably 0.01 or more, particularly preferably 0.05 or more, and usually below 0.4, preferably below 0.2.When this mole Than it is excessive when, the battery behavior after having the tendency that causing High temperature storage reduces, on the contrary, when molar ratio is too small, is difficult to obtain and exists Inhibit the effect of gas generation and capacity deterioration when trickle charge.

In addition, the rings such as gamma-butyrolacton, gamma-valerolactone containing 50 volume % or more in the nonaqueous solvents of nonaqueous electrolytic solution When shape carboxylate compound, preferably LiBF₄Account for the 50mol% or more of the 1st lithium salts (most commonly used lithium salts) total amount.

<1-2. nonaqueous solvents>

As long as the nonaqueous solvents contained by the nonaqueous electrolytic solution of the present invention 1 will not be to battery behavior band when battery is made Carry out dysgenic solvent, 1 in solvent used in the nonaqueous electrolytic solution for being not particularly limited, but being preferably exemplified below Kind or more.

It as the example of usually used nonaqueous solvents, can enumerate: chain and cyclic carbonate, chain and cyclic carboxylic acids Ester, chain and cyclic ether, phosphorous organic solvent, sulfur-bearing organic solvent etc..

In addition, there is no limit as the example of usually used linear carbonate, preferably carbon for the type of linear carbonate Acid dialkyl ester, the carbon atom number for constituting the alkyl of dialkyl carbonate are respectively preferably 1~5, especially preferably 1~4.Specifically Ground can be enumerated: dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl n-propyl ester, carbonic acid ethyl n-propyl ester, Carbonic acid di-n-propyl ester etc..

In above-mentioned linear carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate due to industrial accessibility and Various characteristics in non-aqueous electrolyte secondary battery are good, therefore preferably.

For the type of cyclic carbonate, there is no restriction, as usually used cyclic carbonate, preferably comprises cyclic annular carbon The carbon atom number of the alkylidene of acid esters is 2~6, especially preferably 2~4.Specifically, can enumerate: ethylene carbonate, carbonic acid are sub- Propyl ester, butylene carbonate (2- ethyl carbonate ethyl, cis and trans 2,3- dimethyl ethylene carbonate) etc..

In above-mentioned cyclic carbonate, ethylene carbonate or propylene carbonate are various in non-aqueous electrolyte secondary battery Characteristic is good, therefore preferably.

In addition, for chain carboxylate type also there is no limit, can as the example of usually used chain carboxylate It enumerates: the tertiary fourth of methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, acetic acid Ester, methyl propionate, ethyl propionate, n propyl propionate, isopropyl propionate, n-butyl propionate, isobutyl propionate, propanoic acid tert-butyl ester Deng.

In above-mentioned chain carboxylate, ethyl acetate, methyl propionate, ethyl propionate are due to industrial accessibility and non- Various characteristics in Water-Electrolyte secondary cell are good, therefore preferably.

In addition, for cyclic carboxylic esters type also there is no limit, can as the example of usually used cyclic carboxylic esters Enumerate gamma-butyrolacton, gamma-valerolactone, δ-valerolactone etc..

In above-mentioned cyclic carboxylic esters, gamma-butyrolacton is due to industrial accessibility and in non-aqueous electrolyte secondary battery Various characteristics it is good, therefore preferably.

In addition, also there is no limit can enumerate: dimethoxy as the example of usually used chain ether the type of chain ether Methylmethane, dimethoxy-ethane, diethoxymethane, diethoxyethane, ethoxymethyl) epoxide methane, ethoxymethyl) epoxide second Alkane etc..

In above-mentioned chain ether, dimethoxy-ethane, diethoxyethane are due to industrial accessibility and in non-aqueous solution electrolysis Various characteristics in electrolitc secondary cell are good, therefore preferably.

In addition, also there is no limit as the example of usually used cyclic ether, can enumerate: tetrahydro furan the type of cyclic ether It mutters, 2- methyltetrahydrofuran, oxinane etc..

In addition, the type for phosphorous organic solvent is also not particularly limited, as usually used phosphorous organic solvent Example, can enumerate: the phosphoric acid esters such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate；Trimethyl phosphite, phosphorous acid The phosphorous acid esters such as triethyl, triphenyl phosphite；The oxidation such as trimethyl phosphine oxide, triethyl group phosphine oxide, triphenylphosphine oxide Phosphine etc..

In addition, the type for sulfur-bearing organic solvent is also not particularly limited, as usually using sulfur-bearing organic solvent Example can be enumerated: sulfurous acid glycol ester, 1,3-propane sultone, Isosorbide-5-Nitrae-butyl sultone, methyl mesylate, two methanesulfonic acids Butyl ester, sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, two sulphur of dicyclohexyl Ether, tetramethylthiuram monosulfide, N, N- dimethyl methyl sulfonamide, N, N- diethyl Methanesulfomide etc..

In above-mentioned nonaqueous solvents, chain and cyclic carbonate or chain and cyclic carboxylic esters are secondary in nonaqueous electrolyte Various characteristics in battery are good, therefore preferably, wherein more preferable ethylene carbonate, propylene carbonate, dimethyl carbonate, carbon Sour methyl ethyl ester, diethyl carbonate, ethyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, further preferred carbonic acid Asia second Ester, propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethyl acetate, methyl propionate, gamma-butyrolacton.

Above-mentioned nonaqueous solvents may be used alone or in combination of two or more kinds, and preferably be applied in combination of more than two kinds Compound.For example, it is preferable to by the low viscosities such as cyclic carbonates high dielectric constant solvent and linear carbonate class or chain esters Solvent combination uses.

The preferred combination of nonaqueous solvents first is that combination based on cyclic carbonates and linear carbonate class.Its In, the total amount of cyclic carbonates and linear carbonate class ratio shared in nonaqueous solvents total amount be 80 volume % or more, Preferably 85 volume % or more, more preferably 90 volume % or more, also, the volume of cyclic carbonates is relative to cyclic carbonate Esters and linear carbonate class total amount are 5% or more, preferably 10 volume % or more, more preferably 15 volume % or more, and Usually 50 volume % or less, preferably 35 volume % or less, more preferably 30 volume % or less.Using such nonaqueous solvents Combination when, cycle characteristics and High temperature storage characteristic can be obtained (especially after High temperature storage using battery made of the combination Remaining capacity and high load discharge capacity) it is well balanced, thus preferably.

As the preferred combined specific example of cyclic carbonates and linear carbonate class, can enumerate: ethylene carbonate With dimethyl carbonate, ethylene carbonate and diethyl carbonate, ethylene carbonate and methyl ethyl carbonate, ethylene carbonate and carbonic acid two Methyl esters and diethyl carbonate, ethylene carbonate and dimethyl carbonate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and Methyl ethyl carbonate, ethylene carbonate and dimethyl carbonate and diethyl carbonate and methyl ethyl carbonate etc..

In the combination of above-mentioned ethylene carbonate and linear carbonate class, as preferred combination, it can also enumerate into one The combination of step addition propylene carbonate.When containing propylene carbonate, the volume ratio of ethylene carbonate and propylene carbonate is preferred For 99:1~40:60, especially preferably 95:5~50:50.In addition, when keep propylene carbonate shared in nonaqueous solvents total amount Ratio is 0.1 volume % or more, preferably 1 volume %, more preferably 2 volume % or more, and usually 10 volume % or less, excellent When being selected as 8 volume % or less, more preferably 5 volume % or less, the combination of ethylene carbonate and linear carbonate class can be kept Characteristic, and superior discharge load characteristic is further obtained, therefore preferably.

In said combination, the combination of further preferably asymmetric linear carbonate class, in particular, ethylene carbonate and carbon Dimethyl phthalate and methyl ethyl carbonate, ethylene carbonate and diethyl carbonate and methyl ethyl carbonate, ethylene carbonate and carbonic acid diformazan Contain ethylene carbonate and symmetrical linear carbonate class and asymmetric chain as ester and diethyl carbonate and methyl ethyl carbonate The combination of carbonates or further containing the combination of propylene carbonate, these combinations can obtain cycle characteristics and electric discharge is negative The well balanced of characteristic is carried, therefore preferably.Wherein, preferably asymmetric linear carbonate class is the combination of methyl ethyl carbonate, in addition, The atomic number of alkyl carbon for constituting dialkyl carbonate is preferably 1~2.

Other examples of preferred mixed solvent are the mixed solvent containing chain ester.In particular, from putting for battery is improved From the point of view of electric loading characteristic, preferably contain chain ester in above-mentioned cyclic carbonates and linear carbonate class in the mixed solvent Mixed solvent, as chain ester, particularly preferred ethyl acetate, methyl propionate.The volume of chain ester is usual in nonaqueous solvents 5% or more is accounted for, 8% or more is preferably accounted for, more preferably accounts for 15% or more, and usually accounts for 50% or less, preferably accounts for 35% or less, is more excellent Choosing accounts for 30% or less, further preferably accounts for 25% or less.

As the example of other preferred nonaqueous solvents, can be account for 60 volume % of total amount or more in following solvents 1 kind of organic solvent or the mixed solvent that is made of two or more organic solvent in following solvents, the solvent include: Ethylene carbonate, propylene carbonate and butylene carbonate, gamma-butyrolacton and gamma-valerolactone.It is preferred that the flash-point of this kind of mixed solvent It is 50 DEG C or more, wherein especially preferably 70 DEG C or more.Using the solvent nonaqueous electrolytic solution even if at high temperature using not The evaporation or liquid leakage of solvent easily occurs.Wherein, when the total amount using ethylene carbonate and gamma-butyrolacton is in nonaqueous solvents Shared ratio is 80 volume % or more, preferably 90 volume % or more, and the volume ratio of ethylene carbonate and gamma-butyrolacton is When the solvent of 5:95~45:55, or when using the total amount of ethylene carbonate and propylene carbonate shared in nonaqueous solvents Ratio is 80 volume % or more, preferably 90 volume % or more and the volume ratio of ethylene carbonate and propylene carbonate is 30:70 When the solvent of~80:20, the well balanced of cycle characteristics and discharge load characteristic etc. can be usually obtained.

<1-3. mono-fluor phosphate, difluorophosphoric acid salt>

The nonaqueous electrolytic solution of the present invention 1 contains mono-fluor phosphate and/or difluorophosphoric acid salt as its essential component.In this hair " mono-fluor phosphate and/or difluorophosphoric acid salt " used in bright 1 if by single fluorophosphoric acid radical ion and/or difluorophosphoric acid root from Son and cation are formed, and are not particularly limited to its type, since the nonaqueous electrolytic solution being finally made must can be used as The electrolyte of non-aqueous electrolyte secondary battery, thus need to be selected accordingly.

As a result, the present invention 1 in mono-fluor phosphate, difluorophosphoric acid salt be preferably 1 or more single fluorophosphoric acid radical ion, two Fluorophosphoric acid radical ion and in the periodic table of elements one or more of the 1st race, the 2nd race and the 13rd race metal ion (hereinafter, suitable When referred to as " special metal ion ") formed salt or be with season formed salt.Mono-fluor phosphate and/or difluorophosphoric acid Salt can be used a kind, can also be applied in combination it is any two or more.

<the mono- fluorophosphoric acid metal salt of 1-3-1., difluorophosphoric acid metal salt>

Firstly, being single fluorophosphoric acid radical ion, difluorophosphoric acid root for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention 1 The salt that ion and special metal ion are formed is (hereinafter, also they are referred to as " single fluorophosphoric acid metal salt ", " difluorophosphoric acid metal respectively Salt ") the case where be illustrated.

In for single fluorophosphoric acid metal salt of the present invention 1, the special metal of difluorophosphoric acid metal salt, as period of element The specific example of 1st race's metal of table, can enumerate lithium, sodium, potassium, caesium etc..Wherein, preferably lithium or sodium, particularly preferred lithium.

As the specific example of group II metal in the periodic table of elements, magnesium, calcium, strontium, barium etc. can be enumerated.Wherein, preferably magnesium or Calcium, particularly preferred magnesium.

As the specific example of the 13rd race's metal in the periodic table of elements, aluminium, gallium, indium, thallium etc. can be enumerated.Wherein, preferred aluminium Or gallium, particularly preferred aluminium.

For these specific gold possessed by single fluorophosphoric acid metal salt of every 1 molecule present invention 1, difluorophosphoric acid metal salt There is no limit can be only 1 atom, or more than 2 atoms to the atomicity of category.

Contain the above special metal of 2 atoms in single fluorophosphoric acid metal salt of every 1 molecule present invention 1, difluorophosphoric acid metal salt When, the type of these special metal atoms can be mutually the same, can also be different.In addition it can have 1 or 2 or more Metallic atom other than special metal.

As single fluorophosphoric acid metal salt, the specific example of difluorophosphoric acid metal salt, Li can be enumerated₂PO₃F、Na₂PO₃F、 MgPO₃F、CaPO₃F、Al₂(PO₃F)₃、Ga₂(PO₃F)₃、LiPO₂F₂、NaPO₂F₂、Mg(PO₂F₂)₂、Ca(PO₂F₂)₂、Al (PO₂F₂)₃、Ga(PO₂F₂)₃Deng.Wherein, preferably Li₂PO₃F、LiPO₂F₂、NaPO₂F₂、Mg(PO₂F₂)₂Deng.

< 1-3-2. mono- fluorophosphoric acid seasonSalt, difluorophosphoric acid seasonSalt >

It then, is single fluorophosphoric acid radical ion, difluorophosphoric acid root for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention 1 Ion and seasonThe salt of formation is (hereinafter, also they are referred to as " single fluorophosphoric acid season respectivelySalt ", " difluorophosphoric acid seasonSalt ") Situation is illustrated.

For single fluorophosphoric acid season in the present invention 1Salt, difluorophosphoric acid seasonThe season of saltIt is usually cationic, specifically For, the cation indicated with the following general formula (4) can be enumerated.

[chemical formula 6]

In above-mentioned general formula (4), R^1m~R^4mIt is independently represented each other alkyl.For alkyl type there is no limit.That is, can To be aliphatic alkyl, it is also possible to aromatic hydrocarbyl, can also be hydrocarbon made of aliphatic alkyl is bonded with aromatic hydrocarbyl Base.When it is aliphatic alkyl, it can be chain, be also possible to ring-type, can also be knot made of chain and cyclic annular bonding Structure.When it is chain alkyl, it can be straight-chain, be also possible to branched.Furthermore, it is possible to be saturated hydrocarbyl, can also have There is unsaturated bond.

As R^1m~R^4mAlkyl specific example, alkyl, naphthenic base, aryl, aralkyl etc. can be enumerated.

As the specific example of alkyl, it can be mentioned, for example: methyl, ethyl, 1- propyl, 1- Methylethyl, 1- butyl, 1- first Base propyl, 2- methyl-propyl, 1,1- dimethyl ethyl etc..

Wherein, preferably methyl, ethyl, 1- propyl, 1- butyl etc..

As the specific example of naphthenic base, it can be mentioned, for example: cyclopenta, 2- methylcyclopentyl, 3- methylcyclopentyl, 2,2- Dimethylcyclopentyl, 2,3- dimethylcyclopentyl, 2,4- dimethylcyclopentyl, 2,5- dimethylcyclopentyl, 3,3- diformazan basic ring Amyl, 3,4- dimethylcyclopentyl, 2- ethylcyclopentyl, 3- ethylcyclopentyl, cyclohexyl, 2- methylcyclohexyl, 3- methyl ring Hexyl, 4- methylcyclohexyl, 2,2- Dimethylcyclohexyl, 2,3- Dimethylcyclohexyl, 2,4- Dimethylcyclohexyl, 2,5- diformazan Butylcyclohexyl, 2,6- Dimethylcyclohexyl, 3,4- Dimethylcyclohexyl, 3,5- Dimethylcyclohexyl, 2- ethylcyclohexyl, 3- second Butylcyclohexyl, 4- ethylcyclohexyl, bicyclic [3,2,1] octyl- 1- base, bicyclic [3,2,1] octyl- 2- base etc..

Wherein, preferably cyclopenta, 2- methylcyclopentyl, 3- methylcyclopentyl, cyclohexyl, 2- methylcyclohexyl, 3- methyl Cyclohexyl, 4- methylcyclohexyl etc..

As the specific example of aryl, it can be mentioned, for example: phenyl, 2- aminomethyl phenyl, 3- aminomethyl phenyl, 4- aminomethyl phenyl, 2,3- 3,5-dimethylphenyl etc..

Wherein, preferred phenyl.

As the specific example of aralkyl, it can be mentioned, for example: phenyl methyl, 1- phenylethyl, 2- phenylethyl, diphenyl Methyl, trityl group etc..

Wherein, preferably phenyl methyl, 2- phenylethyl.

R^1m~R^4mAlkyl can also be replaced by 1 or 2 or more substituent group.For the type of substituent group, as long as not There is no limit can enumerate halogen atom, hydroxyl, ammonia as the example of substituent group in the range of the obvious effect for destroying the present invention 1 Base, nitro, cyano, carboxyl, ether, aldehyde radical etc..It should be noted that working as R^1m~R^4mAlkyl there is 2 or more substituent groups When, these substituent groups can be mutually the same, can also be different.

To R more than any two^1m~R^4mWhen alkyl is compared, they can be mutually the same, can also mutual not phase Together.Work as R^1m~R^4mAlkyl have substituent group when, the substituted hydrocarbon radical including these substituent groups can be mutually the same, can also With different.In addition, R^1m~R^4mAlkyl in any 2 or more can also be mutually bonded and form cyclic structure.

R^1m~R^4mAlkyl carbon atom number usually 1 or more, and its upper limit usually below 20, preferably 10 with Under, more preferably below 5.When carbon atom number is excessive, the molal quantity of Unit Weight is reduced, and has cause various effects to reduce to incline To.It should be noted that working as R^1m~R^4mAlkyl have substituent group when, the carbon of the substituted hydrocarbon radical including these substituent groups Atomicity is met the above range.

In addition, in above-mentioned general formula (4), affiliated atom in the 15th race of Q representative element periodic table.Wherein, preferably nitrogen is former Son or phosphorus atoms.

So, the preferred embodiment as season represented by above-mentioned general formula (4) can enumerate aliphatic chain quaternary salt Class, aliphatic cyclic ammonium, aliphatic Huan Zhuan Phosphonium, nitrogen-containing heterocycle aromatic series cation etc..

As aliphatic chain quaternary salt class, particularly preferred tetra-allkylammonium, four alkane base Phosphonium etc..

As the specific example of tetra-allkylammonium, it can be mentioned, for example: tetramethyl-ammonium, ethyl trimethyl ammonium, diethyl-dimethyl Ammonium, triethylmethylammonium, tetraethyl ammonium, tetra-n-butyl ammonium etc..

As the specific example of Si Wan Ji Phosphonium, it can be mentioned, for example: tetramethyl phosphonium, Yi base San Jia Ji Phosphonium, diethyl-dimethyl Phosphonium, triethyl group Jia Ji Phosphonium, tetraethylphosphonium, Si Zheng Ding Ji Phosphonium etc..

As aliphatic cyclic ammonium, particularly preferred pyrrolidinesClass, morpholineClass, imidazolesClass, tetrahydropyrimidineClass, PiperazineClass, piperidinesClass etc..

As pyrrolidinesThe specific example of class, it can be mentioned, for example: N, N- dimethyl pyrrolidineN- ethyl-N-methyl PyrrolidinesN, N- diethyl pyrrolidinesDeng.

As morpholineThe specific example of class, it can be mentioned, for example: N, N- thebaineN- ethyl-N-methylmorpholiniumN, N- diethyl morpholineDeng.

As imidazolesThe specific example of class, it can be mentioned, for example: N, N '-dimethyl imidazolesN- ethyl-N '-methyl miaow AzolesN, N '-diethyl imidazolium1,2,3- tri-methylimidazoliumDeng.

As tetrahydropyrimidineThe specific example of class, it can be mentioned, for example: N, N '-dimethyl tetrahydropyrimidineN- ethyl- N '-methyl tetrahydropyrimidineN, N '-diethyl tetrahydropyrimidine1,2,3- trimethyl tetrahydropyrimidineDeng.

As piperazineThe specific example of class, it can be mentioned, for example: N, N, N ', N '-tetramethyl piperazineN- ethyl-N, N ', N '-tri methyl piperazineN, N- diethyl-N ', N '-dimethyl piperazineN, N, N '-triethyl group-N '-methyl piperazineN, N, N ', N '-tetraethyl piperazineDeng.

As piperidinesThe specific example of class, it can be mentioned, for example: N, N- lupetidineN- ethyl-N-methyl piperidinesN, N- diethyl phenylpiperidinesDeng.

As nitrogen-containing heterocycle aromatic series cation, particularly preferred pyridineClass, imidazolesClass etc..

As pyridineThe specific example of class, it can be mentioned, for example: N- picolineN- ethylpyridine1,2- bis- Methylpyrimidine1,3- dimethyl pyrimidine1,4- dimethyl pyrimidine1- Ethyl-2-Methyl pyrimidineDeng.

As imidazolesThe specific example of class, it can be mentioned, for example: N, N '-dimethyl imidazolesN- ethyl-N '-methyl miaow AzolesN, N '-diethyl imidazolium1,2,3- tri-methylimidazoliumDeng.

That is, the above-mentioned season enumeratedThe salt formed with single fluorophosphoric acid radical ion and/or difluorophosphoric acid radical ion is the present invention 1 In single fluorophosphoric acid seasonSalt, difluorophosphoric acid seasonThe preferred specific example of salt.

<1-3-3. content, detection (source contained), technical scope etc.>

In the nonaqueous electrolytic solution of the present invention 1, a kind of mono-fluor phosphate or difluorophosphoric acid salt can be used only, it can also be with Any combination and ratio are applied in combination mono-fluor phosphate and/or difluorophosphoric acid salt of more than two kinds, but from the secondary electricity of nonaqueous electrolyte The angle that pond can effectively work is set out, it is preferable to use a kind of mono-fluor phosphate or difluorophosphoric acid salt.

In addition, for the molecular weight of mono-fluor phosphate, difluorophosphoric acid salt, there is no restriction, destroys the present invention's 1 unobvious It can be any molecular weight in the range of effect, but usually 100 or more.In addition, upper molecular weight limit is not particularly limited, but In view of the reactivity of this reaction, it is more highly preferred to usually below 1000, when reaching 500 or less from point of view of practicability.

In addition, the preparation method of mono-fluor phosphate, difluorophosphoric acid salt is it is not also specifically limited, can arbitrarily select well known It is prepared by method.

In nonaqueous electrolytic solution, the total amount of mono-fluor phosphate and difluorophosphoric acid salt ratio shared in nonaqueous electrolytic solution total amount Example is preferably 10ppm or more (0.001 weight % or more), more preferably 0.01 weight % or more, particularly preferably 0.05 weight Measure % or more, further preferably 0.1 weight % or more.In addition, the upper limit of its total amount be preferably 5 weight % or less, more preferably For 4 weight % or less, further preferably 3 weight % or less.When the concentration of mono-fluor phosphate or difluorophosphoric acid salt is too low, have When be difficult obtain discharge load characteristic improvement, on the other hand, when the concentration is too high, sometimes result in efficiency for charge-discharge drop It is low.

When mono-fluor phosphate and difluorophosphoric acid salt are actually used in as nonaqueous electrolytic solution the system of non-aqueous electrolyte secondary battery When making, even if dismantling the battery and extracting nonaqueous electrolytic solution again, mono-fluor phosphate therein and two in most cases The content of fluorophosphate can significantly reduce.Therefore, even if only being detected from the nonaqueous electrolytic solution extracted in battery few The mono-fluor phosphate of amount and/or at least one kind of in difluorophosphoric acid salt, the situation are regarded as belonging to the present invention 1.In addition, when single When fluorophosphate and difluorophosphoric acid salt are actually used in the production of non-aqueous electrolyte secondary battery as nonaqueous electrolytic solution, even if tearing open It opens in the case where not containing mono-fluor phosphate and/or difluorophosphoric acid salt in the nonaqueous electrolytic solution extracted again after the battery, Mostly also single fluorine phosphorus can be detected on the anode, cathode or partition of other building blocks as non-aqueous electrolyte secondary battery The presence of hydrochlorate and/or difluorophosphoric acid salt.Therefore, even if being detected at least one kind of building block in anode, cathode, partition At least one kind of into mono-fluor phosphate and/or difluorophosphoric acid salt, which is regarded as belonging to the present invention 1.

In addition, for making mono-fluor phosphate and/or difluorophosphoric acid salt not only be contained in nonaqueous electrolytic solution while also include Situation in anode, cathode, partition at least one kind of building block is also regarded as and belongs to the present invention 1.

On the other hand, in the anode of non-aqueous electrolyte secondary battery made of can also making or positive electrode surface contains in advance Mono-fluor phosphate and/or difluorophosphoric acid salt.At this point, it can be expected that the portion of the mono-fluor phosphate and/or difluorophosphoric acid salt that contain in advance Divide or be all dissolved in nonaqueous electrolytic solution and function, which, which is also regarded as, belongs to the present invention 1.

For making in anode or the positive electrode surface method containing mono-fluor phosphate and/or difluorophosphoric acid salt in advance, spy is had no Different limitation, as specific example, can enumerate it is as described later, when aftermentioned anode is made make mono-fluor phosphate and/or difluoro Phosphate is dissolved in the method in the slurry of preparation；Or it is dissolved in mono-fluor phosphate and/or difluorophosphoric acid salt arbitrarily In nonaqueous solvents, after recycling solution obtained is to manufactured anode is coated or is impregnated with, used in dry, removing Solvent, to make the method etc. that in anode or positive electrode surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.

In addition, in actual fabrication non-aqueous electrolyte secondary battery, can also by comprising at least one kind of mono-fluor phosphate and/ Or the nonaqueous electrolytic solution of difluorophosphoric acid salt makes in anode or positive electrode surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.It is making When making non-aqueous electrolyte secondary battery, since nonaqueous electrolytic solution to be made is impregnated into anode, in most cases in anode Interior or positive electrode surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Thus, for can be from being recovered to when dismantling the battery Anode the case where at least detecting mono-fluor phosphate and/or difluorophosphoric acid salt, be considered as belonging to the present invention 1.

Further, it is also possible to which the cathode of non-aqueous electrolyte secondary battery made of making is interior or negative terminal surface contains single fluorine phosphorus in advance Hydrochlorate and difluorophosphoric acid salt.At this point, it can be expected that some or all of mono-fluor phosphate and/or difluorophosphoric acid salt for containing in advance are molten Solution functions in nonaqueous electrolytic solution, which is considered as belonging to the present invention 1.For making in cathode or negative terminal surface is preparatory Method containing mono-fluor phosphate and difluorophosphoric acid salt, have no it is specifically limited, as specific example, can enumerate it is as described later, Mono-fluor phosphate and difluorophosphoric acid salt is set to be dissolved in the method in the slurry of preparation when cathode is made；Or make single fluorophosphoric acid in advance Salt and difluorophosphoric acid salt are dissolved in arbitrary nonaqueous solvents, and solution obtained is recycled to be coated manufactured cathode Or after being impregnated with, it is dry, remove used in solvent, to make in cathode or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid The method etc. of salt.

It, can also be from including at least one kind of mono-fluor phosphate and two in addition, in actual fabrication non-aqueous electrolyte secondary battery The nonaqueous electrolytic solution of fluorophosphate makes in cathode or negative terminal surface contains mono-fluor phosphate and difluorophosphoric acid salt.Making secondary electricity Chi Shi, since nonaqueous electrolytic solution to be made is impregnated into cathode, in most cases in cathode or negative terminal surface can contain Mono-fluor phosphate and difluorophosphoric acid salt.Thus, for can at least detect list from the cathode being recovered to when dismantling the battery The case where fluorophosphate and difluorophosphoric acid salt, is considered as belonging to the present invention 1.

Further, it is also possible to which the partition of non-aqueous electrolyte secondary battery made of making is interior or baffle surface contains single fluorine phosphorus in advance Hydrochlorate and/or difluorophosphoric acid salt.At this point, it can be expected that some or all of mono-fluor phosphate and difluorophosphoric acid salt for containing in advance are molten Solution functions in nonaqueous electrolytic solution, which is considered as belonging to the present invention 1.For making in partition or baffle surface is preparatory Method containing mono-fluor phosphate and/or difluorophosphoric acid salt, has no specifically limited, as specific example, can enumerate: be made every The method for mixing mono-fluor phosphate and difluorophosphoric acid salt when plate, or make mono-fluor phosphate and the dissolution of difluorophosphoric acid salt in office in advance In the nonaqueous solvents of meaning, and partition is coated or is impregnated with using solution obtained before making non-aqueous electrolyte secondary battery Afterwards, dry, removing solvent, to make the method that in partition or baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.

It, can also be from including mono-fluor phosphate and/or difluoro phosphorus in addition, in actual fabrication non-aqueous electrolyte secondary battery The nonaqueous electrolytic solution of hydrochlorate makes in partition or baffle surface contains mono-fluor phosphate and/or difluorophosphoric acid salt.Making non-water power When solving electrolitc secondary cell, since nonaqueous electrolytic solution to be made is impregnated into partition, in most cases in partition or partition Surface can contain mono-fluor phosphate and difluorophosphoric acid salt.Therefore, for can be from the partition of recycling at least when dismantling the battery The case where detecting mono-fluor phosphate and difluorophosphoric acid salt is considered as belonging to the present invention 1.

<1-4. iron family element>

In the nonaqueous electrolytic solution of the present invention 1, other than above-mentioned mono-fluor phosphate and/or difluorophosphoric acid salt, also containing spy Determine the iron family element of concentration.By making 1 mono-fluor phosphate and/or the iron family element of difluorophosphoric acid salt and certain concentration of the invention It exists simultaneously, can express synergy, especially it is possible to which being obviously improved is being more than to be used as the secondary electricity of common nonaqueous electrolyte The upper limit in pond uses the cycle characteristics under the high voltage condition of the 4.2V of voltage.

For showing the principal element of such synergy, details is still not clear, and the range of the present invention 1 It is not limited by this factor, but can consider it with following mechanism.That is, as the present invention 1 nonaqueous electrolytic solution must In the reduction reaction product of " mono-fluor phosphate and/or the difluorophosphoric acid salt " of palpus ingredient, the cation of iron family element is entered In reaction product, for example, ionomer as P-O-M-O-P key (here, M indicates iron family element) is formed, to be formed more Stable protection envelope.In order to form such protection envelope, it is believed that make non-water power in the charging stage at initial stage for forming envelope It is effective for containing iron family element in solution liquid.

<type of 1-4-1. iron family element>

" iron family element " contained by the nonaqueous electrolytic solution of the present invention 1, specifically ferro element, cobalt element, nickel element. In these iron family elements, from the viewpoint of forming more stable envelope, preferably cobalt element, nickel element.

In the present invention 1, as the method made in nonaqueous electrolytic solution containing iron family element, preferably dissolve iron group compound Method in nonaqueous electrolytic solution.Here, as " the iron group compound " in the present invention 1, it is usually preferred to use iron family element The ionic compound that oxidation number is+2 or+3.

As the specific example of " iron group compound ", it can be mentioned, for example: hexafluorophosphoric acid iron (II), hexafluorophosphoric acid iron (III), The hexafluorophosphates such as hexafluorophosphoric acid cobalt (II), hexafluorophosphoric acid nickel (II)；

The tetrafluoros boron such as tetrafluoro boric acid iron (II), tetrafluoro boric acid iron (III), cobalt (II), tetrafluoro boric acid nickel (II) Hydrochlorate；

The perchlorate such as ferric perchlorate (II), ferric perchlorate (III), cobaltous perchlorate (II), nickelous perchlorate (II)；

The sulfate such as ferric sulfate (II), ferric sulfate (III), cobaltous sulfate (II), nickel sulfate (II)；

The nitrate such as ferric nitrate (II), ferric nitrate (III), cobalt nitrate (II), nickel nitrate (II)；

The acetates such as ferric acetate (II), ferric acetate (III), cobalt acetate (II), nickel acetate (II)；

The carbonate such as ferric carbonate (II), ferric carbonate (III), cobalt carbonate (II), nickelous carbonate (II)；

The oxalates such as ferric oxalate (II), ferric oxalate (III), cobalt oxalate (II), nickel oxalate (II)；

The citrates such as ironic citrate (II), ironic citrate (III), citric acid cobalt (II), citric acid nickel (II)；

The benzoates such as benzoic acid iron (II), benzoic acid iron (III), cobalt benzoate (II), nickel benzoate (II)；

The phosphate such as ferric phosphate (II), ferric phosphate (III), cobalt phosphate (II), nickel phosphate (II)；

The fluorides such as ferric flouride (II), ferric flouride (III), cobaltous fluoride (II), nickel fluoride (II)；

Acetyl acetone iron (II), acetyl acetone iron (III), acetyl acetone cobalt (II), acetyl acetone cobalt (III), the iron family elements acetylacetonate such as nickel acetylacetonate (II)；Etc..

In these iron group compounds, the salt that the anion and cobalt or nickel for being preferably not susceptible to reaction in the battery are formed, example Such as hexafluorophosphoric acid cobalt (II), hexafluorophosphoric acid nickel (II) hexafluorophosphate；Cobalt (II), tetrafluoro boric acid nickel (II) etc. four Borofluoride；The perchlorate such as cobaltous perchlorate (II), nickelous perchlorate (II)；The phosphate such as cobalt phosphate (II), nickel phosphate (II)；Fluorine Change the fluorides such as cobalt (II), nickel fluoride (II).

Wherein, from the point of view of stable this respect in the battery, more preferable hexafluorophosphoric acid cobalt (II), hexafluorophosphoric acid nickel (II) etc. six Fluorophosphate；The fluorides such as cobaltous fluoride (II), nickel fluoride (II).These iron group compounds can be used a kind, can also be any group It closes and uses two or more.In addition, these preferred anhydrides of iron group compound, but hydrate also can be used, as long as it is as needed Aftermentioned dehydration is carried out.

<1-4-2. content and its detection method>

The present invention 1 in iron family element content relative to nonaqueous electrolytic solution total amount be usually 1ppm or more, preferably 2ppm or more, more preferably 3ppm or more, particularly preferably 5ppm or more, most preferably 8ppm or more, and usually 2000ppm Below, be preferably 600ppm or less, more preferably 100ppm or less, particularly preferably 50ppm or less, be most preferably 30ppm with Under.If being lower than the lower limit of the range, the said effect of the present invention 1 is hardly shown sometimes.In addition, being more than the upper limit When, iron family element is sometimes prone to be reduced in cathode and be precipitated on cathode in a metallic form.In addition, also resulting in electrolyte It decomposes, as a result reduces cycle characteristics sometimes.It should be noted that the iron family element of two or more present invention 1 is applied in combination When, the total concentration of used iron family element is in above range.

For the present invention 1, iron family element can be added, iron family element can also be generated in the electrolytic solution.In electrolyte It is common metallic element analysis as the method for iron family element content contained in detection nonaqueous electrolytic solution when middle generation Method, for example, atomic absorption analysis (AAS), inductively coupled plasma body luminescence analysis (ICP), fluorescent X-ray can be passed through Analytical equipment (XRF) etc. is quantified.Especially ICP luminescence analysis, pre-treatment is easy, and precision is also high, is also less prone to It is influenced by other elements, therefore it is preferable to use.

<1-5. additive>

In the range of the unobvious effect for destroying the present invention 1, the nonaqueous electrolytic solution of the present invention 1 can also add containing various Add agent.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that adding Add agent can be used alone, two or more can also be applied in combination with ratio in any combination.

As the example of additive, overcharge preventing agent can be enumerated, for improving the capacity maintenance characteristics after High temperature storage And auxiliary agent of cycle characteristics etc..In these additives, as being used to improve the capacity maintenance characteristics after High temperature storage and circulation The auxiliary agent of characteristic is preferably added to have the carbonic ester of at least one of unsaturated bond and halogen atom (hereinafter sometimes referred to simply as " specific Carbonic ester ").In the following, being illustrated respectively to specific carbonic ester and other additives.

<the specific carbonic ester of 1-5-1.>

Specific carbonic ester is the carbonic ester at least one of unsaturated bond and halogen atom, and specific carbonic ester can only have There is unsaturated bond, can also only have halogen atom, can also have unsaturated bond and halogen atom simultaneously.

The molecular weight of specific carbonic ester is had no it is specifically limited, it is unobvious destroy the present invention 1 effect in the range of Can be any molecular weight, but usually 50 or more, preferably 80 or more, and be usually below 250, preferably 150 or less. When molecular weight is excessive, dissolubility of the specific carbonic ester in nonaqueous electrolytic solution is reduced, and be may cause and is difficult to show sufficient effect Fruit.

In addition, the preparation method for specific carbonic ester is also not particularly limited, well known method can arbitrarily be selected to make It makes.

Furthermore, it is possible to make individually containing any a kind of specific carbonic ester in the nonaqueous electrolytic solution of the present invention 1, it can also be to appoint Meaning combination and and ratio contain two or more simultaneously.

In addition, for specific carbonic ester relative to the present invention 1 nonaqueous electrolytic solution combined amount there is no limit, unobvious It can be any combined amount, but the nonaqueous electrolytic solution relative to the present invention 1 in the range of the effect of the destruction present invention 1, it is contained The ideal concentration of specific carbonic ester is usually 0.01 weight % or more, preferably 0.1 weight % or more, more preferably 0.3 weight % or more is measured, and usually 70 weight % or less, preferably 50 weight % or less, more preferably 40 weight % or less.

If being lower than the lower limit of the range, the nonaqueous electrolytic solution of the present invention 1 is being used for non-aqueous electrolyte secondary battery When, it may cause the non-aqueous electrolyte secondary battery and be difficult to show sufficient cycle characteristics improvement effect.In addition, working as particular carbon When the ratio of acid esters is excessive, when the nonaqueous electrolytic solution of the present invention 1 is used for non-aqueous electrolyte secondary battery, the nonaqueous electrolyte two The High temperature storage characteristic and trickle charge characteristic of primary cell have the tendency that reduction, especially gas generated to increase, and capacity is kept Rate decline.

(1-5-1-1. unsaturated carbon acid ester)

In the specific carbonic ester of the present invention 1, as the carbonic ester with unsaturated bond (hereinafter, sometimes referred to simply as " insatiable hunger And carbonic ester "), as long as the carbonic ester with carbon-to-carbon unsaturated bonds such as carbon-to-carbon double bond, carbon-carbon triple bonds is then without other limits System, can be used arbitrary unsaturated carbon acid ester.It should be pointed out that the carbonic ester with aromatic rings, which also belongs to, has unsaturation The carbonic ester of key.

As the example of unsaturated carbon acid ester, vinylene carbonate derivative species can be enumerated, by with aromatic rings or carbon-to-carbon Ethylene carbonate derivative class, the carbonic acid phenyl ester class, ethylene carbonate esters, allyl esters of the substituent group substitution of unsaturated bond Deng.

As the specific example of vinylene carbonate derivative species, vinylene carbonate, methyl carbonic acid Asia ethylene can be enumerated Ester, 4,5- dimethyl vinylene carbonate, phenyl-carbonic acid vinylene, 4,5- diphenyl vinylene carbonate, catechol carbonic acid Ester etc..

As the specific of the ethylene carbonate derivative class replaced by the substituent group with aromatic rings or carbon-to-carbon unsaturated bond Example can enumerate vinylethylene carbonate, 4,5- divinyl ethylene carbonate, phenyl-carbonic acid ethyl, 4,5- diphenyl Ethylene carbonate etc..

As the specific example of carbonic acid phenyl ester class, diphenyl carbonate, carbonic acid ethyl phenyl ester, methyl phenyl can be enumerated Ester, carbonic acid tert-butyl benzene base ester etc..

As the specific example of ethylene carbonate esters, divinyl carbonate, methyl vinyl esters etc. can be enumerated.

As the specific example of allyl esters, diallyl carbonate, methyl allyl ester etc. can be enumerated.

In these unsaturated carbon acid esters, as specific carbonic ester, preferably vinylene carbonate derivative species, there is virtue The ethylene carbonate derivative class that the substituent group of fragrant ring or carbon-to-carbon unsaturated bond replaces, especially vinylene carbonate, 4,5- bis- Phenyl-carbonic acid vinylene, 4,5- dimethyl vinylene carbonate, vinylethylene carbonate, since stable interface can be formed Envelope is protected, thus is more preferably used.

(1-5-1-2. halocarbonate)

On the other hand, in the specific carbonic ester involved in the present invention 1, as the carbonic ester with halogen atom (hereinafter, having When be referred to as " halocarbonate "), as long as the carbonic ester with halogen atom then has no other specifically limited, can be used arbitrary Halocarbonate.

As the specific example of halogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom can be enumerated.Wherein, preferably fluorine is former Son or chlorine atom, particularly preferred fluorine atom.In addition, Number of Halogen Atoms possessed by halocarbonate is as long as spy no as long as 1 or more Different limitation, but usually 6 hereinafter, preferably 4 or less.When halocarbonate has multiple halogen atoms, these halogen atoms can be with It is mutually the same, it can also be different.

As the example of halocarbonate, ethylene carbonate derivative class, dimethyl carbonate derivative species, carbonic acid can be enumerated Methyl ethyl ester derivative species, diethyl carbonate derivative species etc..

As the specific example of ethylene carbonate derivative class, can enumerate: fluorine ethylene carbonate, vinylene carbonate, 4, 4- difluoro ethylene carbonate, 4,5- difluoro ethylene carbonate, bis- vinylene carbonate of 4,4-, bis- vinylene carbonate of 4,5-, 4- Fluoro- 4- methyl carbonic acid ethyl, the chloro- 4- methyl carbonic acid ethyl of 4-, the fluoro- 4- methyl carbonic acid ethyl of 4,5- bis-, 4,5- bis- are chloro- The fluoro- 5- methyl carbonic acid ethyl of 4- methyl carbonic acid ethyl, 4-, the chloro- 5- methyl carbonic acid ethyl of 4-, the fluoro- 5- methyl of 4,4- bis- Ethylene carbonate, the chloro- 5- methyl carbonic acid ethyl of 4,4- bis-, 4- (methyl fluoride) ethylene carbonate, 4- (chloromethyl) carbonic acid Asia second Ester, 4- (difluoromethyl) ethylene carbonate, 4- (dichloromethyl) ethylene carbonate, 4- (trifluoromethyl) ethylene carbonate, 4- (three Chloromethyl) ethylene carbonate, 4- (methyl fluoride) -4- fluorine ethylene carbonate, 4- (chloromethyl) -4- vinylene carbonate, 4- (fluorine first Base) -5- fluorine ethylene carbonate, 4- (chloromethyl) -5- vinylene carbonate, the fluoro- 4,5- dimethyl ethylene carbonate of 4-, 4- be chloro- 4,5- dimethyl ethylene carbonate, the fluoro- 4,5- dimethyl ethylene carbonate of 4,5- bis-, the chloro- 4,5- dimethyl carbonic acid of 4,5- bis- are sub- Ethyl ester, the fluoro- 5,5- dimethyl ethylene carbonate of 4,4- bis-, the chloro- 5,5- dimethyl ethylene carbonate of 4,4- bis- etc..

It as the specific example of dimethyl carbonate derivative species, can enumerate: methyl methyl fluoride ester, methyl difluoro Methyl ester, methyl methyl ester trifluoroacetate, carbonic acid two (methyl fluoride) ester, carbonic acid two (difluoromethyl) ester, two (fluoroform of carbonic acid Base) ester, methyl chloromethane base ester, methyl dichloromethane base ester, methyl trichloromethyl ester, carbonic acid two (chloromethyl) Ester, carbonic acid two (dichloromethyl) ester, carbonic acid two (trichloromethyl) ester etc..

It as the specific example of methyl ethyl carbonate derivative species, can enumerate: methyl 2- fluoro ethyl ester, carbonic acid ethyl fluoride Methyl ester, methyl 2,2- bis-fluoro ethyls ester, carbonic acid methyl fluoride 2- fluoro ethyl ester, carbonic acid ethyl difluoro methyl ester, carbonic acid first Base 2,2,2- trifluoroethyl ester, carbonic acid methyl fluoride 2,2- bis-fluoro ethyls ester, carbonic acid difluoromethyl 2- fluoro ethyl ester, carbonic acid ethyl three Methyl fluoride ester, methyl 2- chloro-ethyl ester, carbonic acid ethyl chloride methyl ester, methyl 2,2- Dichloroethyl ester, carbonic acid chloromethane Base 2- chloro-ethyl ester, carbonic acid ethyl dichloromethane base ester, methyl 2,2,2- trichloroethyl, bis- chloroethene of carbonic acid chloromethyl 2,2- Base ester, carbonic acid dichloromethyl 2- chloro-ethyl ester, carbonic acid ethyl trichloromethyl ester etc..

It as the specific example of diethyl carbonate derivative species, can enumerate: carbonic acid ethyl (2- fluoro ethyl) ester, carbonic acid ethyl (2,2- bis-fluoro ethyls) ester, carbonic acid two (2- fluoro ethyl) ester, carbonic acid ethyl (2,2,2- trifluoroethyl) ester, carbonic acid 2,2- difluoro second Base -2 '-fluoro ethyl ester, carbonic acid two (2,2- bis-fluoro ethyls) ester, carbonic acid 2,2,2- trifluoroethyl -2 '-fluoro ethyl ester, carbonic acid 2,2, 2- trifluoroethyl -2 ', 2 '-bis-fluoro ethyls esters, carbonic acid two (2,2,2- trifluoroethyl) ester, carbonic acid ethyl (2- chloroethyl) ester, carbon Sour ethyl (2,2- Dichloroethyl) ester, carbonic acid two (2- chloroethyl) ester, carbonic acid ethyl (2,2,2- trichloroethyl) ester, carbonic acid 2,2- Dichloroethyl -2 '-chloro-ethyl ester, carbonic acid two (2,2- Dichloroethyl) ester, carbonic acid 2,2,2- trichloroethyl -2 '-chloro-ethyl ester, carbon Sour 2,2,2- trichloroethyl -2 ', 2 '-Dichloroethyl esters, carbonic acid two (2,2,2- trichloroethyl) ester etc..

In above-mentioned halocarbonate, preferably with the carbonic ester of fluorine atom, more preferably with the carbonic acid Asia second of fluorine atom Ester derivant class, especially since when using fluorine ethylene carbonate, 4- (methyl fluoride) ethylene carbonate, 4,4- difluoro carbonic acid sub- It will form protection envelope in interface when ethyl ester, 4,5- difluoro ethylene carbonate, thus it is more preferable.

(the halogenated unsaturated carbon acid ester of 1-5-1-3.)

In addition, can also use as specific carbonic ester while there is the carbonic ester of unsaturated bond and halogen atom (to be fitted When referred to as " halogenated unsaturated carbon acid ester ").It as halogenated unsaturated carbon acid ester, has no specifically limited, is not destroying this significantly Arbitrary halogenated unsaturated carbon acid ester can be used in the range of the effect of invention 1.

As the example of halogenated unsaturated carbon acid ester, vinylene carbonate derivative species can be enumerated, by with aromatic rings or Ethylene carbonate derivative class, allyl esters that the substituent group of carbon-to-carbon unsaturated bond replaces etc..

It as the specific example of vinylene carbonate derivative species, can enumerate: the fluoro- 5- methyl of fluorine vinylene carbonate, 4- The fluoro- 5- phenyl-carbonic acid vinylene of vinylene carbonate, 4-, 4- (trifluoromethyl) vinylene carbonate, chlorine vinylene carbonate, The chloro- 5- methylvinylene carbonate of 4-, the chloro- 5- phenyl-carbonic acid vinylene of 4-, 4- (trichloromethyl) vinylene carbonate etc..

As the specific of the ethylene carbonate derivative class replaced by the substituent group with aromatic rings or carbon-to-carbon unsaturated bond Example can be enumerated: the fluoro- 4- vinylethylene carbonate of 4-, the fluoro- 5- vinylethylene carbonate of 4-, the fluoro- 4- vinyl of 4,4- bis- Ethylene carbonate, the fluoro- 4- vinylethylene carbonate of 4,5- bis-, the chloro- 5- vinylethylene carbonate of 4-, the chloro- 4- second of 4,4- bis- Alkenyl ethylene carbonate, the chloro- 4- vinylethylene carbonate of 4,5- bis-, the fluoro- 4,5- divinyl ethylene carbonate of 4-, 4,5- bis- Fluoro- 4,5- divinyl ethylene carbonate, the chloro- 4,5- divinyl ethylene carbonate of 4-, the chloro- 4,5- divinyl carbon of 4,5- bis- The fluoro- 4- phenyl-carbonic acid ethyl of sour ethyl, 4-, the fluoro- 5- phenyl-carbonic acid ethyl of 4-, bis- fluoro- 5- phenyl-carbonic acid Asia second of 4,4- Ester, the fluoro- 4- phenyl-carbonic acid ethyl of 4,5- bis-, the chloro- 4- phenyl-carbonic acid ethyl of 4-, the chloro- 5- phenyl-carbonic acid ethyl of 4-, 4,4- Two chloro- 5- phenyl-carbonic acid ethyls, the chloro- 4- phenyl-carbonic acid ethyl of 4,5- bis-, bis- fluoro- 4,5- diphenyl carbonic acid Asia second of 4,5- Ester, the chloro- 4,5- diphenyl ethylene carbonate of 4,5- bis- etc..

It as the specific example of carbonate esters, can enumerate: carbonic acid trifluoromethylphenyl ester, carbonic acid 2- fluoro ethyl phenyl Ester, carbonic acid 2,2- bis-fluoro ethyls phenylester, carbonic acid 2,2,2- trifluoroethyl phenylester, carbonic acid chloromethylbenzene base ester, carbonic acid 2- chlorine Ethyl phenyl ester, carbonic acid 2,2- Dichloroethyl phenylester, carbonic acid 2,2,2- trichloroethyl phenylester etc..

It as the specific example of ethylene carbonate esters, can enumerate: carbonic acid methyl fluoride vinyl esters, carbonic acid 2- fluoro ethyl ethylene Base ester, carbonic acid 2,2- bis-fluoro ethyls vinyl esters, carbonic acid 2,2,2- trifluoroethyl vinyl esters, carbonic acid chloromethyl vinyl base ester, Carbonic acid 2- chloroethyl vinyl base ester, carbonic acid 2,2- Dichloroethyl vinyl esters, carbonic acid 2,2,2- trichloroethyl vinyl esters etc..

It as the specific example of allyl esters, can enumerate: carbonic acid methyl fluoride allyl ester, carbonic acid 2- fluoro ethyl allyl Base ester, carbonic acid 2,2- bis-fluoro ethyls allyl ester, carbonic acid 2,2,2- trifluoroethyl allyl ester, carbonic acid chloromethyl allyl ester, Carbonic acid 2- chloroethyl allyl ester, carbonic acid 2,2- Dichloroethyl allyl ester, carbonic acid 2,2,2- trichloroethyl allyl ester etc..

In the example of above-mentioned halogenated unsaturated carbon acid ester, as specific carbonic ester, particularly preferably using to be selected from individually makes The better vinylene carbonate of the effect of used time, vinylethylene carbonate, fluorine ethylene carbonate and 4,5- difluoro carbonic acid Asia second The compound of one or more of ester and their derivative.

<the other additives of 1-5-2.>

In the following, being illustrated for the additive other than specific carbonic ester.It, can as the additive other than specific carbonic ester Enumerate overcharge preventing agent, auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics etc..

<1-5-2-1. overcharge preventing agent>

As the specific example of overcharge preventing agent, can enumerate:

The toluene derivatives such as toluene, dimethylbenzene；

Biphenyl, 2- methyl biphenyl, 3- methyl biphenyl, 4- methyl biphenyl etc. are non-substituted or are derived by alkyl-substituted biphenyl Object；

Ortho-terphenyl, meta-terphenyl, para-terpheny etc. are non-substituted or by alkyl-substituted terphenyl derivatives；

Part hydride non-substituted or by alkyl-substituted terphenyl derivatives；

The naphthenic base benzene derivative such as cyclopenta benzene, cyclohexyl benzene；

Isopropylbenzene, 1,3- diisopropyl benzene, 1,4- diisopropyl benzene etc. have the alkane of tertiary carbon of the Direct Bonding on phenyl ring Base benzene derivative；

Tert-butyl benzene, tert-amyl benzene, tertiary hexyl benzene etc. have the benzene derivative of quaternary carbon of the Direct Bonding on phenyl ring；

Diphenyl ether, dibenzofurans etc. have the aromatic compounds such as the aromatic compound of oxygen atom；Equal aromatic series Compound.

In addition, the specific example as other overcharge preventing agents, can also enumerate: fluorobenzene, toluene fluoride, fluoroform Benzene, 2- fluorine biphenyl, adjacent cyclohexyl fluorobenzene, to the partially fluorinated object of the above-mentioned aromatic compound such as cyclohexyl fluorobenzene；2,4- difluoro Fluorine-containing benzyl ether compounds such as methyl phenyl ethers anisole, 2,5- difluoroanisole, 1,6- difluoroanisole etc..

It should be noted that these overcharge preventing agents can be used alone a kind, 2 can also be used simultaneously in any combination Kind or more.In addition, in any combination simultaneously in use, belong to same category of compound in the above-mentioned example that can be used in combination, Different classes of compound can also be applied in combination.

As specific example when being applied in combination different classes of compound, can enumerate:

Toluene derivative and biphenyl derivatives；

Toluene derivative and terphenyl derivatives；

The part hydride of toluene derivative and terphenyl derivatives；

Toluene derivative and naphthenic base benzene derivative；

The benzene derivative of toluene derivative and the tertiary carbon with Direct Bonding on phenyl ring；

The benzene derivative of toluene derivative and the quaternary carbon with Direct Bonding on phenyl ring；

Toluene derivative and aromatic compound with oxygen atom；

The partially fluorinated object of toluene derivative and aromatic compound；

Toluene derivative and fluorine-containing benzyl ether compounds；

Biphenyl derivatives and terphenyl derivatives；

The part hydride of biphenyl derivatives and terphenyl derivatives；

Biphenyl derivatives and naphthenic base benzene derivative；

The benzene derivative of biphenyl derivatives and the tertiary carbon with Direct Bonding on phenyl ring；

The benzene derivative of biphenyl derivatives and the quaternary carbon with Direct Bonding on phenyl ring；

Biphenyl derivatives and aromatic compound with oxygen atom；

The partially fluorinated object of biphenyl derivatives and aromatic compound；

Biphenyl derivatives and fluorine-containing benzyl ether compounds；

The part hydride of terphenyl derivatives and terphenyl derivatives；

Terphenyl derivatives and naphthenic base benzene derivative；

The benzene derivative of terphenyl derivatives and the tertiary carbon with Direct Bonding on phenyl ring；

The benzene derivative of terphenyl derivatives and the quaternary carbon with Direct Bonding on phenyl ring；

Terphenyl derivatives and aromatic compound with oxygen atom；

The partially fluorinated object of terphenyl derivatives and aromatic compound；

Terphenyl derivatives and fluorine-containing benzyl ether compounds；

The part hydride of terphenyl derivatives and naphthenic base benzene derivative；

The part hydride of terphenyl derivatives and the benzene derivative of the tertiary carbon with Direct Bonding on phenyl ring；

The part hydride of terphenyl derivatives and the benzene derivative of the quaternary carbon with Direct Bonding on phenyl ring；

The part hydride of terphenyl derivatives and aromatic compound with oxygen atom；

The part hydride of terphenyl derivatives and the partially fluorinated object of aromatic compound；

The part hydride and fluorine-containing benzyl ether compounds of terphenyl derivatives；

The benzene derivative of naphthenic base benzene derivative and the tertiary carbon with Direct Bonding on phenyl ring；

The benzene derivative of naphthenic base benzene derivative and the quaternary carbon with Direct Bonding on phenyl ring；

Naphthenic base benzene derivative and aromatic compound with oxygen atom；

The partially fluorinated object of naphthenic base benzene derivative and aromatic compound；

Naphthenic base benzene derivative and fluorine-containing benzyl ether compounds；

The benzene derivative of tertiary carbon with Direct Bonding on phenyl ring and quaternary carbon with Direct Bonding on phenyl ring Benzene derivative；

The benzene derivative of tertiary carbon with Direct Bonding on phenyl ring and aromatic compound with oxygen atom；

The benzene derivative of tertiary carbon with Direct Bonding on phenyl ring and the partially fluorinated object of aromatic compound；

The benzene derivative of tertiary carbon with Direct Bonding on phenyl ring and fluorine-containing benzyl ether compounds；

The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and aromatic compound with oxygen atom；

The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and the partially fluorinated object of aromatic compound；

The benzene derivative of quaternary carbon with Direct Bonding on phenyl ring and fluorine-containing benzyl ether compounds；

The partially fluorinated object of aromatic compound and aromatic compound with oxygen atom；

Aromatic compound and fluorine-containing benzyl ether compounds with oxygen atom；

The partially fluorinated object and fluorine-containing benzyl ether compounds of aromatic compound.

It as the specific example of said combination, can be listed below: combination, biphenyl and the meta-terphenyl of biphenyl and ortho-terphenyl Combination, biphenyl and terphenyl derivatives the combination of part hydride, the combination of biphenyl and isopropylbenzene, biphenyl and cyclopenta benzene Combination, the combination of biphenyl and cyclohexyl benzene, the combination of biphenyl and tert-butyl benzene, the combination of biphenyl and tert-amyl benzene, biphenyl and The combination of diphenyl ether, the combination of biphenyl and dibenzofurans, the combination of biphenyl and fluorobenzene, the combination of biphenyl and benzotrifluoride, The combination of biphenyl and 2- fluorine biphenyl, combination, biphenyl and the combination to fluorine cyclohexyl benzene of biphenyl and adjacent fluorine cyclohexyl benzene, biphenyl and The combination of 2,4 difluorobenzene methyl ether；

The combination of the part hydride of ortho-terphenyl and terphenyl derivatives, the combination of ortho-terphenyl and isopropylbenzene, neighbour three The combination of biphenyl and cyclopenta benzene, the combination of ortho-terphenyl and cyclohexyl benzene, the combination of ortho-terphenyl and tert-butyl benzene, neighbour three The combination of benzene and tert-amyl benzene, the combination of ortho-terphenyl and diphenyl ether, the combination of ortho-terphenyl and dibenzofurans, neighbour three The combination of benzene and fluorobenzene, the combination of ortho-terphenyl and benzotrifluoride, ortho-terphenyl and 2- fluorine biphenyl combination, ortho-terphenyl and neighbour Combination, ortho-terphenyl and the combination to fluorine cyclohexyl benzene, the combination of ortho-terphenyl and 2,4 difluorobenzene methyl ether of fluorine cyclohexyl benzene；

The combination of the part hydride of meta-terphenyl and terphenyl derivatives, the combination of meta-terphenyl and isopropylbenzene, three The combination of biphenyl and cyclopenta benzene, the combination of meta-terphenyl and cyclohexyl benzene, the combination of meta-terphenyl and tert-butyl benzene, three The combination of benzene and tert-amyl benzene, the combination of meta-terphenyl and diphenyl ether, the combination of meta-terphenyl and dibenzofurans, three The combination of benzene and fluorobenzene, the combination of meta-terphenyl and benzotrifluoride, meta-terphenyl and 2- fluorine biphenyl combination, meta-terphenyl and neighbour Combination, meta-terphenyl and the combination to fluorine cyclohexyl benzene, the combination of meta-terphenyl and 2,4 difluorobenzene methyl ether of fluorine cyclohexyl benzene；

The combination of part hydride and isopropylbenzene, the part hydride of terphenyl derivatives and the ring penta of terphenyl derivatives The combination of base benzene, the combination of the part hydride of terphenyl derivatives and cyclohexyl benzene, terphenyl derivatives part hydride The combination of the part hydride and tert-amyl benzene of combination, terphenyl derivatives with tert-butyl benzene, terphenyl derivatives part The combination of hydride and diphenyl ether, the combination of the part hydride of terphenyl derivatives and dibenzofurans, terphenyl are derivative The combination of part hydride and fluorobenzene of object, the part hydride of terphenyl derivatives and the combination of benzotrifluoride, terphenyl spread out The group of the biological combination of part hydride and 2- fluorine biphenyl, the part hydride of terphenyl derivatives and adjacent fluorine cyclohexyl benzene It closes, the part hydride of terphenyl derivatives and the part hydride and 2 to the combination of fluorine cyclohexyl benzene, terphenyl derivatives, The combination of 4- difluoroanisole；

The combination of isopropylbenzene and cyclopenta benzene, the combination of isopropylbenzene and cyclohexyl benzene, the combination of isopropylbenzene and tert-butyl benzene, The combination of isopropylbenzene and tert-amyl benzene, the combination of isopropylbenzene and diphenyl ether, isopropylbenzene and dibenzofurans combination, isopropylbenzene The combination of combination, isopropylbenzene and benzotrifluoride with fluorobenzene, the combination of isopropylbenzene and 2- fluorine biphenyl, isopropylbenzene and adjacent fluorine cyclohexyl Combination, isopropylbenzene and the combination to fluorine cyclohexyl benzene, the combination of isopropylbenzene and 2,4 difluorobenzene methyl ether of benzene；

The combination of cyclohexyl benzene and tert-butyl benzene, the combination of cyclohexyl benzene and tert-amyl benzene, cyclohexyl benzene and diphenyl ether Combination, the combination of cyclohexyl benzene and dibenzofurans, the combination of cyclohexyl benzene and fluorobenzene, cyclohexyl benzene and benzotrifluoride group It closes, the combination of cyclohexyl benzene and 2- fluorine biphenyl, the combination of cyclohexyl benzene and adjacent fluorine cyclohexyl benzene, cyclohexyl benzene and to fluorine cyclohexyl The combination of benzene, the combination of cyclohexyl benzene and 2,4 difluorobenzene methyl ether；

The combination of tert-butyl benzene and tert-amyl benzene, the combination of tert-butyl benzene and diphenyl ether, tert-butyl benzene and dibenzo furan The combination of combination, tert-butyl benzene and the fluorobenzene muttered, the combination of tert-butyl benzene and benzotrifluoride, tert-butyl benzene and 2- fluorine biphenyl group Conjunction, combination, tert-butyl benzene and the combination to fluorine cyclohexyl benzene of tert-butyl benzene and adjacent fluorine cyclohexyl benzene, tert-butyl benzene and 2,4- bis- The combination of fluoroanisole；

The combination of tert-amyl benzene and diphenyl ether, the combination of tert-amyl benzene and dibenzofurans, tert-amyl benzene and fluorobenzene Combination, tert-amyl benzene and the combination of benzotrifluoride, the combination of tert-amyl benzene and 2- fluorine biphenyl, tert-amyl benzene and adjacent fluorine cyclohexyl benzene Combination, tert-amyl benzene and the combination to fluorine cyclohexyl benzene, the combination of tert-amyl benzene and 2,4 difluorobenzene methyl ether；

The combination of diphenyl ether and dibenzofurans, the combination of diphenyl ether and fluorobenzene, diphenyl ether and benzotrifluoride Combination, the combination of diphenyl ether and 2- fluorine biphenyl, the combination of diphenyl ether and adjacent fluorine cyclohexyl benzene, diphenyl ether and to fluorine hexamethylene The combination of base benzene, the combination of diphenyl ether and 2,4 difluorobenzene methyl ether, the combination of dibenzofurans and fluorobenzene, dibenzofurans and The combination of benzotrifluoride, the combination of dibenzofurans and 2- fluorine biphenyl, dibenzofurans and adjacent fluorine cyclohexyl benzene combination, hexichol And furans and the combination to fluorine cyclohexyl benzene, the combination of dibenzofurans and 2,4 difluorobenzene methyl ether；

The combination of fluorobenzene and benzotrifluoride, the combination of fluorobenzene and 2- fluorine biphenyl, fluorobenzene and adjacent fluorine cyclohexyl benzene combination, fluorine Benzene and the combination to fluorine cyclohexyl benzene, the combination of fluorobenzene and 2,4 difluorobenzene methyl ether；

The combination of benzotrifluoride and 2- fluorine biphenyl, the combination of benzotrifluoride and adjacent fluorine cyclohexyl benzene, benzotrifluoride and to fluorine The combination of cyclohexyl benzene, the combination of benzotrifluoride and 2,4 difluorobenzene methyl ether；

Combination, 2- fluorine biphenyl and the combination to fluorine cyclohexyl benzene of 2- fluorine biphenyl and adjacent fluorine cyclohexyl benzene, 2- fluorine biphenyl and The combination of 2,4 difluorobenzene methyl ether；

Adjacent fluorine cyclohexyl benzene and to the combination of the combination of fluorine cyclohexyl benzene, adjacent fluorine cyclohexyl benzene and 2,4 difluorobenzene methyl ether, To fluorine cyclohexyl benzene and 2, the combination, etc. of 4- difluoroanisole.

When the nonaqueous electrolytic solution of the present invention 1 contains overcharge preventing agent, in the model of the unobvious effect for destroying the present invention 1 In enclosing, concentration can be any concentration, but relative to nonaqueous electrolytic solution total amount, ideal concentration is usually 0.1 weight %~5 The range of weight %.

It is anti-containing overcharge in the nonaqueous electrolytic solution for making the present invention 1 in the range of the unobvious effect for destroying the present invention 1 Only agent, even if application method mistake or charging unit exception etc. can occur in additives for overcharge protection circuit non-normal working in contingency Situation and when leading to overcharge, can also improve the safety of non-aqueous electrolyte secondary battery, therefore preferably.

<1-5-2-2. auxiliary agent>

On the other hand, the concrete example as the auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics Son can be enumerated: the acid anhydrides of the dicarboxylic acids such as succinic acid, maleic acid, phthalic acid；Carbonic acid erythrite ester (エ リ ス リ タ ン カ ー ボ ネ ー ト), carbonic acid spiral shell-bis--dimethylene ester (ス ピ ロ-ビ ス-ジ メ チ レ ン カ ー ボ ネ ー ト) etc. is in addition to suitable Carbonate products other than the carbonic ester of specific carbonic ester；

Sulfurous acid glycol ester, 1,3- propane sultone, 1,4- butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, Sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, a sulphur Change tetra methylthiuram, N, N- dimethyl methyl sulfonamide, N, the sulfur-containing compounds such as N- diethyl Methanesulfomide；

1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2-Oxazolidone, 1,3- dimethyl -2- imidazoles The nitrogenous compounds such as alkanone, N- methyl succimide；

The hydrocarbon compounds such as heptane, octane, cycloheptane；

Aromatic fluorine compounds such as fluorobenzene, difluorobenzene, benzotrifluoride etc..

<preparation method of 1-6. nonaqueous electrolytic solution>

The present invention 1 nonaqueous electrolytic solution can by nonaqueous solvents dissolve electrolyte, the present invention 1 " mono-fluor phosphate And/or difluorophosphoric acid salt ", it is prepared by " iron group compound ", " other auxiliary agents " used as needed.

When preparing nonaqueous electrolytic solution, preferably to the various raw materials of nonaqueous electrolytic solution, i.e., lithium salts, the present invention 1 single fluorine phosphorus Hydrochlorate and/or difluorophosphoric acid salt, iron group compound, nonaqueous solvents and other auxiliary agents are dehydrated in advance.Journey as dehydration Degree, it is often desirable that dehydration is dehydrated to 50ppm or less, preferably to 30ppm or less.It should be noted that described in the present specification Ppm, refer to the ratio based on weight basis.

If there is water in nonaqueous electrolytic solution, then the electrolysis of water, the reacting of water and lithium metal, the hydrolysis of lithium salts may occur Deng not preferably.The method of dehydration is not particularly limited, for example, when being dehydrated object is the liquid such as nonaqueous solvents, can be used point Son sieve etc..In addition, can be dried below the temperature decomposed when being dehydrated object is the solids such as electrolyte.Iron group When compound is hydrate, iron group compound can be dissolved in nonaqueous solvents, then reuse molecular sieve etc. and be dehydrated.

[2. non-aqueous electrolyte secondary battery]

The non-aqueous electrolyte secondary battery of the present invention 1 has the nonaqueous electrolytic solution of aforementioned present invention 1 and can occlude and put The anode and cathode of ion out.

<2-1. battery structure>

For other structures other than cathode and nonaqueous electrolytic solution in the non-aqueous electrolyte secondary battery of the present invention 1, It is identical as known non-aqueous electrolyte secondary battery, usually have and clips the more of the nonaqueous electrolytic solution for being saturated with the present invention 1 Anode and cathode are laminated and they are accommodated in the form in shell (packaging body) by pore membrane (partition).Thus, for the present invention The shape of 1 non-aqueous electrolyte secondary battery is not particularly limited, and can be cylinder-shaped, rectangular, stacking shape, coin-shaped, large size Equal any shapes.

<2-2. nonaqueous electrolytic solution>

As nonaqueous electrolytic solution, the nonaqueous electrolytic solution of aforementioned present invention 1 can be used.It should be noted that without departing from this In the range of the main points of invention 1, other nonaqueous electrolytic solutions can also be mixed into the nonaqueous electrolytic solution of the present invention 1.

<2-3. cathode>

In the following, being illustrated for the negative electrode active material for cathode.As negative electrode active material, as long as being capable of electricity The negative electrode active material for chemically occluding/releasing lithium ion, then be not particularly limited.It is sub as its concrete example, carbonaceous can be enumerated Material, alloy material, metallic composite oxides material containing lithium etc..

<2-3-1. carbonaceous material>

As the carbonaceous material for being used as negative electrode active material, since the carbonaceous material in following (1)~(4) can get Initial stage irreversible capacity, high current density charge-discharge characteristic it is well balanced, thus preferably.In addition, the carbonaceous material of (1)~(4) Material can be used alone, can also in any combination and two or more is applied in combination in ratio.The carbonaceous material of (1)~(4) Material are as follows: (1) natural graphite；(2) 1 is carried out to artificial carbonaceous material and artificial graphite substance in the range of 400~3200 DEG C Carbonaceous material obtained from the secondary above heat treatment；(3) negative electrode active material layer is by least two kinds of above with different crystalline carbon Texture at, and/or its different crystalline carbonaceous there are the carbonaceous materials at the interface being in contact；(4) negative electrode active material layer by At least two kinds of above carbonaceous with different orientation constitute, and/or the carbonaceous of its different orientation has the interface being in contact Carbonaceous material.

As the artificial carbonaceous material of above-mentioned (2) and the specific example of artificial graphite substance, natural graphite, coal can be enumerated Class coke, petroleum-type coke, coal class pitch, petroleum-type pitch or to these pitches carry out oxidation processes obtained from substance, Needle coke, pitch coke and by they part be graphitized obtained from carbon material；Furnace black, acetylene black, pitch-based carbon fiber It waits thermal decomposition product, the organic matter that can be carbonized and their carbide of organic matters or is dissolved in the organic matter that can be carbonized Solution obtained from the small molecular organic solvents such as benzene,toluene,xylene, quinoline, n-hexane and their carbide etc..

Wherein, the specific example as the organic matter carbonized, can enumerate the coal tar from maltha to pitch The coals class heavy oil such as pitch or destructive distillation liquefaction oil；The direct currents class heavy oil such as atmospheric resids, decompression residual oil, the thermal decomposition such as crude oil, naphtha When by-product ethylene bottom oil etc. decompose class black petroleum products；And the aromatic hydrocarbon such as acenaphthylene, decacyclene, anthracene, phenanthrene；Azophenlyene or acridine etc. contain There is the heterocyclic compound of nitrogen-atoms；The heterocyclic compounds containing sulphur atom such as thiophene, union II thiophene；The polyphenyl such as biphenyl, terphenyl； Polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, their insoluble processed material, nitrogenous polyacrylonitrile, polypyrrole etc. are organic high Molecule；The organic polymers such as polythiophene, the polystyrene of sulfur-bearing；With cellulose, lignin, mannocarolose, polygalacturonic acid, The natural polymers such as chitosan, the polysaccharide that sucrose is representative；The thermoplastic resins such as polyphenylene sulfide, polyphenylene oxide；Furfuryl alcohol resin, phenol Thermosetting resins such as urea formaldehyde, imide resin etc..

<structure, physical property, the preparation method of 2-3-2. carbonaceous cathode>

Property about carbonaceous material, the negative electrode containing carbonaceous material and electric polarization method, collector, nonaqueous electrolyte Secondary cell preferably meets wantonly 1 or multinomial in (1)~(18) as follows simultaneously.

(1) X-ray parameter

D value (the interlayer of lattice plane (002 face) calculated by X-ray diffraction is carried out to carbonaceous material by using vibration method Distance) it is usually 0.335~0.340nm, preferably 0.335~0.338nm, especially preferably 0.335~0.337nm.In addition, By using learn vibration method X-ray diffraction calculated by crystallite dimension (Lc) be usually 1.0nm or more, preferably 1.5nm or more, Especially preferably 2nm or more.

As the carbonaceous material obtained from amorphous carbon coating graphite surface, the crystalline substance preferably found out with X-ray diffraction The d value in lattice face (002 face) is the graphite of 0.335~0.338nm as nuclear material, and adheres on its surface and asked by X-ray diffraction The d value of lattice plane (002 face) out is greater than the carbonaceous material of the nuclear material, and nuclear material and the lattice found out by X-ray diffraction The d value in face (002 face) is greater than the carbonaceous material that the ratio of the carbonaceous material of the nuclear material is 99/1~80/20 with weight ratio meter. When using this carbonaceous material, it is possible to produce there is high capacity and be not easy the cathode reacted with electrolyte.

(2) ash content

Relative to the total weight of carbonaceous material, ash content contained in carbonaceous material is 1 weight % or less, is wherein preferably 0.5 weight % or less, 0.1 weight % is especially preferably hereinafter, its lower limit is preferably in 1ppm or more.If the weight ratio of ash content More than above range, battery performance can be caused ignorable deterioration occur because reacting with nonaqueous electrolytic solution in charge and discharge. On the other hand, when be lower than above range when, then be necessary for manufacture take a significant amount of time, energy and for prevent pollution set It is standby, further result in increased costs.

(3) volume-based average particle size

The volume-based average particle size of carbonaceous material is the average grain of the volume reference found out using laser diffraction/scattering method Diameter (median particle diameter), it typically is 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, especially preferably 7 μm or more, And usually 100 μm or less, preferably 50 μm or less, more preferably 40 μm or less, be more preferably 30 μm or less, it is especially excellent It is selected as 25 μm or less.If volume-based average particle size is lower than above range, irreversible capacity is made to increase and cause sometimes Initial cell capacitance loss.In addition, when being more than above range, it is easy to form non-uniform when using coating to prepare electrode Coated face is sometimes undesirable in battery production process.

Volume-based average particle size is measured using following methods: being dispersed in carbon dust as the poly- of surfactant In the 0.2 weight % aqueous solution (about 10mL) of ethylene oxide (20) Span-20, and utilize laser diffraction/scattering Formula particle size distribution meter (LA-700 of Ku Chang manufacturing company manufacture) is measured.The median particle diameter found out by the measurement is determined Justice is the volume-based average particle size of the carbonaceous material of the present invention 1.

(4) Raman R value, Raman half breadth

The Raman R value of carbonaceous material is the value measured using argon laser Raman spectroscopy, it typically is 0.01 or more, Preferably 0.03 or more, be more preferably 0.1 or more, and usually 1.5 or less, preferably 1.2 or less, more preferably 1 or less, it is outstanding It is preferably 0.5 or less.

When Raman R value is lower than above range, the crystallinity of particle surface is excessively high, may cause Li entrance with charge and discharge The site (サ イ ト) of interlayer tails off.That is, may cause charge acceptance reduction.In addition, passing through after being coated on the current collector When compacting carries out densification to cathode, crystallizes and be orientated readily along the direction parallel with electrode plate, may cause load characteristic It reduces.When on the other hand, more than above range, the crystallinity of particle surface is reduced, and causes to increase with the reactivity of nonaqueous electrolytic solution Add, the gas that may cause efficiency reduces or generate increases.

In addition, for carbonaceous material in 1580cm^-1Neighbouring Raman half breadth is not particularly limited, usually 10cm^-1 It above, is preferably 15cm^-1More than, and usually 100cm^-1It below, is preferably 80cm^-1Below, it is more preferably 60cm^-1Below, especially It is preferably 40cm^-1Below.

When Raman half breadth is lower than above range, the crystallinity of particle surface is excessively high, may cause with charge and discharge The site that Li enters interlayer tails off.That is, may cause charge acceptance reduction.In addition, passing through pressure after being coated on the current collector It when system carries out densification to cathode, crystallizes and is orientated readily along the direction parallel with electrode plate, may cause load characteristic drop It is low.When on the other hand, more than above range, the crystallinity of particle surface is reduced, and causes to increase with the reactivity of nonaqueous electrolytic solution, The gas that may cause efficiency reduces or generate increases.

The measurement of Raman spectrum is as described below: raman splitter (raman splitter of Japanese light splitting company manufacture) is used, It falls sample naturally and is filled in cell (cell), argon laser is irradiated to the surface of sample in pond, while making to survey Determine to rotate in the vertical face of Chi Yu laser, thus be measured.For the Raman spectrum of acquisition, measure in 1580cm^-1Near Peak P_AIntensity I_AAnd in 1360cm^-1Neighbouring peak P_BIntensity I_B, and calculate the intensity ratio R (R=I of the two_B/I_A).It will The Raman R value of carbonaceous material in the present invention 1 is defined as using the Raman R value that the measurement is found out.In addition, measuring obtained Raman Spectrum is in 1580cm^-1Neighbouring peak P_AHalf breadth, be defined as the present invention 1 in carbonaceous material Raman half breadth.

In addition, the condition of above-mentioned Raman measurement is as follows.

Argon laser wavelength: 514.5nm

Laser power on sample: 15~25mW

Resolution ratio: 10~20cm^-1

Measurement range: 1100cm^-1~1730cm^-1

Raman R value, the analysis of Raman half breadth: background (background) processing

Smoothly (smoothing) is handled: simple average, 5 points of convolution (5 point of convolution)

(5) BET specific surface area

Value using the BET specific surface area of the carbonaceous material of BET method measurement is usually 0.1m²·g^-1Above, preferably 0.7m²·g^-1Above, it is more preferably 1.0m²·g^-1Above, it is especially preferably 1.5m²·g^-1More than, and usually 100m²·g^-1 It below, is preferably 25m²·g^-1Below, it is more preferably 15m²·g^-1Below, it is especially preferably 10m²·g^-1Below.

When the value of BET specific surface area is lower than the range, lithium when being easy to cause charging when being used as negative electrode material Acceptance is deteriorated, lithium is easy to be precipitated to electrode surface, and then may cause stability reduction.When on the other hand, more than the range, Cause to increase with the reactivity of nonaqueous electrolytic solution when being used as negative electrode material, be easy to generate more gas, and then may be difficult To obtain ideal battery.

Carry out by the following method using when BET method measurement the specific area: using surface area meter, (Okura development is made complete Automatic surface accumulate measurement device), under nitrogen flowing, at 350 DEG C to sample carry out predrying in 15 minutes after, using nitrogen relative to The relative pressure of atmospheric pressure is accurately adjusted to 0.3 nitrogen helium mixed gas, by using the N2 adsorption BET 1 of gas flow method Point method is measured.The specific surface area found out using the measurement is defined as to the BET specific surface area of carbonaceous material in the present invention 1.

(6) micropore diameter is distributed

The micropore diameter distribution of carbonaceous material is found out by measurement mercury intrusion.By using mercury porosimeter (water Silver-colored plunging) it measures it is found that in carbonaceous material, draw by the particle internal pore of carbonaceous material, because particle surface is uneven Micropore caused by concave-convex and interparticle contact surface risen etc. is equivalent to the micropore that diameter is 0.01 μm~1 μm, carbonaceous material In preferably have following micropore diameters distribution: be usually 0.01cm³·g^-1It above, is preferably 0.05cm³·g^-1Above, more preferably 0.1cm³·g^-1More than, and usually 0.6cm³·g^-1It below, is preferably 0.4cm³·g^-1Below, it is more preferably 0.3cm³·g^-1 Below.

When micropore diameter distribution is more than above range, a large amount of adhesive may be needed when carrying out plates polarizing.Another party Face, if being lower than above range, may cause high current density charge-discharge characteristic reduces and can not obtain in charge and discharge The alleviation effects that electrode expansion is shunk.

In addition, found out using mercury porosimeter (mercury penetration method), diameter be equivalent to 0.01 μm~100 μm of micropore Micropore total measurement (volume) be usually 0.1cm³·g^-1It above, is preferably 0.25cm³·g^-1Above, it is more preferably 0.4cm³·g^-1With On, and usually 10cm³·g^-1It below, is preferably 5cm³·g^-1Below, it is more preferably 2cm³·g^-1Below.When micropore total measurement (volume) When more than above range, a large amount of adhesive may be needed when carrying out plates polarizing.On the other hand, if being lower than above range, It then may cause in the dispersion effect for carrying out being unable to reach thickener or binder when plates polarizing.

In addition, mean pore diameter is usually 0.05 μm or more, preferably 0.1 μm or more, more preferably 0.5 μm or more, and Usually 50 μm or less, preferably 20 μm or less, more preferably 10 μm or less.It, can when mean pore diameter is more than above range It can need a large amount of adhesive.On the other hand, if being lower than above range, it may cause high current density charge-discharge characteristic drop It is low.

Mercury intrusion is measured using following methods: using mercury void determination instrument (AutoPore9520, The manufacture of Micrometritics company) as the device for being used as mercury porosimeter.As pre-treatment, about 0.2g sample is enclosed In powder container, (50 μm of Hg or less) deaerate within 10 minutes in vacuum at room temperature.Then, it is decompressed to 4psia (about 28kPa), and import mercury, make pressure from 4psia (about 28kPa) is stage rise to 40000psia (about 280MPa) after, then drop To 25psia (about 170kPa).By in boost process number of stages be arranged at 80 grades or more, in each stage in, pass through 10 seconds Equilibration time after measure mercury intrusion.

Curve is pressed by the mercury obtained in said determination using Washburn formula and calculates micropore diameter distribution.This In, the surface tension (γ) of mercury is set as 485dynecm^-1(1dyne=10 μ N), contact angle (φ) are 140 °.It is average micro- Micropore diameter when aperture uses accumulation micro pore volume to reach 50%.

(7) circularity

When measuring spherical degree of the circularity to evaluate carbonaceous material, circular degree is within following ranges.It needs Illustrate, the definition of circularity following formula: the circularity=(week of the equivalent circular with area identical with particle projection of shape It is long)/(perimeter of particle projection of shape).When circularity is 1, become theoretical proper sphere.

Partial size is that the circularity of the particle of 3~40 μ ms is more ideal closer to 1, also, it is round in carbonaceous material Degree is preferably 0.1 or more, is wherein preferably 0.5 or more, is more preferably 0.8 or more, is more preferably 0.85 or more, especially excellent It is selected as 0.9 or more.

When circularity is bigger, high current density charge-discharge characteristic is more excellent.Thus, when circularity is lower than above range, The fillibility of negative electrode active material reduces, resistance increases between particle, may cause short time high current density charge-discharge characteristic drop It is low.

Circularity is measured using flow-type particle image analysis device (FPIA of Sysmex company manufacture).It will about The 0.2 weight % that 0.2g sample is dispersed in polyoxyethylene (20) Span-20 as surfactant is water-soluble In liquid (about 50mL), and after being irradiated 1 minute with the ultrasonic wave of 28kHz with the output power of 60W, specify 0.6~400 μm for detection Range, the particle to partial size in 3~40 μ ms are measured.The circularity found out using the measurement is defined as the present invention 1 The circularity of middle carbonaceous material.

The method for improving circularity is had no specifically limited, but is handled by implementing spheroidization and by particle convert spherical shape The shape for being applied to may be implemented inter-particle voids afterwards when electrode body is neat uniform, therefore preferably.Reality as spheroidization processing Example can be enumerated and be had by applying shearing force, compressing force come method mechanically close to spherical shape, using adhesive or particle itself Some adhesive force carries out machinery/physical treatment method of the granulation of multiple particles etc..

(8) real density

The real density of carbonaceous material is usually 1.4gcm^-3It above, is preferably 1.6gcm^-3Above, more preferably 1.8g·cm^-3Above, it is especially preferably 2.0gcm^-3More than, and usually 2.26gcm^-3Below.When real density is lower than upper When stating range, the crystallinity of carbon is too low, may cause the increase of initial stage irreversible capacity.It should be noted that above range is upper It is limited to the theoretical upper limit value of graphite real density.

The real density of carbonaceous material is measured by using the Liquid displacement methods (hydrometer method) of butanol.The survey will be utilized Surely the value found out is defined as the real density of carbonaceous material in the present invention 1.

(9) tap density

The tap density of carbonaceous material is usually 0.1gcm^-3It above, is preferably 0.5gcm^-3Above, more preferably 0.7g·cm^-3Above, it is especially preferably 1gcm^-3More than, and preferably 2gcm^-3Below, it is more preferably 1.8gcm^-3With Under, especially preferably 1.6gcm^-3Below.

If tap density is lower than above range, it is difficult to improve packed density when being used as cathode, may cause can not obtain Obtain the battery of high capacity.In addition, the inter-particle voids in electrode become very few, it is difficult to ensure particle when being more than above range Between electric conductivity, may cause can not obtain ideal battery behavior.

Tap density is measured by following methods: sample being made to drop into 20cm after the sieve by 300 μm of mesh³'s In jolt ramming container, until sample is filled to the upper surface of container, using powder density analyzer (for example, Seishin enterprise The Tap densor of company's manufacture) carry out the vibration that 1000 lengths of stroke are 10mm, by this time volume and sample weight ask Calculate tap density.The tap density calculated using the measurement is defined as to the tap density of carbonaceous material in the present invention 1.

(10) orientation ratio

The orientation ratio of carbonaceous material is usually 0.005 or more, preferably 0.01 or more, more preferably 0.015 or more, and logical It is often 0.67 or less.If orientation ratio is lower than above range, the reduction of high density charge-discharge characteristic may cause.It needs to illustrate It is that the upper limit of above range is the theoretical upper limit value of carbonaceous material orientation ratio.

Orientation ratio is to be measured after being press-formed to sample using X-ray diffraction.It is to be filled in 0.47g sample Diameter is in the molding machine of 17mm, in 58.8MNm^-2Lower compression obtains formed body, then fixes the formed body with clay, make its with The face of measurement sample frame is the same face, to carry out X-ray diffraction measure.By obtained carbon (110) diffraction with (004) peak intensity of diffraction calculates the ratio indicated with (110) diffraction peak intensity/(004) diffraction peak intensity.The survey will be utilized Surely the orientation ratio found out is defined as the orientation ratio of carbonaceous material in the present invention 1.

The determination condition of X-ray diffraction is as described below.Wherein, " 2 θ " represents the angle of diffraction.

Target: Cu (K alpha ray) graphite monochromatic photometer

Slit:

Divergent slit=0.5 degree

By optical slits=0.15mm

Scatter slit=0.5 degree

Measurement range and stepping angle/minute:

(110) face: 75 Dus≤2 1 degree of θ≤80 degree/60 seconds

(004) face: 52 Dus≤2 1 degree of θ≤57 degree/60 seconds

(11) draw ratio (powder)

The draw ratio of carbonaceous material is usually 1 or more, and usually 10 or less, preferably 8 or less, more preferably 5 or less. If draw ratio is more than above range, striped may be generated when carrying out plates polarizing, can not obtain uniform coated face, high electricity Current density charge-discharge characteristic reduces.It should be noted that the lower limit of above range is the theory lower bound value of carbonaceous material draw ratio.

The measurement of draw ratio is carried out and amplifying observation using particle of the scanning electron microscope to carbonaceous material.Selection is solid Any 50 graphite particles being scheduled on thick 50 microns of metal end faces below, rotation, inclination are fixed with the loading of these samples Platform measures the longest diameter A and perpendicular shortest diameter B of the carbonaceous material particle observed when carry out 3 is tieed up and observed respectively, and Find out the average value of A/B.The draw ratio (A/B) found out using the measurement is defined as to the draw ratio of carbonaceous material in the present invention 1.

(12) auxiliary material mixes

So-called auxiliary material mixing, refers to different containing two or more property in negative electrode and/or in negative electrode active material Carbonaceous material.The property therein refers to: selected from X-ray diffraction parameter, median particle diameter, draw ratio, BET specific surface area, taking To than one or more of, Raman R value, tap density, real density, micropore distribution, circularity, ash amount characteristic.

As the particularly preferred example of above-mentioned auxiliary material mixing, can enumerate: volume reference size distribution is with intermediate value grain Diameter is left-right asymmetry when being center, contains the different carbonaceous material of two or more Raman R value and X-ray parameter difference etc..

It as one of the example of effect of auxiliary material mixing, can enumerate: by containing graphite such as natural graphite, artificial graphites The carbonaceous materials such as the amorphous carbon such as the carbon blacks such as (graphite), acetylene black, needle coke can enable resistance to drop as conductive material It is low.

When hybrid conductive material is mixed as auxiliary material, a kind can be individually mixed, it can also in any combination and ratio Mix two or more.In addition, the mixing ratio of conductive material and carbonaceous material is usually 0.1 weight % or more, preferably 0.5 weight % or more, more preferably 0.6 weight % or more are measured, and usually 45 weight % or less, preferably 40 weight % or less.If mixed Composition and division in a proportion is lower than above range, then may cause and be difficult to obtain the effect for improving electric conductivity.In addition, if it exceeds above range, then It may cause the increase of initial stage irreversible capacity.

(13) electrode fabrication

In the range of not significantly limiting the effect of the present invention 1, electrode can be prepared using any known method.Example Such as, can by into negative electrode active material add adhesive, solvent, as needed and add thickener, conductive material, fill out Fill material etc., slurry be made, and be coated on the current collector, it is dry after suppressed to form electrode.

Battery close on nonaqueous electrolytic solution injection process before stage, negative electrode active material layer on each face on battery Thickness be usually 15 μm or more, preferably 20 μm or more, more preferably 30 μm or more, and usually 150 μm or less, be preferably 120 μm or less, more preferably 100 μm or less.The thickness of negative electrode active material is if it exceeds the range, then due to nonaqueous electrolytic solution It is difficult to be impregnated near current collection body interface, it is thus possible to lead to the reduction of high current density charge-discharge characteristic.On the other hand, if it is low In the range, then the volume ratio that may cause collector and negative electrode active material increases, and battery capacity is reduced.Furthermore it is possible to will Negative electrode active material carries out roller molding and makes mosaic electrode to make pellet electrode, or by compression forming.

(14) collector

As the collector that negative electrode active material can be made to be maintained, well known collector can be arbitrarily used.As negative The collector of pole, it can be mentioned, for example the metal materials such as copper, nickel, stainless steel, nickel-plated steel, examine in terms of processing simplification and cost Consider, particularly preferred copper.

In addition, the shape as collector, when collector is metal material, it can be mentioned, for example metal foil, metal cylinder, Wire coil, metal plate, metallic film, expansion alloy, perforated metal, foaming metal etc..Wherein, preferred metallic film, more excellent Copper foil is selected, the obtained rolled copper foil of rolling process and the electrolytic copper foil obtained using electrolysis method is further preferably utilized, appoints among the above One can be used as collector use.

In addition, copper alloy (phosphor bronze, titanium copper, section that intensity is higher than fine copper can be used when copper thickness is less than 25 μm Gloomy alloy, Cu-Cr-Zr alloy etc.).

In the collector being made of the copper foil made using rolling process, arranged since copper is crystallized along rolling direction, because Even if this is at an acute angle by cathode crimping very close or curling, still it is not easily broken, is applicable to small cylinder shape battery.

Electrolytic copper foil is obtained by following methods: for example: metal drum is immersed in the non-water power dissolved with copper ion It solves in liquid, galvanization while rotating the drum, so that copper is precipitated on drum surface, is removed to obtain electrolytic copper foil.May be used also Copper is precipitated on above-mentioned rolled copper foil surface using electrolysis method.The one or both sides of copper foil can also be roughened Or surface treatment (for example, thickness is in base treatments such as the chromic acid salt treatment of several nm~1 μm or so, Ti etc.).

Current collection structure base board further preferably has following physical property.

(14-1) average surface roughness (Ra)

The negative electrode active material film forming face of current collection structure base board specified in the method recorded for JISB0601-1994 Average surface roughness (Ra) be not particularly limited, usually 0.05 μm or more, preferably 0.1 μm or more, be more preferably 0.15 μm or more, and usually 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.0 μm or less.This is because: when collection The average surface roughness (Ra) of electric structure base board within the above range when, it can be expected that good charge/discharge cycle characteristics；Also, with The interfacial area of negative electrode active material film becomes larger, and improves with the adhesiveness of negative electrode active material film.It should be noted that right Had no in the upper limit value of average surface roughness (Ra) it is specifically limited, when average surface roughness (Ra) is more than 1.5 μm, usually It is difficult to obtain the foil that thickness is practical when using as battery, therefore generallys use 1.5 μm of average surface roughness (Ra) below.

(14-2) tensile strength

So-called tensile strength, refer to when test film is broken required maximum pull divided by the sectional area of test film and Obtained value.Tensile strength in the present invention 1 is using identical with the record of JISZ2241 (material during tensile test method) Device and method measurement.

The tensile strength of current collection structure base board is not particularly limited, usually 100Nmm^-2More than, preferably 250N mm^-2More than, more preferably 400Nmm^-2More than, especially preferably 500Nmm^-2More than.The the value of tensile strength the high then more It is preferred that, it is contemplated that industrial accessibility, usually 1000Nmm^-2Below.If it is the high current collection structure base board of tensile strength, then It can inhibit the cracking of the current collection structure base board as caused by negative electrode active material film expansion/contraction in charge/discharge process, It is hereby achieved that good cycle characteristics.

(14-3) 0.2% yield strength

So-called 0.2% yield strength refers to that the plasticity for generating 0.2% is (permanent) and strains necessary payload size, applies After the load of the size, even if still keeping 0.2% deformation except unloading.0.2% yield strength utilizes and measurement tensile strength Identical device and method measurement.

Specifically limited, usually 30Nmm is had no for 0.2% yield strength of current collection structure base board^-2Above, preferably 150N·mm^-2Above, it is especially preferably 300Nmm^-2More than.The the value of 0.2% yield strength the high then more preferred, from industry The angle of accessibility is set out, it is often preferred that 900Nmm^-2Below.If it is the high current collection structure base board of 0.2% yield strength, The modeling of the current collection structure base board as caused by negative electrode active material film expansion/contraction in charge/discharge process can then be inhibited Property deformation, it is hereby achieved that good cycle characteristics.

The thickness of (14-4) collector

Collector can be any thickness, but usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and Usually 1mm or less, preferably 100 μm or less, more preferably 50 μm or less.When the thickness of metal epithelium is less than 1 μm, due to Intensity decline, thus may cause coating and become difficult.In addition, then may cause the electricity of winding etc. when thickness is greater than 100 μm Pole shape deforms.It should be noted that collector can be it is netted.

(15) thickness of collector and negative electrode active material layer ratio

The thickness ratio of collector and negative electrode active material layer is had no it is specifically limited, but " (closing on nonaqueous electrolytic solution note The thickness of the negative electrode active material layer on single face before entering)/(thickness of collector) " value be preferably 150 or less, it is more excellent 20 or less, especially preferably 10 are selected as hereinafter, and preferably 0.1 or more, more preferably 0.4 or more, especially preferably 1 or more.

If the thickness of collector and negative electrode active material layer ratio is more than above range, in high current density charge and discharge When, collector may cause heat release because of Joule heat.In addition, collector is relative to negative when thickness ratio is lower than above range The volume ratio of pole active material increases, and may cause battery capacity reduction.

(16) electrode density

Electrode structure when negative electrode active material to be made to electrode is not particularly limited, is present in negative on collector The density of pole active material is preferably 1gcm^-3Above, it is more preferably 1.2gcm^-3Above, it is especially preferably 1.3gcm^-3 More than, and preferably 2gcm^-3Below, it is more preferably 1.9gcm^-3It below, is more preferably 1.8gcm^-3Below, especially It is preferably 1.7gcm^-3Below.When the density for the negative electrode active material being present on collector is more than above range, cathode Active material particle will receive destruction, cause the increase of initial stage irreversible capacity, nonaqueous electrolytic solution in collector/negative electrode active material Impregnability near interface reduces, and then high current density charge-discharge characteristic is caused to deteriorate.In addition, if being lower than above-mentioned model It encloses, then the electric conductivity that may cause between negative electrode active material reduces, and cell resistance increases, and the capacity of unit volume reduces.

(17) adhesive

It is used as the adhesive of bonding negative electrode active material, when as long as being manufactured relative to nonaqueous electrolytic solution and electrode The material of solvent-stable, then be not particularly limited.

As specific example, polyethylene, polypropylene, polyethylene terephthalate, poly-methyl methacrylate can be enumerated The resinaes macromolecule such as ester, aromatic polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), isoprene rubber, fourth The rubber-like macromolecules such as diene rubber, fluorubber, NBR (nitrile rubber), EP rubbers；S-B-S block Copolymer or its hydride；EPDM (ethylene/propylene/diene terpolymer), styrene ethylene butadiene-styrene are total The thermoplastic elastomer (TPE)s shape macromolecule such as polymers, styrene-isoprene-styrene block copolymer or its hydride；Between advise it is vertical The soft resins such as structure 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers Shape macromolecule；The fluorine class high scores such as Kynoar, polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer Son；The polymeric composition etc. with ionic conductivity of alkali metal containing ion (especially lithium ion).Above-mentioned material can be single 1 kind is solely used, it can also in any combination and two or more is applied in combination in ratio.

As the solvent for being used to form slurry, as long as negative electrode active material, adhesive, Yi Jigen can be dissolved or be dispersed The solvent of the thickener and conductive material that use according to needs is not particularly limited its type, can be used aqueous molten Any one of agent or organic solvent.

As the example of aqueous solvent, water, alcohol etc. can be enumerated；As the example of organic solvent, N- methyl pyrrole can be enumerated Pyrrolidone (NMP), dimethylformamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl Base triamine, N, N- dimethylamino propylamine, tetrahydrofuran (THF), toluene, acetone, ether, hexamethyl phosphoramide, dimethyl sulfoxide, Benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc..

In particular, preferably making while using thickener wherein containing dispersing agent etc., and adopt when using aqueous solvent It is carried out with latex such as SBR slurried.It, can also in any combination and ratio combination makes in addition, above-mentioned solvent can be used alone a kind Use two or more.

Adhesive relative to the ratio of negative electrode active material be preferably 0.1 weight % or more, more preferably 0.5 weight % with Upper, especially preferably 0.6 weight % or more, and it is preferably 20 weight % or less, more preferably 15 weight % or less, further excellent It is selected as 10 weight % or less, especially preferably 8 weight % or less.If adhesive is more than relative to the ratio of negative electrode active material Above range does not then have the ratio of contributive adhesive to increase battery capacity in amount of binder, may cause battery capacity drop It is low.In addition, may cause the strength reduction of negative electrode when being lower than above range.

In particular, adhesive is living relative to cathode when in main component containing using SBR as the rubber-like macromolecule of representative Property substance ratio be usually 0.1 weight % or more, preferably 0.5 weight % or more, more preferably 0.6 weight % or more, and Usually 5 weight % or less, preferably 3 weight % or less, more preferably 2 weight % or less.

In addition, when in main component containing using Kynoar as the fluorine class macromolecule of representative, it is living relative to cathode Property substance ratio be usually 1 weight % or more, preferably 2 weight % or more, more preferably 3 weight % or more, and be usually 15 weight % or less, preferably 10 weight % or less, more preferably 8 weight % or less.

Thickener is commonly used in adjusting the viscosity of slurry.As thickener, have no it is specifically limited, it is specific enumerable: carboxylic first Base cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, enzyme egg Their salt etc. of bletilla.Above-mentioned thickener can be used alone, can also in any combination and ratio be applied in combination 2 kinds with On.

In addition, when using thickener, thickener relative to the ratio of negative electrode active material be usually 0.1 weight % with Upper, preferably 0.5 weight % or more, more preferably 0.6 weight % or more, and usually 5 weight % or less, preferably 3 weights Measure % or less, more preferably 2 weight % or less.If thickener is lower than above range relative to the ratio of negative electrode active material, It then may cause the significant decrease of coating.On the other hand, when being more than above range, negative electrode active in negative electrode active material layer The decline of ratio shared by substance, the resistance that may cause between the problem of battery capacity reduces and negative electrode active material increase.

(18) pole plate orientation ratio

Pole plate orientation ratio is usually 0.001 or more, preferably 0.005 or more, more preferably 0.01 or more, and is usually 0.67 or less.If pole plate orientation ratio is lower than above range, the reduction of high density charge-discharge characteristic may cause.It needs to illustrate It is that the upper limit of above range is the theoretical upper limit value of carbonaceous material pole plate orientation ratio.

The measurement of pole plate orientation ratio carries out by the following method: negative electrode being suppressed to target density, is spread out using X-ray Penetrate the negative electrode active material orientation ratio of the electrode of measurement at this time.Specific method is not particularly limited, as standard method, is adopted Use asymmetric Pearson (ピ ア ソ Application) VII as distribution (profile) function, to (110) of the carbon obtained by X-ray diffraction Diffraction maximum and (004) diffraction maximum are fitted, and thus carry out peak separation, are spread out to calculate separately (110) diffraction maximum and (004) Penetrate the integrated intensity at peak.It is calculated by resulting integrated intensity with (110) diffraction integral intensity/(004) diffraction integral intensity table The ratio shown.The negative electrode active material orientation ratio of the electrode found out using the measurement is defined as by carbonaceous material in the present invention 1 The pole plate orientation ratio of the electrode of formation.

X-ray diffraction measure condition is as described below.Wherein, " 2 θ " represents the angle of diffraction.

Target: Cu (K alpha ray) graphite monochromatic photometer

Slit:

Divergent slit=1 degree

By optical slits=0.1mm

Scatter slit=1 degree

Measurement range and stepping angle/minute:

(110) face: 76.5 Dus≤2 0.01 degree of θ≤78.5 degree/3 seconds

(004) face: 53.5 Dus≤2 0.01 degree of θ≤56.0 degree/3 seconds

Sample preparation: electrode is fixed on a glass with the double faced adhesive tape of 0.1mm thickness

< 2-3-3. metal compound species material and used metal compound species material cathode structure, physical property, system Preparation Method >

As the metal compound species material for being used as negative electrode active material, as long as energy occlusion/releasing lithium, can be to be formed Metal simple-substance or alloy or their oxide, carbide, nitride, silicide, sulfide, phosphide of lithium alloy etc. are changed Any materials in object are closed, are had no specifically limited.As the metallic compound, can enumerate containing Ag, Al, Ba, Bi, Cu, Ga, The compound of the metals such as Ge, In, Ni, P, Pb, Sb, Si, Sn, Sr, Zn.Wherein, metal simple-substance or the conjunction of lithium alloy are preferably formed as Gold preferably comprises the 13rd race and the 14th race's metal/metalloid element (that is, in addition to carbon) material, more preferable silicon (Si), tin (Sn) or lead (Pb) (hereinafter, sometimes by this 3 kinds of elements be known as " special metal element ") metal simple-substance or include these atoms Alloy or these metals (special metal element) compound.Above-mentioned material can be used alone, can also be to appoint Two or more is applied in combination in meaning combination and ratio.

As the example of the negative electrode active material with atom at least one kind of in special metal element, it can enumerate and appoint Anticipate a kind of special metal element metal simple-substance, be made of two or more special metal element alloy, by one kind or two or more spy The alloy and contain one kind or two or more special metal member that metallic element and other one kind or two or more metallic elements are constituted The Composite of plain oxide, carbide, nitride, silicide, sulfide, the phosphide of compound or the compound etc. Close object.As negative electrode active material, the Gao Rong of battery can be realized by using these metal simple-substances, alloy or metallic compound Quantization.

In addition, the example as above-mentioned complex chemical compound, can also enumerate and metal simple-substance, alloy or nonmetalloid The compound of equal multiple elements complex combination.More specifically, such as silicon or tin, can be used these elements and can not send out as cathode Wave the alloy of the metal of effect.In addition, such as tin, can be used through combination tin and can be used as cathode performance work in addition to silicon The metal used and can not as obtained from the metal and nonmetalloid that cathode plays a role containing 5~6 kinds of elements Complex compound.

In above-mentioned negative electrode active material, metal simple-substance, two or more special metal of preferably wantonly a kind of special metal element The alloy of element, the oxide of special metal element, carbide or nitride etc., this is because their every lists when battery is made The capacity of position weight is larger, and considers the capacity and the load caused by environment, particularly preferred silicon and/or tin of per unit weight Metal simple-substance, alloy, oxide, carbide or nitride etc..

In addition, when using metal simple-substance or alloy, although the capacity of per unit weight is deteriorated, since cycle characteristics is excellent It is different, thus still preferably comprise following compounds of silicon and/or tin.

" oxide of silicon and/or tin ", wherein the element ratio of silicon and/or tin and oxygen is usually 0.5 or more, is preferably 0.7 or more, be more preferably 0.9 or more, and usually 1.5 or less, preferably 1.3 or less, more preferably 1.1 or less.

" nitride of silicon and/or tin ", wherein the element ratio of silicon and/or tin and nitrogen is usually 0.5 or more, is preferably 0.7 or more, be more preferably 0.9 or more, and usually 1.5 or less, preferably 1.3 or less, more preferably 1.1 or less.

" carbide of silicon and/or tin ", wherein the element ratio of silicon and/or tin and carbon is usually 0.5 or more, is preferably 0.7 or more, be more preferably 0.9 or more, and usually 1.5 or less, preferably 1.3 or less, more preferably 1.1 or less.

It, can also in any combination and ratio group it should be noted that above-mentioned negative electrode active material can be used alone wantonly a kind It closes and uses two or more.

Well known any means preparation can be used in cathode in the non-aqueous electrolyte secondary battery of the present invention 1.Specifically, As the manufacturing method of cathode, it can be mentioned, for example: binder and conductive material etc. are added in Xiang Shangshu negative electrode active material, then right The method that obtained material directly carries out roller molding pellet electrode is made；The side of mosaic electrode is made up of compression forming Method.But generally use be using the methods of rubbing method, vapour deposition method, sputtering method, plating cathode collector (hereinafter, Be called " negative electrode collector ") on formed containing above-mentioned negative electrode active material film layer (negative electrode active material layer) method. At this point, binder, thickener, conductive material, solvent etc. are added into above-mentioned negative electrode active material, be made pulp-like, then by its It is coated on negative electrode collector and dry, is then suppressed so that its densification, bears to be formed on negative electrode collector Pole active material layer.

As the material of negative electrode collector, steel, copper alloy, nickel, nickel alloy, stainless steel etc. can be enumerated.In these materials, In view of being easily processed into film and cost aspect, preferably copper foil.

The thickness of negative electrode collector is usually 1 μm or more, preferably 5 μm or more, and usually 100 μm or less, be preferably 50 μm or less.If the thickness of negative electrode collector is blocked up, the capacity of entire battery may become too low, whereas if it is excessively thin, It then may cause operating difficulties.

It should be pointed out that in order to which the bond effect for the negative electrode active material layer for forming surface is improved, preferably in advance First the surface of above-mentioned negative electrode collector is roughened.As the method for surface roughening, following methods can be enumerated: spray Sand processing, is rolled using rough surface roller, be fixed with the abrasive cloth paper of abrasive particle, sandstone, Carborundum wheel, with steel Mechanical milling method, electrolytic polishing method, chemical grinding method that wire brush of line etc. etc. grinds collector surface etc..

In addition, can also make to reduce the weight of negative electrode collector to improve the energy density of battery per unit weight With the negative electrode collector of the open-cells such as expansion alloy or perforated metal.Such negative electrode collector can also be by changing it Aperture opening ratio carrys out any change weight.In addition, when forming negative electrode active material layer on the two sides of such negative electrode collector, Due to there is the anchoring effect for running through the hole, negative electrode active material layer can be made to be more difficult peeling-off.But if aperture opening ratio mistake Height, it will cause the contacts area between negative electrode active material layer and negative electrode collector to become smaller, and may instead result in adhesion strength It reduces.

The slurry of negative electrode active material layer is used to form usually ands adding binder, thickener etc. into negative electrode material It is made.Exist it should be noted that " negative electrode material " described in this specification refers to including negative electrode active material and conductive material Interior material.

Content of the negative electrode active material in negative electrode material be usually 70 weight % or more, especially preferably 75 weight % with On, and usually 97 weight % or less, especially preferably 95 weight % or less.It, can when the content of negative electrode active material is very few The capacity for the secondary cell for having used cathode obtained can be caused to tend to be insufficient；If content is excessive, due to that can cause to glue The content relative deficiency for tying agent etc., the intensity that may cause obtained cathode tend to be insufficient.It should be noted that when combination makes When with two or more negative electrode active material, as long as meeting the above range the total amount of negative electrode active material.

As the conductive material for cathode, the metal materials such as copper, nickel can be enumerated；Carbon materials such as graphite, carbon black etc..These Conductive material can be used alone, can also in any combination and two or more is applied in combination in ratio.In particular, when using carbon When material is as conductive material, since carbon material can also play the effect of active material, preferably.Leading in negative electrode material The content of electric material be usually 3 weight % or more, particularly preferably 5 weight % or more, and usually 30 weight % or less, especially Preferably 25 weight % or less.If conductive material content is very few, it may cause electric conductivity and tend to be insufficient, when excessive, due to It can make the content relative deficiency of negative electrode active material etc., thus may cause battery capacity and intensity has a declining tendency.It needs Illustrate, when conductive material of more than two kinds is applied in combination, as long as meeting the above range the total amount of conductive material.

As the binder for cathode, as long as to the material of the solvent and electrolyte safety that are used when manufacturing electrode , arbitrary binder can be used.Such as it can enumerate: Kynoar, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, butylbenzene Rubber, isoprene rubber, butadiene rubber, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer etc..It is above-mentioned viscous Knot agent can be used alone, can also in any combination and two or more is applied in combination in ratio.Relative to 100 weight of negative electrode material Measure part, the content of binder is usually 0.5 parts by weight or more, particularly preferably more than 1 parts by weight, and usually 10 parts by weight with Under, particularly preferably below 8 parts by weight.If the content of binder is very few, the intensity that may cause obtained cathode becomes In deficiency, when excessive, due to the content relative deficiency of negative electrode active material etc., it may cause battery capacity and electric conductivity tend to not Foot.It should be noted that when two or more binder is applied in combination, as long as meeting the above range the total amount of binder.

As the thickener for cathode, carboxymethyl cellulose, methylcellulose, hydroxymethyl cellulose, ethyl can be enumerated Cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein etc..These thickeners can be used alone, can also be with In any combination and two or more is applied in combination in ratio.Thickener can according to need and use, when using thickener, thickener Content in negative electrode active material layer is preferably generally the range of 0.5 weight of weight %~5 %.

The slurry for being used to form negative electrode active material layer can be by mixing required conduction into above-mentioned negative electrode active material Material and binder, thickener, and be formulated using aqueous solvent or organic solvent as decentralized medium.As aqueous solvent, Usually using water, but can also be the alcohols such as ethyl alcohol or N- first is applied in combination relative to the ratio that water is the left and right 30 weight % or less Other solvents than water such as cyclic amides such as base pyrrolidones.In addition, can usually enumerate N- methyl as organic solvent The cyclic amides such as pyrrolidones；The straight-chains amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide；Methyl phenyl ethers anisole, The arenes such as toluene, dimethylbenzene；The alcohols such as butanol, cyclohexanol.Wherein, preferred cyclic amides such as N-Methyl pyrrolidone； Straight-chains amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide etc..Wherein, above-mentioned solvent can be used alone any Kind, can also in any combination and two or more is applied in combination in ratio.

As long as the viscosity of slurry reaches the viscosity that can be coated on collector, have no specifically limited.As can apply The viscosity of cloth, can be by changing solvent usage etc. when preparing slurry come appropriate adjustment.

Obtained slurry is coated on above-mentioned negative electrode collector and after drying, forms cathode by being suppressed Active material layer.The method of coating is had no specifically limited, itself known method can be used.For dry method Also it is not particularly limited, the known methods such as natural drying, heat drying can be used, be dried under reduced pressure.

Electrode structure when negative electrode active material to be made up to electrode of the above method is not particularly limited, but is existed In the density of the active material on collector be preferably 1gcm^-3Above, it is more preferably 1.2gcm^-3Above, especially preferably 1.3g·cm^-3More than, and preferably 2gcm^-3Below, it is more preferably 1.9gcm^-3It below, is more preferably 1.8g cm^-3Below, it is especially preferably 1.7gcm^-3Below.

It is more than above range if there is the density in the active material on collector, then active material particle will receive brokenly It is bad, it may cause the impregnability of the increase of initial stage irreversible capacity and nonaqueous electrolytic solution near collector/reactive species interface It reduces, and then high current density charge-discharge characteristic is caused to deteriorate.On the other hand, if being lower than above range, it may cause activity Electric conductivity between substance reduces, cell resistance increases, and the capacity of unit volume reduces.

The knot of < 2-3-4. lithium metal composite oxide material and the cathode using lithium metal composite oxide material Structure, physical property, preparation method >

As the lithium metal composite oxide material for being used as negative electrode active material, as long as energy occlusion/releasing lithium, does not have It is specifically limited, but the lithium-contained composite metal oxide material of titanium is preferably comprised, the composite oxides of particularly preferred lithium and titanium are (following Referred to as " lithium-titanium composite oxide ").That is, sharp brilliant containing having in anode for nonaqueous electrolyte secondary battery active material when making When the lithium-titanium composite oxide of stone structure, output resistance can decline to a great extent, thus particularly preferably.

It is also preferable to the lithium or titanium in lithium-titanium composite oxide be by other metallic elements, for example, selected from Na, K, Co, Al, Composite oxides obtained from least one kind of element in Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb replaces.

Above-mentioned metal oxide is the lithium-titanium composite oxide indicated with general formula (5), meet in the general formula (5) 0.7≤x≤ 1.5, when 1.5≤y≤2.3,0≤z≤1.6, stable structure of the lithium ion in doping/dedoping, therefore preferably.

Li_xTi_yM_zO₄ (5)

[in general formula (5), M represents at least one kind of in Na, K, Co, Al, Fe, Ti, Mg, Cr, Ga, Cu, Zn and Nb Element.]

In the composition represented by above-mentioned general formula (5), following (a), (b), (c) structure battery performance can obtain well Balance, therefore particularly preferably.

(a) 1.2≤x≤1.4,1.5≤y≤1.7, z=0

(b) 0.9≤x≤1.1,1.9≤y≤2.1, z=0

(c) 0.7≤x≤0.9,2.1≤y≤2.3, z=0

It as typical composition particularly preferred in above compound, can be listed below: be Li in (a)_4/3Ti_5/3O₄、(b) In be Li₁Ti₂O₄, be Li in (c)_4/5Ti_11/5O₄.In addition, it can be mentioned, for example Li for the structure of Z ≠ 0_4/3Ti_4/3Al_1/3O₄Make To preferably constitute.

It is used as the lithium-titanium composite oxide of negative electrode active material in the present invention 1 other than above-mentioned requirements to be met, it is also excellent Select at least one kind of in the features such as physical property and shape described in further satisfaction following (1)~(13), particularly preferred satisfaction 2 simultaneously Kind or more.

(1) BET specific surface area

The value of the BET specific surface area of lithium-titanium composite oxide measured using BET method, as negative electrode active material is preferred For 0.5m²·g^-1Above, it is more preferably 0.7m²·g^-1It above, is more preferably 1.0m²·g^-1Above, especially preferably 1.5m²·g^-1More than, and preferably 200m²·g^-1Below, it is more preferably 100m²·g^-1It below, is more preferably 50m²·g^-1Below, it is especially preferably 25m²·g^-1Below.

If BET specific surface area is lower than above range, reacted when being used as negative electrode material with what nonaqueous electrolytic solution was in contact Area reduces, and may cause output resistance increase.When on the other hand, more than above range, titanium-containing metal oxide can be caused Plane of crystal and end face part increase, and thus cause crystal defect (askew), and then will lead to irreversible capacity and become to neglect Depending on so that ideal battery can not be obtained.

Carried out as follows using when BET method measurement the specific area: using surface area meter (Okura development make it is complete from Dynamic surface area determination unit), after carrying out predrying in 15 minutes to sample at nitrogen stream, 350 DEG C, using nitrogen relative to atmosphere The relative pressure of pressure is accurately adjusted to 0.3 nitrogen helium mixed gas, by using 1 method of N2 adsorption BET of gas flow method It is measured.The specific surface area found out using the measurement is defined as to the BET specific surface of lithium-titanium composite oxide in the present invention 1 Product.

(2) volume-based average particle size

It is compound that the average grain diameter (median particle diameter) of the volume reference measured using laser diffraction/scattering method is defined as lithium titanium The volume-based average particle size of oxide (the case where forming secondary for primary particle agglomeration is secondary particle size).

The volume-based average particle size of lithium-titanium composite oxide is usually 0.1 μm or more, is preferably 0.5 μm or more, more excellent It is selected as 0.7 μm or more, and usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less, especially preferably 25 μm Below.

Volume-based average particle size is measured using following methods: being dispersed in lithium-titanium composite oxide living as surface Property agent polyoxyethylene (20) Span-20 0.2 weight % aqueous solution (about 10mL) in, and utilize laser Diffraction/scattering formula particle size distribution meter (LA-700 of Ku Chang manufacturing company manufacture) is measured.By what is found out by the measurement Median particle diameter is defined as the volume-based average particle size of carbonaceous material in the present invention 1.

If the volume average particle size of lithium-titanium composite oxide is lower than above range, needed when preparing electrode a large amount of viscous Agent is tied, as a result, may cause battery capacity reduction.When on the other hand, more than above range, when preparing electrode pad, hold Non-uniform applicator surface is easily formed, on battery preparation section not preferably.

(3) primary particle average grain diameter

In the case where primary particle agglomeration forms secondary, the primary particle average grain diameter of lithium-titanium composite oxide is logical It is often 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.1 μm or more, especially preferably 0.2 μm or more, and usually It is 2 μm or less, preferably 1.6 μm or less, more preferably 1.3 μm or less, especially preferably 1 μm or less.If at the beginning of volume reference Grade average particle size is more than above range, then is difficult to the glomerate secondary of shape, brings adverse effect to powder fillibility, Or specific surface area reduces, and thus may cause the reduction of the battery performances such as output characteristics.In addition, if volume reference primary particle is flat Equal partial size is lower than above range, then due to usually crystallizing not exclusively, thus may cause the secondary electricity such as poorly reversible of charge and discharge The problem of pond performance declines.

It should be noted that primary particle diameter is measured by being observed using scanning electron microscope (SEM).Specifically, It confirms under the multiplying power of particle, in the photo that for example multiplying power is 10000~100000 times, for arbitrary 50 primary grains Son, finds out the greatest length of intercept obtained by the left bounding lines straight line relative to horizontal direction of primary particle, then is averaged and Find out primary particle average grain diameter.

(4) shape

The shape of particle of lithium-titanium composite oxide can be used the bulk used in the past, polyhedral, it is spherical, oval it is spherical, Plate, needle-shaped, column etc., wherein preferred primary particle agglomeration forms secondary, and secondary be preferably shaped to it is spherical Or it is oval spherical.

In general, electrochemical element, with charge and discharge process, the active material in electrode can expand contraction, therefore, It is easy to cause the deterioration of the destruction of active material and conductive on-off etc. in the presence of the stress.As a result, with there is only primary grains The case where single particle active material of son is compared, and preferably primary particle agglomeration forms secondary, this is because, being formed secondary When particle, dilation stress is mitigated, and can prevent from deteriorating.

In addition, compared with the isometric orientation particle of plate, the case where more preferably spherical or oval spherical particle, this be by In, orientation of the spherical or oval spherical particle in electrode moulding is weaker, and the dilation of electrode is also less when charge and discharge, and The also uniform mixing easy to accomplish when carrying out the mixing with conductive material when preparing electrode.

(5) tap density

The tap density of lithium-titanium composite oxide is preferably 0.05gcm^-3Above, it is more preferably 0.1gcm^-3Above, Further preferably 0.2gcm^-3Above, it is especially preferably 0.4gcm^-3More than, and preferably 2.8gcm^-3Below, more excellent It is selected as 2.4gcm^-3Below, it is especially preferably 2gcm^-3Below.If tap density is lower than above range, it is used as When cathode, packed density is difficult to improve, and interparticle contact area is reduced, thus may cause interparticle resistance and increase, Output resistance increases.In addition, interparticle gap is very few in electrode when being more than above range, the flow path of nonaqueous electrolytic solution is reduced, Thus it may cause output resistance increase.

Tap density can be measured by following methods: sample being made to drop into 20cm after the sieve by 300 μm of mesh³ Jolt ramming container in, until sample is filled to the upper surface of container, then using powder density analyzer (for example, Seishin is looked forward to The Tap densor of industry company manufacture) vibration that 1000 lengths of stroke are 10mm is carried out, by the weight of volume and sample at this time Amount finds out density.The tap density calculated using the measurement is defined as to the tap density of lithium-titanium composite oxide in the present invention 1.

(6) circularity

When measuring spherical degree of the circularity as lithium-titanium composite oxide, circular degree is within following ranges. Circularity following formula definition: circularity=(perimeter with equivalent circular of the same area with particle projection of shape)/(particle projection The perimeter of shape).When circularity is 1, become theoretical proper sphere.

The circularity of lithium-titanium composite oxide closer to 1 then more preferably, usually 0.10 or more, preferably 0.80 with Upper, more preferably 0.85 or more, especially preferably 0.90 or more.The more big then high current density charge-discharge characteristic of circularity is higher. Thus, when circularity is lower than above range, the fillibility decline of negative electrode active material, interparticle resistance increase, and may lead Short time high current density charge-discharge characteristic is caused to reduce.

Circularity is by using flow-type particle image analysis device (for example, what Sysmex Industrial company manufactured FPIA it) is measured.About 0.2g sample is dispersed in polyoxyethylene (20) sorbitan list laurel as surfactant In 0.2 weight % aqueous solution (about 50mL) of acid esters, and after being irradiated 1 minute with the ultrasonic wave of 28kHz with the output power of 60W, Specified 0.6~400 μm is detection range, and the particle to partial size in 3~40 μ ms is measured.By what is found out using the measurement Circularity is defined as the circularity of lithium-titanium composite oxide in the present invention 1.

(7) draw ratio

The draw ratio of lithium-titanium composite oxide is usually 1 or more, and usually 5 or less, preferably 4 or less, more preferably 3 Below, 2 or less are especially preferably.When draw ratio is more than above range, striped may be generated when pole plate is made, can not be obtained Uniform coated face is obtained, the reduction of short time high current density charge-discharge characteristic is caused.It should be noted that the lower limit of above range For the theory lower bound value of the draw ratio of lithium-titanium composite oxide.

Draw ratio amplifies observation to lithium-titanium composite oxide particle to measure by using scanning electron microscope.Selection is fixed Any 50 particles on thick 50 μm of metal end faces below, rotation, inclination are fixed with the objective table of sample, measure respectively The longest diameter A and perpendicular shortest diameter B of particle when 3 dimension observation, and find out the average value of A/B.It will be found out using the measurement Draw ratio (A/B) be defined as the present invention 1 in lithium-titanium composite oxide draw ratio.

(8) preparation method of negative electrode active material

As the preparation method of lithium-titanium composite oxide, as long as having no spy in the range of without departing from the main points of the present invention 1 Different limitation, can enumerate several method.As the manufacturing method of inorganic compound, usual way can be used.

For example, can enumerate the titanium materials such as titanium oxide substance, as needed and the raw material of other elements that uses and LiOH、Li₂CO₃、LiNO₃The equal source Li uniformly mixes and is sintered the method to obtain active material at high temperature.

In particular, it is contemplated that various methods prepare spherical or oval spherical active material.It, can as an example therein Enumerate following methods: by the titanium materials such as titanium oxide substance and the as needed dissolution of the raw material of other elements for using or powder It is broken to be scattered in water equal solvent, pH value is adjusted while being stirred, and is made and is collected spherical precursor, as needed by it It is dry, LiOH, Li is then added₂CO₃、LiNO₃The equal source Li, and be sintered at high temperature, thus the method for obtaining active material.

In addition, as another example, following methods can be enumerated: by the titanium materials such as titanium oxide substance and as needed and use Other elements raw material dissolution or grinding dispersion in water equal solvent, be dried molding using spray dryer etc., Spherical or oval spherical precursor is made, LiOH, Li are added thereto₂CO₃、LiNO₃The equal source Li, and be sintered at high temperature, thus The method for obtaining active material.

Alternatively method can also enumerate following methods: by the titanium materials such as titanium oxide substance, LiOH, Li₂CO₃、 LiNO₃The equal source Li and as needed and the raw material dissolution of other elements used or grinding dispersion in water equal solvent, benefit It is dried molding with spray dryer etc., spherical or oval spherical precursor is made, it is sintered at high temperature, to obtain The method of active material.

In addition, in above-mentioned operation, can also in the metal oxide structures of titaniferous and/or with phase containing titanyl compound There are other elements other than Ti in the form of contact, such as: Al, Mn, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg,Ga,Zr,C,Si,Sn,Ag.By containing above-mentioned element, the control to the operating voltage and capacity of battery may be implemented.

(9) production of electrode

Electrode can be made using any known method.For example, electrode can be formed by following methods: to negative Adhesive, solvent, as needed thickener, conductive material, packing material of addition etc. are added in the active material of pole, and slurry is made Material is coated on the current collector and is dried, then forms electrode by suppressing.

Battery close on nonaqueous electrolytic solution injection process before stage, the reason of the negative electrode active material layer on each face Think that thickness is usually 15 μm or more, preferably 20 μm or more, more preferably 30 μm or more, the upper limit is 150 μm or less, is preferably 120 μm or less, more preferably 100 μm or less.

When more than the range, since nonaqueous electrolytic solution is difficult to infiltrate near current collection body interface, it is close to may cause high current Spending charge-discharge characteristic reduces.In addition, may cause volume of the collector relative to negative electrode active material if being lower than the range Than increasing, battery capacity is reduced.Furthermore it is possible to which negative electrode active material is carried out roller molding to make pellet electrode, or pass through pressure Type is shortened into make mosaic electrode.

(10) collector

As the collector that negative electrode active material can be made to be maintained, any known collector can be used.As cathode Collector, the metal materials such as copper, nickel, stainless steel, nickel-plated steel can be enumerated, wherein from processing simplification and cost from the aspect of, Particularly preferred copper.

In addition, the shape as collector, when collector is metal material, it can be mentioned, for example metal foil, metal cylinder, Wire coil, metal plate, metallic film, expansion alloy, perforated metal, foaming metal etc..Wherein, preferably comprise copper (Cu) and/ Or the metal foil film of aluminium (Al), more preferable copper foil, aluminium foil, the rolled copper foil and utilization electricity further preferably obtained using rolling process The electrolytic copper foil that solution obtains can be used as collector use either one or two of among the above.

In addition, when the thickness of copper foil is less than 25 μm, can be used intensity higher than fine copper copper alloy (phosphor bronze, titanium copper, Corson alloy, Cu-Cr-Zr alloy etc.).Further, since the specific gravity of aluminium foil is lighter, as collector in use, can make electricity The weight in pond is reduced, thus is preferably used.

In the collector being made of the copper foil prepared using rolling process, arranged since copper is crystallized along rolling direction, because Even if this is at an acute angle by cathode crimping very close or curling, still it is not easily broken, is applicable to small cylinder shape battery.

Electrolytic copper foil can be obtained by following methods: for example, being immersed in metal drum dissolved with the non-aqueous of copper ion In electrolyte, galvanization while rotating the drum is removed to obtain electrolytic copper foil so that copper is precipitated on drum surface.Also Can use electrolysis method is precipitated copper on above-mentioned rolled copper foil surface.Can also the one or both sides to copper foil carry out at roughening Reason or surface treatment (for example, thickness is in base treatments such as the chromic acid salt treatment of several nm~1 μm or so, Ti etc.).

In addition, current collection structure base board further preferably has following physical property.

(10-1) average surface roughness (Ra)

The negative electrode active material film forming face of current collection structure base board specified in the method recorded for JISB0601-1994 Average surface roughness (Ra) be not particularly limited, usually 0.01 μm or more, preferably 0.03 μm or more, and be usually 1.5 μm or less, preferably 1.3 μm or less, more preferably 1.0 μm or less.

This is because, when the average surface roughness (Ra) of current collection structure base board within the above range when, it can be expected that good Charge/discharge cycle characteristics.In addition, the interfacial area with active material film increases, mentioned with the adhesiveness of negative electrode active material film It is high.Wherein, the upper limit value of average surface roughness (Ra) is had no specifically limited, but is more than as average surface roughness (Ra) At 1.5 μm, it is difficult to obtain thickness practical foil when using as battery, therefore it is thick to generally use 1.5 μm of average surfaces below Rugosity (Ra).

(10-2) tensile strength

So-called tensile strength, refer to when test film is broken required maximum pull divided by the sectional area of test film and Obtained value.Tensile strength in the present invention 1 is using identical with the record of JISZ2241 (material during tensile test method) Device and method measurement.

The tensile strength of current collection structure base board is not particularly limited, usually 50Nmm^-2It above, is preferably 100N mm^-2Above, it is more preferably 150Nmm^-2More than.The tensile strength values the high then more preferred, it is contemplated that industrial accessibility is led to It is often 1000Nmm^-2Below.

If it is the high current collection structure base board of tensile strength, then can inhibit thin by active material in charge/discharge process The cracking of current collection structure base board caused by membrane swelling/contraction, can obtain good cycle characteristics.

(10-3) 0.2% yield strength

So-called 0.2% yield strength refers to that the plasticity for generating 0.2% is (permanent) and strains necessary payload size, applies After the load, even if still keeping 0.2% deformation except unloading.0.2% yield strength utilizes identical with measurement tensile strength Device and method measurement.

Specifically limited, usually 30Nmm is had no for 0.2% yield strength of current collection structure base board^-2Above, preferably 100N·mm^-2Above, it is especially preferably 150Nmm^-2More than.The the value of 0.2% yield strength the high then more preferred, from industry The angle of accessibility is set out, it is often preferred that 900Nmm^-2Below.

If it is the high current collection structure base board of 0.2% yield strength, then can inhibit in charge/discharge process by active matter The plastic deformation of current collection structure base board caused by matter film expansion/contraction, can obtain good cycle characteristics.

The thickness of (10-4) collector

Collector can be any thickness, but usually 1 μm or more, preferably 3 μm or more, more preferably 5 μm or more, and Usually 1mm or less, preferably 100 μm or less, more preferably 50 μm or less.

When the thickness of collector is less than 1 μm, since intensity can decline, thus it may cause coating and become difficult.In addition, When thickness is greater than 100 μm, then the electrode shape that may cause winding etc. deforms.It should be noted that collector can be with It is netted.

(11) thickness of collector and active material layer ratio

The thickness ratio of collector and active material layer is had no specifically limited, but " (injects it closing on nonaqueous electrolytic solution The thickness of active material layer on preceding single face)/(thickness of collector) " value be usually 150 or less, preferably 20 with Under, more preferably 10 hereinafter, and usually 0.1 or more, preferably 0.4 or more, more preferably 1 or more.

If the thickness of collector and negative electrode active material layer ratio is more than above range, when high current density charge and discharge, Collector may cause heat release because of Joule heat.In addition, collector is living relative to cathode when thickness ratio is lower than above range Property substance volume ratio increase, may cause battery capacity reduction.

(12) electrode density

Electrode structure when negative electrode active material to be made to electrode is not particularly limited, is present in negative on collector The density of pole active material is preferably 1gcm^-3Above, it is more preferably 1.2gcm^-3It above, is more preferably 1.3gcm^-3Above, it is especially preferably 1.5gcm^-3More than, and preferably 3gcm^-3Below, it is more preferably 2.5gcm^-3Below, into one Step is preferably 2.2gcm^-3Below, it is especially preferably 2gcm^-3Below.

When the density for the active material being present on collector is more than above range, collector and negative electrode active material Bonding dies down, and may cause electrode and is separated with active material.In addition, it is living to may cause cathode if being lower than above range Property substance between electric conductivity reduce, cell resistance increase.

(13) adhesive

It is used as the adhesive of bonding negative electrode active material, when as long as being manufactured relative to nonaqueous electrolytic solution and electrode The material of solvent-stable, then be not particularly limited.

As specific example, polyethylene, polypropylene, polyethylene terephthalate, poly-methyl methacrylate can be enumerated The resinaes macromolecule such as ester, polyimides, aromatic polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), isoamyl two The rubber-like macromolecules such as alkene rubber, butadiene rubber, fluorubber, NBR (nitrile rubber), EP rubbers；Styrene-butadiene- Styrene block copolymer and its hydride；EPDM (ethylene/propylene/diene terpolymer), styrene-ethylene-fourth two The thermoplastic elastomer (TPE)s such as alkene-styrol copolymer, styrene-isoprene-styrene block copolymer and its hydride shape is high Molecule；Syndiotactic 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymerization The soft resinous macromolecule such as object；Kynoar, polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer The fluorine class macromolecule such as object；The polymeric composition etc. with ionic conductivity of alkali metal containing ion (especially lithium ion).On Stating material can be used alone, can also in any combination and two or more is applied in combination in ratio.

As the solvent for being used to form slurry, as long as negative electrode active material, adhesive, Yi Jigen can be dissolved or be dispersed The solvent of the thickener and conductive material that use according to needs is not particularly limited its type, can be used aqueous molten Any one of agent or organic solvent.

As the example of aqueous solvent, water, alcohol etc. can be enumerated；As the example of organic solvent, N- methyl pyrrole can be enumerated Pyrrolidone (NMP), dimethylformamide, dimethyl acetamide, methyl ethyl ketone, cyclohexanone, methyl acetate, methyl acrylate, diethyl Base triamine, N, N- dimethylamino propylamine, tetrahydrofuran (THF), toluene, acetone, dimethyl ether, hexamethyl phosphoramide, diformazan are sub- Sulfone, benzene, dimethylbenzene, quinoline, pyridine, methyl naphthalene, hexane etc..In particular, preferably using thickener when using aqueous solvent While addition dispersing agent etc., and carried out using latex such as SBR slurried.In addition, above-mentioned solvent can be used alone, It can in any combination and two or more is applied in combination in ratio.

Adhesive relative to the ratio of negative electrode active material be usually 0.1 weight % or more, preferably 0.5 weight % with Upper, more preferably 0.6 weight % or more, and usually 20 weight % or less, preferably 15 weight % or less, more preferably 10 weights Measure % or less, especially preferably 8 weight % or less.

If adhesive is more than above range relative to the ratio of negative electrode active material, to battery capacity in amount of binder Do not have the ratio of contributive adhesive to increase, may cause battery capacity reduction.In addition, may cause when being lower than above range The strength reduction of negative electrode, it is not preferred from the aspect of the manufacture craft of battery.

In particular, adhesive is relative to active matter when in main component containing using SBR as the rubber-like macromolecule of representative The ratio of matter is usually 0.1 weight % or more, preferably 0.5 weight % or more, more preferably 0.6 weight % or more, and usual For 5 weight % or less, preferably 3 weight % or less, more preferably 2 weight % or less.

In addition, when in main component containing using Kynoar as the fluorine class macromolecule of representative, relative to active matter The ratio of matter be 1 weight % or more, preferably 2 weight % or more, more preferably 3 weight % or more, usually 15 weight % with Under, preferably 10 weight % or less, more preferably 8 weight % or less.

Thickener is commonly used in adjusting the viscosity of slurry.As thickener, specifically limited, specific enumerable carboxymethyl is had no Cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein And their salt etc..Above-mentioned thickener can be used alone, can also in any combination and two or more is applied in combination in ratio.

In addition, when using thickener, thickener relative to the ratio of negative electrode active material is 0.1 weight % or more, excellent Be selected as 0.5 weight % or more, more preferably 0.6 weight % or more, and usually 5 weight % or less, preferably 3 weight % with Under, more preferably 2 weight % or less.If thickener is lower than above range relative to the ratio of negative electrode active material, may Lead to the significant decrease of coating.On the other hand, when being more than above range, in negative electrode active material layer shared by active material Ratio reduces, and may cause resistance between the problem of battery capacity reduces and negative electrode active material and increase.

<2-4. anode>

It is illustrated below for anode used in the non-aqueous electrolyte secondary battery in the present invention 1.

<2-4-1. positive active material>

It is illustrated below for the positive active material for anode.

(1) it forms

As a positive electrode active material, it is not particularly limited as long as it can electrochemically occlude/release lithium ion, for example, excellent Select the substance containing lithium and at least one kind of transition metal.As specific example, lithium-compound transition metal oxide can be enumerated, contained The transition metal phosphate compound of lithium.

As the transition metal in lithium-compound transition metal oxide, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu etc., make For lithium-compound transition metal oxide specific example, LiCoO can be enumerated₂Equal lithium-cobalt composite oxides, LiNiO₂Equal lithiums-nickel Composite oxides, LiMnO₂、LiMn₂O₄、Li₂MnO₄Equal lithium-manganese composite oxides, with Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Transition metal in the above-mentioned lithium-compound transition metal oxide of other metal substitutes such as Cu, Zn, Mg, Ga, Zr, Si as main body Composite oxides obtained from a part in atom etc..

As the specific example of composite oxides obtained from substitution, it can be mentioned, for example LiNi_0.5Mn_0.5O₂、 LiNi_0.85Co_0.10Al_0.05O₂、LiNi_0.33Co_0.33Mn_0.33O₂、LiMn_1.8Al_0.2O₄、LiMn_1.5Ni_0.5O₄Deng.

As the transition metal in the transition metal phosphate compound containing lithium, preferably V, Ti, Cr, Mn, Fe, Co, Ni, Cu Deng as the specific example of the transition metal phosphate compound containing lithium, it can be mentioned, for example LiFePO₄、Li₃Fe₂(PO₄)₃、 LiFeP₂O₇Equal ferric phosphates class, LiCoPO₄Equal cobalt phosphates class, with Al, Ti, V, Cr, Mn, Fe, Co, Li, Ni, Cu, Zn, Mg, Ga, As one in the transition metal atoms of main body in the above-mentioned lithium of other metal substitutes such as Zr, Nb, Si-transition metal phosphate compound Compound obtained from part etc..

(2) surface coats

It can also use and be attached with and the object as main body composition positive active material on above-mentioned positive active material surface Matter forms different substances (hereinafter, suitably referred to as " surface attachment ").As the example of surface attachment, can enumerate The oxides such as aluminium oxide, silica, titanium oxide, zirconium oxide, magnesia, calcium oxide, boron oxide, antimony oxide, bismuth oxide, sulfuric acid The sulfate such as lithium, sodium sulphate, potassium sulfate, magnesium sulfate, calcium sulfate, aluminum sulfate, carbonate such as lithium carbonate, calcium carbonate, magnesium carbonate etc..

These surface attachments can be made to be attached to positive active material surface by following methods, for example, making surface Attachment material is dissolved or suspended in solvent, and makes its impregnation addition in positive active material, the side being then dried again Method；It is dissolved or suspended in surface attachment precursor in solvent, and makes its impregnation addition in positive active material, then lead to Cross the method that heating etc. reacts it；Surface attachment is added in positive active material precursor, while being sintered Method etc..

Relative to the weight of positive active material, the weight for being attached to the surface attachment on positive active material surface is logical Often be 0.1ppm or more, preferably 1ppm or more, more preferably 10ppm or more, and usually 20% or less, preferably 10% with Under, more preferably 5% or less.

It can inhibit nonaqueous electrolytic solution that oxidation reaction occurs on positive active material surface by surface attachment, in turn Improve battery life.But if adhesion amount is lower than above range, effect is unable to fully embody；And when more than above-mentioned model When enclosing, the discrepancy of lithium ion can be caused to hinder, may cause resistance increase, therefore preferred above range.

(3) shape

The shape of particle as a positive electrode active material, can be used bulk, polyhedral, spherical, oval spherical, plate, Shape used by needle-shaped, column etc. is previous, wherein preferred primary particle agglomeration forms secondary, the secondary It is preferably shaped to spherical or oval spherical.

In general, electrochemical element, with charge and discharge, the active material in electrode can expand contraction, therefore be easy Cause the destruction of active material and the deterioration of conductive on-off etc. under the stress.As a result, with there is only the single of primary particle The case where particle active material is compared, and preferably primary particle agglomeration forms secondary, this is because, aggregation forms secondary When, dilation stress is mitigated, and can prevent from deteriorating.

In addition, compared with the isometric orientation particle of plate, the case where more preferably spherical or oval spherical particle, this be by In, orientation of the spherical or oval spherical particle in electrode moulding is weaker, and the dilation of electrode is also less when charge and discharge, and The also uniform mixing easy to accomplish when carrying out the mixing with conductive material when preparing electrode.

(4) tap density

The tap density of positive active material is usually 1.3gcm^-3It above, is preferably 1.5gcm^-3Above, more preferably For 1.6gcm^-3Above, it is especially preferably 1.7gcm^-3More than, and usually 2.5gcm^-3It below, is preferably 2.4g cm^-3Below.

By using the high metal compound oxide powder of tap density, highdensity positive electrode active material layer can be formed. Thus, if the tap density of positive active material is lower than above range, necessary to forming positive electrode active material layer The amount of decentralized medium increases, while the necessary amount of conductive material and binder increases, and positive active material is in positive active material Filling rate in layer is restricted, and may cause battery capacity and is restricted.In addition, the tap density usually the big more preferably, There is no the special upper limit, but if being lower than above range, then in positive electrode active material layer using nonaqueous electrolytic solution as the lithium of medium from The diffusion of son becomes the factor for determining speed, may cause load characteristic reduction.

Tap density measures as follows: sample being made to drop into 20cm after the sieve by 300 μm of mesh³Vibration In real container, until sample is full of the volume of container, then using powder density analyzer (for example, Seishin enterprise-like corporation system The Tap densor made) carry out the vibration that 1000 lengths of stroke are 10mm, by this time volume and sample weight find out jolt ramming Density.The tap density calculated using the measurement is defined as to the tap density of positive active material in the present invention 1.

(5) median particle diameter d50

The median particle diameter d50 of the particle of positive active material is (when primary particle agglomeration forms secondary, for secondary grain Diameter) it is measured using laser diffraction/scattering formula particle size distribution device.

Median particle diameter d50 is usually 0.1 μm or more, preferably 0.5 μm or more, more preferably 1 μm or more, is especially preferably 3 μm or more, and usually 20 μm or less, preferably 18 μm or less, more preferably 16 μm or less, especially preferably 15 μm or less. If median particle diameter d50 is lower than above range, the high product of volume density possibly can not be obtained, and when more than above range When, then since the diffusion of lithium in particle needs the time, it may cause battery behavior reduction, or anode is being made, is adopting Active material and conductive material or adhesive etc. carried out with solvent slurried and then when being coated into film-form, generates striped etc. Situation.

It should be noted that can also by by two or more positive active material with different median particle diameter d50 to appoint Meaning ratio mixes to improve the fillibility when anode is made.

Median particle diameter d50 can be measured by following methods: be that dispersion is situated between with the sodium hexametaphosphate solution of 0.1 weight % Matter, the LA-920 for using Ku Chang manufacturing company to manufacture is as particle size distribution meter, after carrying out ultrasonic wave dispersion in 5 minutes, if Surely measurement refractive index is 1.24 to be measured.

(6) primary particle average grain diameter

When primary particle agglomeration forms secondary, the primary particle average grain diameter of positive active material is usually 0.01 μm or more, preferably 0.05 μm or more, more preferably 0.08 μm or more, be especially preferably 0.1 μm or more, and usually 3 μm with Under, preferably 2 μm or less, more preferably 1 μm or less, be especially preferably 0.6 μm or less.If primary particle average grain diameter is more than Above range is then hardly formed spherical secondary, can cause adverse effect to powder fillibility, or will lead to specific surface Product is greatly reduced, and thus may cause the reduction of the battery performances such as output characteristics；In addition, if primary particle average grain diameter is lower than upper Range is stated, then normally results in crystallization not exclusively, and then the poorly reversible performance drop for waiting secondary cells of charge and discharge may be caused It is low.

In addition, primary particle average grain diameter can be by observe measuring using scanning electron microscope (SEM).Specifically, Be in 10000 times of photo in multiplying power, for arbitrary 50 primary particles, find out the left bounding lines of primary particle relative to The greatest length of intercept obtained by the straight line of horizontal direction, then be averaged to find out primary particle average grain diameter.

(7) BET specific surface area

Value using the BET specific surface area of the positive active material of BET method measurement is usually 0.2m²·g^-1Above, preferably For 0.3m²·g^-1Above, it is more preferably 0.4m²·g^-1More than, and usually 4.0m²·g^-1It below, is preferably 2.5m²·g^-1With Under, more preferably 1.5m²·g^-1Below.If the value of BET specific surface area is lower than above range, battery performance is easily reduced. On the other hand, if it exceeds above range, then tap density is not easy to improve, it may cause the painting when forming positive active material Cloth reduces.

BET specific surface area is measured using surface area meter (the full-automatic surface area determination unit that Okura development is made). Predrying in 30 minutes is carried out to sample at nitrogen stream, 150 DEG C, is then used nitrogen is quasi- relative to the relative pressure of atmospheric pressure It is really adjusted to 0.3 nitrogen helium mixed gas, is measured by using 1 method of N2 adsorption BET that gas flow method carries out.It will The BET specific surface area of positive active material in the present invention 1 is defined as using the specific surface area that the measurement is found out.

(8) preparation method of positive active material

Preparation method as a positive electrode active material, without departing from the present invention 1 main points range then without special limit System, can enumerate several method, but the manufacturing method as inorganic compound, usual way can be used.

In particular, it is contemplated that various methods prepare spherical or oval spherical active material.For example, as one of method, Following methods can be enumerated: by the transition metal such as transition metal nitrate, sulfate raw material and as needed and use its The raw material dissolution of its element or grinding dispersion in water and other solvents, pH are adjusted while being stirred, prepares and collects Spherical precursor is as needed dried the precursor, and LiOH, Li is then added₂CO₃、LiNO₃The equal source Li, and at high temperature Sintering, thus the method for obtaining active material.

In addition, the example as another method, can enumerate following methods: by transition metal nitrate, sulfate, hydroxide The transition metal such as object, oxide raw material and the as needed dissolution of the raw material of other elements for using or grinding dispersion In water equal solvent, using spray dryer etc. to its drying and moulding, spherical or oval spherical precursor is made, then adds thereto Enter LiOH, Li₂CO₃、LiNO₃The equal source Li, is sintered, at high temperature thus the method for obtaining active material.

Alternatively method can also enumerate following methods: by transition metal nitrate, sulfate, hydroxide, The transition metal such as oxide raw material and LiOH, Li₂CO₃、LiNO₃The equal source Li and other elements that are as needed and using Raw material dissolution or grinding dispersion in water equal solvent, molding is dried to it using spray dryer etc., ball is made Shape or oval spherical precursor, it are sintered at high temperature, thus the method for obtaining active material.

<2-4-2. electrode structure and production method>

Hereinafter, being illustrated for the positive structure and preparation method thereof used in the present invention 1.

(1) positive production method

Anode and forming the positive electrode active material layer containing positive active material particle and binder on the current collector It is made.It can be prepared using well known any means using the manufacture of the anode of positive active material.I.e., it is possible to by positive-active Substance and binder and conductive material and thickener etc. as needed and use carry out dry type mixing and sheet are made, then The flaky material is attached on positive electrode collector, or these materials is dissolved or dispersed in liquid medium, slurry is made, and The slurry is coated on positive electrode collector and is dried, to form positive electrode active material layer on the current collector, and then is obtained It obtains positive.

Content of the positive active material in positive electrode active material layer is usually 10 weight % or more, preferably 30 weight % Above, 50 weight % or more are especially preferably, and usually 99.9 weight % or less, preferably 99 weight % or less.This be by In, when the positive active material content in positive electrode active material layer be lower than above range when, may cause capacitor and become inadequate； And when content is more than above range, the intensity that may cause anode is insufficient.It should be noted that the anode in the present invention 1 is living Property material powder can be used alone, can also in any combination and ratio be applied in combination two or more with it is different composition or The positive electrode active material powder of different powder properties.

(2) conductive material

As conductive material, any known conductive material can be used.As specific example, the metals such as copper, nickel can be enumerated Material；The graphite such as natural graphite, artificial graphite (graphite)；The carbon blacks such as acetylene black；The carbonaceous materials such as the amorphous carbon such as needle coke Deng.Wherein, above-mentioned conductive material can be used alone, can also in any combination and two or more is applied in combination in ratio.

Conductive material contained in positive electrode active material layer be usually 0.01 weight % or more, preferably 0.1 weight % with Upper, more preferably 1 weight % or more, and usually 50 weight % or less, preferably 30 weight % or less, more preferably 15 weights Measure % or less.When content is lower than above range, electric conductivity deficiency may cause.And when being more than above range, it may cause Battery capacity reduces.

(3) binder

As long as the binder used when manufacturing positive electrode active material layer is relative in manufacture nonaqueous electrolytic solution or electrode When used solvent-stable binder, then be not particularly limited.

The material in liquid medium used when using rubbing method, when as long as being dissolved or dispersed in manufacture electrode is i.e. Can, as specific example, polyethylene, polypropylene, polyethylene terephthalate, polymethyl methacrylate, virtue can be enumerated The resinaes macromolecule such as fragrant polyamide, cellulose, NC Nitroncellulose；SBR (butadiene-styrene rubber), NBR (nitrile rubber), fluorine rubber The rubber-like macromolecule such as glue, isoprene rubber, butadiene rubber, EP rubbers；S-B-S block is total Polymers or its hydride, EPDM (ethylene/propylene/diene terpolymer), styrene ethylene butadiene-ethylene copolymer The thermoplastic elastomer (TPE)s shape macromolecule such as object, styrene-isoprene-styrene block copolymer or its hydride；Syndiotactic The soft resinous such as 1,2- polybutadiene, polyvinyl acetate, vinyl-vinyl acetate copolymer, propylene-alpha-olefin copolymers Macromolecule；The fluorine class such as Kynoar (PVdF), polytetrafluoroethylene (PTFE), fluorination Kynoar, polytetrafluoroethylene (PTFE)-ethylene copolymer Macromolecule；The polymeric composition etc. of ionic conductivity with alkali metal ion (especially lithium ion).Above-mentioned substance can be with 1 kind of exclusive use, can also in any combination and two or more is applied in combination in ratio.

In positive electrode active material layer ratio shared by binder be usually 0.1 weight % or more, preferably 1 weight % with Upper, more preferably 3 weight % or more, and usually 80 weight % or less, preferably 60 weight % or less, more preferably 40 weights Measure % or less, especially preferably 10 weight % or less.If the ratio of binder be lower than above range, positive active material without Method is sufficiently maintained, and may cause the degradation of cell performance such as mechanical strength deficiency, the cycle characteristics of anode.In addition, being more than upper When stating range, then may cause battery capacity or electric conductivity reduces.

(4) liquid medium

As the liquid medium for being used to form slurry, as long as can dissolve or disperse positive active material, conductive material, Binder and the as needed solvent of thickener that uses, are not particularly limited its type, can be used aqueous Any one of solvent and organic solvent.

The example of aqueous medium, it can be mentioned, for example blending agents of water, alcohol and water etc..As the example of organic medium, It can enumerate: the fat hydrocarbons such as hexane；The arenes such as benzene,toluene,xylene, methyl naphthalene；The heterocyclic compounds such as quinoline, pyridine； The ketones such as acetone, methyl ethyl ketone, cyclohexanone；The esters such as methyl acetate, methyl acrylate；Diethylenetriamines, N, N- dimethylamino The amines such as base propylamine；The ethers such as ether, tetrahydrofuran (THF)；N-Methyl pyrrolidone (NMP), dimethylformamide, dimethyl The amides such as acetamide；Aprotic polar solvents such as hexamethyl phosphoramide, dimethyl sulfoxide etc..It is given an account of on it should be noted that Matter can be used alone, can also in any combination and two or more is applied in combination in ratio.

(5) thickener

When using aqueous medium as the liquid medium for being used to form slurry, it is preferable to use thickener and butadiene-styrene rubber (SBR) etc. latex is slurried to carry out.Thickener usually can be used to adjust the viscosity of slurry.

As thickener, system limit, specific enumerable carboxymethyl are had no in the range of not significantly limiting the effect of the present invention 1 Cellulose, methylcellulose, hydroxymethyl cellulose, ethyl cellulose, polyvinyl alcohol, oxidized starch, phosphorylated starch, zymoprotein And their salt etc..Above-mentioned thickener can be used alone, can also in any combination and two or more is applied in combination in ratio.

In addition, when using thickener, thickener is usually 0.1 weight % or more, preferably relative to the ratio of active material For 0.5 weight % or more, more preferably 0.6 weight % or more, and usually 5 weight % or less, preferably 3 weight % or less, More preferably 2 weight % or less.If being lower than above range, the significant decrease of coating may cause, and when more than above-mentioned When range, active material ratio decline shared in positive electrode active material layer, may cause the problem of battery capacity reduces or The problem of resistance increases between positive active material.

(6) it is compacted

In order to improve the packed density of positive active material, preferably process is coated with by hand press, roll squeezer etc., Positive electrode active material layer obtained from drying is compacted.The density of positive electrode active material layer is preferably 1gcm^-3Above, more excellent It is selected as 1.5gcm^-3Above, it is especially preferably 2gcm^-3More than, and preferably 4gcm^-3Below, more preferably in 3.5g cm^-3Below, particularly preferably in 3gcm^-3Below.

If the density of positive electrode active material layer is more than above range, nonaqueous electrolytic solution is to collector/active material circle Impregnability near face reduces, in particular, the charge-discharge characteristic that may cause at higher current densities reduces.And work as positive-active When the density of material layer is lower than above range, the electric conductivity that may cause between active material is reduced, and cell resistance increases.

(7) collector

It as the material of positive electrode collector, is not particularly limited, can arbitrarily use well known material.As specific example, The metal materials such as aluminium, stainless steel, nickel plating, titanium, tantalum can be enumerated；The carbonaceous materials such as carbon cloth, carbon paper.Wherein, preferred metal materials, especially Its preferred aluminium.

Metal foil, metal cylinder, wire coil, gold can be enumerated when material is metal material as the shape of collector Belong to plate, metallic film, expansion alloy, perforated metal, foaming metal etc.；When material is carbonaceous material, it is thin that carbon plate, carbon can be enumerated Film, carbon cylinder etc..In these materials, preferred metallic film.It should be noted that it is netted that film, which can be suitably formed,.

Collector can be any thickness, but usually 1 μm or more, preferably 3 μm or more, be more preferably 5 μm or more, and Usually 1mm or less, preferably 100 μm or less, more preferably 50 μm or less.If film thickness is less than above range, can The necessary intensity as collector can be caused insufficient.And when film thickness is greater than above range, operability may be destroyed.

<2-5. partition>

It is short-circuit in order to prevent, partition is usually sandwiched between a positive electrode and a negative electrode.At this point, usually making the non-water power of the present invention 1 Solution liquid is soaked in the partition and uses.

The material and shape of partition are not particularly limited, as long as in the range for the effect for not destroying the present invention 1 significantly It is interior, well known material and shape can be used arbitrarily.Wherein, it can be used with the material shape stable to nonaqueous electrolytic solution of the invention At resin, glass fibre, inorganic matter etc., it is preferable to use porous sheet or non-woven fabric-like form with excellent liquid retention Material etc..

As resin, the separator material of glass fibre, the polyolefin such as polyethylene, polypropylene, polytetrafluoroethyl-ne can be used Alkene, polyether sulfone, glass filter etc..Wherein, preferably glass filter, polyolefin, particularly preferred polyolefin.These materials can be with 1 kind of exclusive use, can also in any combination and two or more is applied in combination in ratio.

Aforementioned barriers can be any thickness, but usually 1 μm or more, preferably 5 μm or more, be more preferably 10 μm with On, and usually 50 μm or less, preferably 40 μm or less, more preferably 30 μm or less.If block board thickness is less than above range, Then may cause insulating properties or mechanical strength reduces.In addition, then not only may cause speed when block board thickness is more than above range Spending the battery performances such as characteristic reduces, it is also possible to cause the energy density decline of non-aqueous electrolyte secondary battery entirety.

In addition, the voidage of partition is any when using the porous materials such as porous sheet or non-woven fabrics as partition , but usually 20% or more, preferably 35% or more, more preferably 45% or more, and usually 90% or less, preferably 85% or less, it is more preferably 75% or less.If voidage is less than above range, film resistance increases, and may cause speed spy Property be deteriorated.And when voidage is excessive compared with above range, the mechanical strength that may cause partition reduces, insulating properties decline.

In addition, the average pore size of partition is also arbitrary, but usually 0.5 μm or less, preferably 0.2 μm hereinafter, and logical It is often 0.05 μm or more.If average pore size is more than above range, it is easy to happen short circuit.On the other hand, if average pore size Lower than above range, then it may cause film resistance increase, speed characteristics reduce.

On the other hand, as inorganic material, can be used the oxide-based, aluminium nitride such as aluminium oxide or silica or The Sulfates such as silicon nitride etc. is nitride-based, barium sulfate or calcium sulfate, can be used the inorganic matter of shape of particle or fiber shape Material.

As form, the thin film shapes such as non-woven fabrics, woven fabric, microporous membrane can be used.As thin film shape, it is suitble to use hole Diameter is 0.01~1 μm, with a thickness of 5~50 μm of films.Other than above-mentioned independent thin film shape, can also use it is following every Plate: it is formed on the surface layer of anode and/or cathode using the binder of resin and contains the compound porous of above-mentioned inorganic particles Partition obtained from layer.It is, for example, possible to use fluororesin as binder, and aluminium oxide particles of 90% partial size less than 1 μm is made to exist Porous layer is formed on the two sides of anode.

<2-6. battery design>

[electrode group]

Electrode group can be laminar structure and folder obtained from clipping the above-mentioned positive plate of aforementioned barriers lamination and negative plate Aforementioned barriers above-mentioned positive plate and negative plate are wound into any one in spiral helicine structure.The volume of electrode group is in electricity Shared ratio (hereinafter referred to as electrode group occupancy rate) is usually 40% or more, preferably 50% or more in the internal volume of pond, and Usually 90% or less, preferably 80% or less.If electrode group occupancy rate is lower than above range, it will lead to battery capacity and subtract It is small.And when electrode group occupancy rate is more than above range, void space is small, and when battery is in high temperature, component can be caused to expand, or The vapour pressure for causing the liquid component of electrolyte increases, and internal pressure rises, repeated charge performance and high temperature as battery The various characteristics such as preservation reduce, and then gas release valve may be needed to work to help internal pressure to discharge to outside.

[current collecting]

Current collecting is not particularly limited, but is caused to more effectively realize by the nonaqueous electrolytic solution of the present invention 1 Flash-over characteristic raising, be preferably made the structure for reducing wiring part and bonding part resistance.So, make internal electricity When resistance reduces, especially can excellently it be played using the effect of the nonaqueous electrolytic solution of the present invention 1.

In the case where electrode group is above-mentioned laminar structure, it is preferred to use following structures: by the metal core of each electrode layer Divide the structure for tying together that simultaneously welding is formed on terminal.Since when increasing the area of 1 piece of electrode, internal resistance increases therewith Add, thus it is also preferred that dropping low-resistance method using multiple terminals are arranged in electrode.It is above-mentioned winding-structure in electrode group In the case where, multiple pin configurations can be respectively set on anode and cathode, and be bundled on terminal to reduce internal resistance.

[battery case (exterior ケ ー ス)]

As the material of battery case, as long as the substance stable to the nonaqueous electrolyte used, has no special limit System.Specifically, the folded of the metals such as nickel-clad steel plate, stainless steel, aluminum or aluminum alloy, magnesium alloy class or resin and aluminium foil can be used Tunic (stacked film)., it is preferable to use the metal of aluminum or aluminum alloy, stacked film from the aspect of lightweight.

In the battery case for stating metal class in use, the shell with following structures can be enumerated: by laser welding, Resistance welding, ultrasonic bonding will seal closed structure made of welding mutual between metal；Or it is used through resin washer upper The riveted structure stating metal class and being formed.In the battery case for stating stacked film in use, it can enumerate by will be between resin layer Mutually it is hot-melted and manufactured sealing closed structure etc..In order to improve leakproofness, can also be sandwiched between above-mentioned resin layer with The different resin of resin for stacked film.In particular, closed to be formed being hot-melted by current-collecting terminals to resin layer When structure, due to mutually bonding between metal and resin, thus it is preferable to use the resin with polar group or polarity has been imported The modified resin of group is as the resin being clamped between resin layer.

[protection element]

As above-mentioned protection element, the increased PTC of resistance when abnormal heat release or super-high-current are flowed through can be enumerated (Positive Temperature Coefficient, positive temperature coefficient), temperature fuse, thermistor, in abnormal heat release When sharply increased by cell internal pressure or internal temperature and block valve for flowing through electric current in circuit (current blocking valve) etc..On The element that protection element preferably selects idle condition when the routine of high current uses is stated, the angle exported from height, More preferably it is made the design for being also unlikely to be abnormal heat release or thermal runaway even if there be no protection element.

[shell (exterior body)]

The non-aqueous electrolyte secondary battery of the present invention 1 is usually to receive above-mentioned nonaqueous electrolytic solution, cathode, anode, partition etc. It is contained in shell and constitutes.For the shell, there is no limit, can be in the range of not destroying the effect of the present invention 1 significantly Well known shell is used arbitrarily.

Specifically, shell can be any material, but usually using for example implement the iron of nickel plating, stainless steel, aluminium or Its alloy, nickel, titanium etc..

In addition, the shape of shell is also arbitrary, can be such as cylinder type, rectangular, laminated type, Coin shape, large size In arbitrary shape.

<nonaqueous electrolytic solution 2, non-aqueous electrolyte secondary battery 2>

[1. non-aqueous electrolyte for secondary battery]

The non-aqueous electrolyte for secondary battery of the present invention 2 is by electrolyte and to dissolve the nonaqueous solvents of the electrolyte for main structure At nonaqueous electrolytic solution, the nonaqueous electrolytic solution contains selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, with the virtue of halogen atom At least one kind of compound (hreinafter referred to as " compound of the present invention 2 in fragrant compounds of group class and ethers with fluorine atom Group "), also contain mono-fluor phosphate and/or difluorophosphoric acid salt

<1-1. electrolyte>

For the electrolyte of nonaqueous electrolytic solution for the present invention 2, there is no restriction, wherein can be used arbitrarily and containing in mesh It can be used as the well known electrolyte that electrolyte uses in mark non-aqueous electrolyte secondary battery.In addition, by the non-aqueous solution electrolysis of the present invention 2 When liquid is used for non-aqueous electrolyte secondary battery, electrolyte is preferably lithium salts.

As the specific example of electrolyte, it can be mentioned, for example: be documented in identical electrolyte in the present invention 1.

Wherein, preferably LiPF₆、LiBF₄、LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂, two (oxalate conjunction) boric acid Lithium, particularly preferred LiPF₆Or LiBF₄。

The ratio of the type of electrolyte when for electrolyte is applied in combination, electrolyte when being applied in combination, and is documented in this Situation in invention 1 is identical.

In addition, lithium salt, preferred concentration etc. in the final composition of the nonaqueous electrolytic solution of the present invention 2, and it is documented in this Situation in invention 1 is identical.In addition, when deviateing numberical range there is a situation where the phenomenon that also be documented in the present invention 1 in phase Together.

In particular, for nonaqueous electrolytic solution nonaqueous solvents with carbonic acid as alkylene carbonates or dialkyl carbonate It is the case where based on ester compounds, also identical as situation about being documented in the present invention 1.Occur when in addition, deviateing numberical range Phenomenon is also identical as situation about being documented in the present invention 1.

In addition, when the gamma-butyrolacton containing 50 volume % or more, gamma-valerolactone in the nonaqueous solvents in nonaqueous electrolytic solution Etc. cyclic carboxylic acids ester compounds when, also be documented in the present invention 1 in situation it is identical.

<1-2. nonaqueous solvents>

The present invention 2 nonaqueous electrolytic solution contained by nonaqueous solvents be documented in the present invention 1 nonaqueous electrolytic solution contained by Nonaqueous solvents in situation it is identical.

<the compound group of the 1-3. present invention 2>

" the compound group of the present invention 2 " is selected from chain saturated hydrocarbons, cyclic saturated hydrocarbons, the aromatic series with halogen atom At least one kind of compound in compounds and ethers with fluorine atom is high from the climbing of output characteristics in these compounds From the perspective of, preferably cyclic saturated hydrocarbons or the ethers with fluorine atom.The chemical combination selected from the compound group of the present invention 2 Object can be used a kind, can also be used in any combination two or more.In the following, to the " chemical combination of the present invention 2 constituted in the present invention 2 Each compound of object group " is more specifically illustrated.

<1-3-1. chain saturated hydrocarbons>

As chain saturated hydrocarbons, be not particularly limited, but from the viewpoint of operation, preferably at normal temperature for liquid simultaneously And the chain saturated hydrocarbons that toxicity is low；From the viewpoint of battery behavior, the smaller chain saturated hydrocarbons of preferred molecular weight.More And specifically, it is preferable to the chain saturated hydrocarbons of carbon atom number 5~20, the chain saturated hydrocarbons of particularly preferred carbon atom number 7~16.

And specifically, it is preferable to such as pentane, hexane, heptane, octane, nonane, decane, hendecane, 12 carbon alkane, 13 carbon Alkane, tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane or icosane, particularly preferred heptan Alkane, octane, nonane, decane, hendecane, 12 carbon alkane, tridecane, tetradecane, pentadecane or hexadecane.These Chain saturated hydrocarbons can be straight-chain, be also possible to branched.It, can also be in addition, these chain saturated hydrocarbons can be used a kind It is used in any combination two or more.

<1-3-2. cyclic saturated hydrocarbons>

It as cyclic saturated hydrocarbons, is not particularly limited, but the cyclic saturated hydrocarbons of preferably carbon atom number 3~20, especially It is preferred that the cyclic saturated hydrocarbons of carbon atom number 5~16.

And specifically, it is preferable to cyclopropane, cyclobutane, pentamethylene, hexamethylene, cycloheptane, cyclooctane, cyclononane, cyclodecane, ring Hendecane, 12 carbon alkane of ring, ring tridecane, ring tetradecane, ring pentadecane, ring hexadecane, ring heptadecane, ring Octadecane, ring nonadecane or ring icosane, particularly preferred pentamethylene, hexamethylene, cycloheptane, cyclooctane, cyclononane, ring Decane, ring hendecane, 12 carbon alkane of ring, ring tridecane, ring tetradecane, ring pentadecane or ring hexadecane.

In addition, these cyclic saturated hydrocarbons can also have straight chained alkyl in the molecule, there is no limit excellent for the straight chained alkyl Select the alkyl of carbon atom number 1~8.Specifically, it such as can enumerate: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl or pungent Base.The most preferred example of cyclic saturated hydrocarbon is hexamethylene.These cyclic saturated hydrocarbons can be used a kind, can also be any group It closes and uses two or more.

<the aromatic compound species that 1-3-3. has halogen atom>

It as the aromatic compound species with halogen atom, is not particularly limited, as halogen atom, preferably fluorine atom or chlorine Atom, particularly preferred fluorine atom.In addition, halogen atom can Direct Bonding on aromatic rings, can also be former containing halogen in substituent group Son.

It as the specific example of the aromatic compound species with halogen atom, such as can enumerate: fluorobenzene, chlorobenzene, 1,2- bis- Fluorobenzene, 1,3- difluorobenzene, 1,4- difluorobenzene, 1,2- dichloro-benzenes, 1,3- dichloro-benzenes, 1,4- dichloro-benzenes, 1,2,4- trifluoro-benzene, 1,3, 5- trifluoro-benzene, 1,2,4,6- phenyl tetrafluoride, phenyl-hexafluoride, 2- toluene fluoride, 3- toluene fluoride, 4- toluene fluoride, methyl fluoride benzene, difluoromethyl The fluoro- 1- trifluoromethylbenzene of benzene, trifluoromethylbenzene, 2-, the fluoro- 1- trifluoromethylbenzene of 4-, 2- fluorine biphenyl, adjacent cyclohexyl fluorobenzene, to ring Hexyl fluorobenzene etc..It is preferred that fluorobenzene, 2- toluene fluoride, 4- toluene fluoride or trifluoromethylbenzene.These " aromatic compounds with halogen atom Species " can be used a kind, can also be used in any combination two or more.

<ethers that 1-3-4. has fluorine atom>

It as the ethers with fluorine atom, is not particularly limited, if ethers is expressed as " R with general formula⁵-O-R⁶", then " ethers with fluorine atom " is in R⁵Or R⁶At least one group in contain fluorine atom.Wherein, if R⁵It is containing fluorine atom Group, then R⁵The alkyl of the carbon atom number 1~20 preferably replaced by 1~30 fluorine atom.

Wherein, it as preferred specific example, such as can enumerate:

Methyl fluoride, difluoromethyl, trifluoromethyl；

1- fluoro ethyl, 2- fluoro ethyl, 1,1- bis-fluoro ethyls, 1,2- bis-fluoro ethyls, 2,2- bis-fluoro ethyls, 1,1,2- trifluoro second Base, 1,2,2- trifluoroethyl, 2,2,2- trifluoroethyl, tetra- fluoro ethyl of 1,1,2,2-, tetra- fluoro ethyl of 1,2,2,2-, pentafluoroethyl group；

3- fluoropropyl, bis- fluoropropyl of 3,3-, 3,3,3- trifluoro propyl, 2,2,3,3,3- pentafluoropropyl group, heptafluoropropyl；

4- fluorine butyl, 4,4- difluorobutyl groups, 4,4,4- triRuorobutyl, five fluorine butyl of 3,3,4,4,4-, 2,2,3,3,4,4, Seven fluorine butyl of 4-, nona-fluoro butyl group；

5- fluorine amyl group, bis- fluorine amyl group of 5,5-, tri- fluorine amyl group of 5,5,5-, five fluorine amyl group of 4,4,5,5,5-, 3,3,4,4,5,5, Seven fluorine amyl group of 5-, nine fluorine amyl group of 2,2,3,3,4,4,5,5,5-, 11 fluorine amyl groups；

6- fluorine hexyl, 6,6- difluoro hexyl, 6,6,6- trifluoro hexyl, ten trifluoro hexyls etc..

In addition, R⁶Preferably optionally specifically removed by the alkyl for the carbon atom number 1~20 that the substituent groups such as halogen atom replace R⁵In it is cited containing other than fluoroalkyl, can also enumerate: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, pungent The common chain-like alkyl such as base, nonyl, decyl, undecyl, dodecyl (straight-chain or branched)；And containing other than fluorine Naphthenic base such as alkylhalide group, cyclohexyl etc..

As the specific example of fluorine-containing ethers, can enumerate: ethyl 2- fluoro ethyl ether, two (2- fluoro ethyl) ethers, ethyl 2,2, 2- trifluoroethyl ether, two (2,2,2- trifluoroethyl) ethers, two (pentafluoroethyl group) ethers, methyl 3- fluoropropyl ether, 3- fluoropropyl fluorine first Base ether, 3- fluoropropyl trifluoromethyl ethers, 3- fluoropropyl ethylether, 3- fluoropropyl 2- fluoro ethyl ether, methyl 3,3,3- trifluoro propyl Ether, ethyl 3,3,3- trifluoro propyl ether, 3,3,3- trifluoro propyl 2- fluoro ethyl ether, 3,3,3- trifluoro propyl 2,2,2- trifluoroethyl Ether, methyl heptafluoropropyl ether, ethyl heptafluoropropyl ether, heptafluoropropyl 2,2,2- trifluoroethyl ether, heptafluoropropyl pentafluoroethyl group ether, Methyl 4- fluorine butyl ether, ethyl 4- fluorine butyl ether, 4- fluorine butyl 2- fluoro ethyl ether, ethyl 4,4,4- triRuorobutyl ether, 4,4,4- TriRuorobutyl 2- fluoro ethyl ether, 4,4,4- triRuorobutyl 2,2,2- trifluoroethyl ether, 4,4,4- triRuorobutyl pentafluoroethyl group ether, first Base nona-fluoro butyl group ether, ethyl no nafluoro butyl ether, nona-fluoro butyl group 2- fluoro ethyl ether, nona-fluoro butyl group 2,2,2- trifluoroethyl ether, nine fluorine Butyl pentafluoroethyl group ether etc..

Wherein, preferably ethyl 2- fluoro ethyl ether, two (2- fluoro ethyl) ethers, ethyl 2,2,2- trifluoroethyl ether, two (2,2,2- Trifluoroethyl) ether, ethyl heptafluoropropyl ether or ethyl no nafluoro butyl ether.These fluorine-containing ethers can be used a kind, can also be any Two or more is applied in combination.

<1-3-5. content>

Content as " present invention 2 compound groups " relative to nonaqueous electrolytic solution total amount, is not particularly limited, but from electricity From the viewpoint of the characteristic of pond, preferably 0.01 weight % or more, more preferably 0.1 weight % or more, particularly preferably 0.3 weight % or more is measured, on the other hand, the upper limit is preferably 15 weight % or less, more preferably 12 weight % or less, particularly preferably 10 Weight % or less.When the content of " the compound group of the present invention 2 " is very few, it is possible to not contribute to aftermentioned " mono-fluor phosphate And/or difluorophosphoric acid salt " possessed " output " and " being exported after circulation " excellent effect.

<1-4. mono-fluor phosphate, difluorophosphoric acid salt>

" mono-fluor phosphate and/or difluorophosphoric acid salt " used in the present invention 2 is identical as the present invention 1.Preferred range It is identical as invention 1.

<the mono- fluorophosphoric acid metal salt of 1-4-1., difluorophosphoric acid metal salt>

It is single fluorophosphoric acid radical ion, difluorophosphoric acid root firstly, for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention 2 The case where salt that ion and special metal ion are formed, specific example can be enumerated and 1 identical example of the invention.

< 1-4-2. mono- fluorophosphoric acid seasonSalt, difluorophosphoric acid seasonSalt >

Secondly, being single fluorophosphoric acid radical ion, difluorophosphoric acid root for mono-fluor phosphate, the difluorophosphoric acid salt in the present invention 2 Ion and seasonThe case where salt of formation, specific example can be enumerated and 1 identical example of the invention.

<1-4-3. content, detection (source contained), technical scope etc.>

In the nonaqueous electrolytic solution of the present invention 2, a kind of mono-fluor phosphate or difluorophosphoric acid salt can be used only, it can also be with Arbitrary combination and ratio use mono-fluor phosphate of more than two kinds and/or difluorophosphoric acid salt simultaneously, but from making nonaqueous electrolyte two , it is preferable to use a kind of mono-fluor phosphate or difluorophosphoric acid salt from the viewpoint of primary cell effectively works.

In addition, the molecular weight of mono-fluor phosphate and difluorophosphoric acid salt, preparation method, ratio in nonaqueous electrolytic solution etc., It is identical illustrated in the present invention 1.

In addition, the detection period (period contained) of mono-fluor phosphate or difluorophosphoric acid salt, the place initially contained first (source contained), the method contained are considered as containing the detection place of (or having contained) etc. in nonaqueous electrolytic solution, with this It is identical illustrated in invention 1.

<1-5. additive>

In the range of not destroying the effect of the present invention 2 significantly, it can also contain in the nonaqueous electrolytic solution of the present invention 2 various Additive.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that Additive can be used alone, two or more can also be applied in combination with ratio in any combination.

As the example of additive, overcharge preventing agent can be enumerated or keep special for improving the capacity after High temperature storage Property and the auxiliary agent of cycle characteristics etc..Wherein, as improving helping for the capacity maintenance characteristics after High temperature storage and cycle characteristics Agent, preferably addition have the carbonic ester of at least one of unsaturated bond and halogen atom (hereinafter, sometimes referred to simply as " specific carbonic acid Ester ").

<the specific carbonic ester of 1-5-1.>

The specific example of specific carbonic ester can be enumerated and specific carbonic ester same in the present invention 1.

<the other additives of 1-5-2.>

In the following, being illustrated for other additives other than specific carbonic ester.As the addition other than specific carbonic ester Agent can enumerate overcharge preventing agent, auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics etc..

<1-5-2-1. overcharge preventing agent>

As the specific example of overcharge preventing agent, following aromatic compounds can be enumerated:

The toluene derivatives such as toluene, dimethylbenzene；

Biphenyl, 2- methyl biphenyl, 3- methyl biphenyl, 4- methyl biphenyl etc. are non-substituted or are derived by alkyl-substituted biphenyl Object；

Ortho-terphenyl, meta-terphenyl, para-terpheny etc. are non-substituted or by alkyl-substituted terphenyl derivatives；

Part hydride non-substituted or by alkyl-substituted terphenyl derivatives；

The naphthenic base benzene derivative such as cyclopenta benzene, cyclohexyl benzene；

Isopropylbenzene, 1,3- diisopropyl benzene, 1,4- diisopropyl benzene etc. have the alkane of tertiary carbon of the Direct Bonding on phenyl ring Base benzene derivative；

Tert-butyl benzene, tert-amyl benzene, tertiary hexyl benzene etc. have the benzene derivative of quaternary carbon of the Direct Bonding on phenyl ring；

Diphenyl ether, dibenzofurans etc. have the aromatic compound etc. of oxygen atom.

It should be noted that these overcharge preventing agents can be used alone a kind, 2 can also be used simultaneously in any combination Kind or more.In addition, in any combination simultaneously in use, belong to same category of compound in the above-mentioned example that can be used in combination, Different classes of compound can also be applied in combination.

Specific example when different classes of compound is applied in combination is identical as the present invention 1.

When the nonaqueous electrolytic solution of the present invention 2 contains overcharge preventing agent, concentration, its effect are identical as the present invention 1.

<1-5-2-2. auxiliary agent>

As the specific example of the auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics, can enumerate It is as follows:

The acid anhydrides of the dicarboxylic acids such as succinic acid, maleic acid, phthalic acid；

Carbonic acid erythrite ester, carbonic acid spiral shell-bis--dimethylene ester etc. is other than being equivalent to the carbonic ester of specific carbonic ester Carbonate products；

Sulfurous acid glycol ester, 1,3- propane sultone, 1,4- butyl sultone, methyl mesylate, 1,4-dimethane sulfonoxybutane, Sulfolane, cyclobufene sultone, dimethyl sulfone, diphenyl sulfone, methyl phenyl sulfone, dibutyl disulfide, dicyclohexyldisulfide, a sulphur Change tetra methylthiuram, N, N- dimethyl methyl sulfonamide, N, the sulfur-containing compounds such as N- diethyl Methanesulfomide；

1-Methyl-2-Pyrrolidone, 1- methyl -2- piperidones, 3- methyl -2-Oxazolidone, 1,3- dimethyl -2- imidazoles The nitrogenous compounds such as alkanone, N- methyl succimide；

<preparation method of 1-6. nonaqueous electrolytic solution>

The preparation method of nonaqueous electrolytic solution 2 is identical as the present invention 1.

[2. non-aqueous electrolyte secondary battery]

The non-aqueous electrolyte secondary battery of the present invention 2 has the nonaqueous electrolytic solution of aforementioned present invention 2 and can occlude and put The cathode and anode of ion out.

Battery structure；Cathode；Carbonaceous material；Structure, physical property, the preparation method of carbonaceous cathode；Metal compound species material, And structure, physical property, the preparation method of the cathode using metal compound species material；Anode；Partition；Battery design etc. and the present invention 1 record it is identical.

<effect>

By using simultaneously containing selected from the present invention 2 " the compound group of the present invention 2 " compound and mono-fluor phosphate Though and/or difluorophosphoric acid salt nonaqueous electrolytic solution and so that non-aqueous electrolyte secondary battery is shown the effect of high output characteristic, principle It is so also indefinite, but it is regarded as following mechanism.But the present invention 2 is not limited to effect below, principle.That is, as be described hereinafter " present invention 2 comparative examples 6 " like that, a degree of high output can also be obtained even if only containing difluorophosphoric acid salt, and such as " comparative example 2~5 of the present invention 2 " like that, the compound only selected from " the compound group of the present invention 2 " does not show then clear Effect, thus, it is believed that the compound of " present invention 2 compound groups " selected from the present invention 2 is to mono-fluor phosphate and difluoro Phosphatic effect has booster action.Specifically, it is believed that pass through compound and electrode selected from " the compound group of the present invention 2 " Interaction and make the mono-fluor phosphate for being improved effect to output or difluorophosphoric acid Salt treatment to electrode active material layer Deeper inside, to improve the interaction with electrode.

<nonaqueous electrolytic solution 3, non-aqueous electrolyte secondary battery 3>

[1. nonaqueous electrolytic solution]

The nonaqueous electrolytic solution of the present invention 3 is identical as common nonaqueous electrolytic solution, containing electrolyte and dissolves the electrolyte Nonaqueous solvents.

<1-1. electrolyte>

Electrolyte contained in nonaqueous electrolytic solution for the present invention 3 has no system limit, can be used arbitrarily and contain The well known electrolyte that can be used as electrolyte in target non-aqueous electrolyte secondary battery.It should be noted that this is sent out When bright 3 nonaqueous electrolytic solution is used for lithium ion secondary battery, it is preferable to use lithium salts for electrolyte.

As the specific example of electrolyte, such as it can enumerate and be documented in identical electrolyte in the present invention 1.

Wherein, preferably LiPF₆、LiBF₄、LiCF₃SO₃、LiN(CF₃SO₂)₂、LiN(C₂F₅SO₂)₂, two (oxalate conjunction) boric acid Lithium, particularly preferred LiPF₆Or LiBF₄。

The ratio of the type of electrolyte when for electrolyte is applied in combination, electrolyte when being applied in combination, and is documented in this Situation in the nonaqueous electrolytic solution of invention 1 is identical.

In addition, lithium salt, preferred concentration etc. in the final composition of the nonaqueous electrolytic solution of the present invention 3, non-with being documented in Situation in water electrolysis liquid 1 is identical.In addition, when deviateing numberical range there is a phenomenon where also be documented in nonaqueous electrolytic solution 1 The case where it is identical.

In particular, for nonaqueous electrolytic solution nonaqueous solvents with carbonic acid as alkylene carbonates or dialkyl carbonate It is the case where based on ester compounds, also identical as the situation in the nonaqueous electrolytic solution for being documented in the present invention 1.In addition, deviateing numerical value When range there is a situation where the phenomenon that also be documented in the present invention 1 nonaqueous electrolytic solution in it is identical.

In addition, when the gamma-butyrolacton containing 50 volume % or more, gamma-valerolactone in the nonaqueous solvents in nonaqueous electrolytic solution Etc. cyclic carboxylic acids ester compounds when, also be documented in the present invention 1 in situation it is identical.

<compound represented by 1-2. general formula (1)>

In the present invention 3, compound represented by general formula (1) is compound below.

[chemical formula 7]

[R¹、R²、R³、R⁴It is respectively independent, it is organic group or halogen atom, R¹、R²、R³、R⁴At least one of be direct with X The atom of bonding is heteroatomic group, R¹、R²、R³、R⁴Identical or different, X is the atom other than carbon atom.]

In the general formula (1) of the present invention 3, for X, as long as the atom other than carbon atom, is not particularly limited, but reflect In the stability etc. in nonaqueous electrolytic solution, preferably silicon atom or titanium atom.

R¹、R²、R³、R⁴Each independently represent organic group or halogen atom.The organic group is not particularly limited, " institute State organic group " in, it is the group of carbon atom as the atom being bonded with X, alkyl, alkene optionally with substituent group can be enumerated Base, alkynyl etc..The carbon atom number of these organic groups is more preferably 1~10.

Specifically, it as alkyl, can enumerate: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, isopropyl Base, isobutyl group, 2- methyl-propyl, 1- methyl butyl, 2- methyl butyl, 3- methyl butyl, 1,2- dimethyl propyl, neopentyl Deng；It as alkenyl, can enumerate: vinyl, allyl, isopropenyl, 1- acrylic, cyclobutenyl, butadienyl, pentenyl Deng；It as alkynyl, can enumerate: acetenyl, 1- propinyl, 1- butynyl, 1- pentynyl, 2-propynyl, 2- butynyl, 3- butine Base etc..

The substituent group of these groups is not particularly limited, and can enumerate: fluorine atom, chlorine atom, methacryloxy, mercapto Base, alkyl amino, arylamino, glycidoxy, benzoyloxy group, acetoxyl group etc..

It as halogen atom, can enumerate: fluorine atom, chlorine atom, bromine atom, iodine atom, particularly preferred chlorine atom or fluorine atom.

In addition, R¹、R²、R³、R⁴At least one of be with X-shaped at direct key atom be heteroatomic group.Hetero atom As long as the atom other than carbon atom, is not particularly limited, but since the reactivity of B, N, O, P, S or halogen atom is high, knot Fruit can get excellent cycle characteristics, therefore preferably.Wherein, particularly preferred halogen atom, oxygen atom or nitrogen-atoms.

In " atom with X Direct Bonding is heteroatomic group ", when hetero atom is oxygen atom, specifically, example can be enumerated Such as: methoxyl group, ethyoxyl, propoxyl group, butoxy, amoxy, isopropoxy, 1- methyl propoxyl group, 2- methyl propoxyl group, tertiary fourth The alkoxies such as oxygroup；Benzoyloxy group, acetoxyl group etc..In addition, when hetero atom is nitrogen-atoms, specifically, it can be mentioned, for example: diformazan Base amino, diethylamino, ethylmethylamino etc..Wherein, due to reason same as described above, more preferable methoxyl group, ethoxy The alkoxies such as base, propoxyl group, butoxy.

" atom with X Direct Bonding is heteroatomic group " can be halogen atom.Halogen atom at this time is preferably fluorine original Son, chlorine atom, bromine atom or iodine atom, due to reason same as described above, more preferable chlorine atom.

" atom with X Direct Bonding is heteroatomic group " optionally has substituent group, but due to reason same as described above By not having the alkoxy or chlorine atom of substituent group more preferably.

Represented by the general formula (1) in the present invention 3 for compound, R¹、R²、R³、R⁴In at least one be direct with X The atom of bonding is heteroatomic group, preferably R¹、R²、R³、R⁴In at least two be with the atom of X Direct Bonding be hetero atom Group, particularly preferred R¹、R²、R³、R⁴In 2 or 3 be " atom with X Direct Bonding is heteroatomic group ".This When, the excellent non-aqueous electrolyte for secondary battery of cycle characteristics can be obtained.

As its reason, when electrode interacts with " atom with X Direct Bonding is heteroatomic group ", if " being heteroatomic group with the atom of X Direct Bonding " is very few, then the very little sometimes of the interaction between these groups, in addition, Especially R¹、R²、R³、R⁴When this 4 groups are " being heteroatomic group with the atom of X Direct Bonding ", due to non-water power The group that solution liquid interacts disappears, and therefore, cannot be sufficiently carried out the stabilisation of electrode sometimes.

In general formula (1), R¹、R²、R³、R⁴It can be the same or different.

As the specific example of compound represented by 3 formula ofs (1) of the invention, it can be mentioned, for example: vinyl trichlorine silicon Alkane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, 3- methyl Acryloxypropyl triethoxysilane, 3- methacryloxypropyl methyl dimethoxysilane, 3- methacryloxypropyl third Ylmethyl diethoxy silane, 3- methyl allyl acyloxypropyl trimethoxysilane, 2- methacryloxypropyl trimethoxy Silane, 3- r-chloropropyl trimethoxyl silane, 3- mercaptopropyl trimethoxysilane, N- (2- aminoethyl)-γ-aminopropyl trimethoxy Silane, N- (2- aminoethyl)-gamma-aminopropyl-triethoxy-silane, N- (2- aminoethyl)-γ-aminopropyltriethoxy dimethoxy silicon Alkane, 3- aminopropyl trimethoxysilane, 3- aminopropyl triethoxysilane, N- phenyl -3- aminopropyl trimethoxysilane, 3- ring The third oxygen propyl trimethoxy silicane of oxygen, 3- epoxypropoxy triethoxysilane, (the positive butoxy carbonyl benzoyloxy group of 2-) three fourths Oxygroup titanium, diisopropoxy titanium diisostearate (ジ イ ソ プ ロ Port キ シ チ タ Application ジ イ ソ ス テ ア レ ー ト), stearic acid Titanium etc..Above compound can be used singly or in combination of two or more.

When X is titanium, preferably the chelate compounds such as acetylacetone,2,4-pentanedione, Acetacetic acid alkyl ester are coordinated titanium and what is formed has Machine titanium chelate compound etc..Above compound can be used singly or in combination of two or more.

<compound represented by 1-3. general formula (2)>

In the present invention 3, compound represented by general formula (2) is compound below.

[chemical formula 8]

[R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, R⁵、R⁶、R⁷At least one of be and Y Direct Bonding Atom be hetero atom (include halogen atom) group, R⁵、R⁶、R⁷Identical or different, Y is the atom other than carbon atom.]

In the general formula (2) of the present invention 3, R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, here, for organic Group or halogen atom, documented organic group or halogen atom are applicable in general formula (1).In addition, R⁵、R⁶、R⁷In at least one A be with the atom of Y Direct Bonding is heteroatomic group, for " hetero atom " and " is miscellaneous with the atom of Y Direct Bonding here The group of atom ", documented hetero atom and corresponding group are applicable in general formula (1).

For the Y in the general formula (2) of the present invention 3, if it is considered that stability etc. in the electrolytic solution, preferably aluminium atom.

R⁵、R⁶、R⁷At least one of be " being heteroatomic group with the atom of Y Direct Bonding ", but preferred R⁵、R⁶、R⁷ Any 2 be with Y shape at direct key atom be heteroatomic group.At this point it is possible to obtain excellent secondary of cycle characteristics Nonaqueous electrolyte for battery.

As its reason, when electrode interacts with " atom with Y Direct Bonding is heteroatomic group ", R⁵、R⁶、R⁷In " being heteroatomic group with the atom of Y Direct Bonding " it is very few in the case where, the interaction between these groups Sometimes too small, in addition, R¹、R²、R³When this 3 groups are " being heteroatomic group with the atom of Y Direct Bonding ", due to The group that nonaqueous electrolytic solution interacts disappears, and therefore, cannot be sufficiently carried out the stabilisation of electrode sometimes.

In general formula (2), R⁵、R⁶、R⁷It can be the same or different.

Specifically acetylacetone,2,4-pentanedione diisopropyl aluminium etc. can be enumerated as compound represented by 3 formula ofs (2) of the invention. These compounds can be used alone a kind, two or more can also be applied in combination.

For aluminium, other than the acetylacetone,2,4-pentanedione of above-mentioned concrete example, can also enumerate coordination has alkyl acetylacetonate Etc. the organo-aluminium chelate compound etc. of other chelate compounds.These compounds can be used alone a kind, can also be applied in combination 2 Kind or more.

<content of compound represented by compound represented by 1-4. general formula (1) and general formula (2)>

Compound represented by 3 formula ofs (1) of the invention, compound represented by 3 formula ofs (2) of the invention total amount exist Shared ratio is preferably the 0.001 weight % of weight %~10, particularly preferably 0.01 weight %~5 in nonaqueous electrolytic solution total amount The ratio of weight %.Relative to nonaqueous electrolytic solution total amount, compound represented by 3 formula ofs (1) of the invention leads in the present invention 3 It when the total content of compound represented by formula (2) is very few, cannot give full play to its effect, it is possible to it is excellent cycle characteristics cannot to be obtained Different non-aqueous electrolyte for secondary battery；On the other hand, lead in compound, the present invention 3 represented by 3 formula ofs (1) of the invention When the total content of compound represented by formula (2) is excessive, due to the reaction of its own, the capacity of battery is possible to impaired.

It is preferred that preparing nonaqueous electrolytic solution as follows, that is, relative to nonaqueous electrolytic solution total amount, 3 formula of of the present invention (1) of addition Or the total amount of compound represented by general formula (2) is 0.001 weight of weight %~10 %；In the present invention 3 particularly preferably added The total amount of compound represented by general formula (1) or general formula (2) is 0.01 weight of weight %~5 %.

<1-5. nonaqueous solvents>

Nonaqueous solvents contained by the nonaqueous electrolytic solution of the present invention 3 is non-aqueous contained by with the nonaqueous electrolytic solution of the present invention 1 Solvent is identical.

<1-6. mono-fluor phosphate, difluorophosphoric acid salt>

The nonaqueous electrolytic solution of the present invention 3 contains mono-fluor phosphate and/or difluorophosphoric acid salt as essential component.The present invention 3 Used in " mono-fluor phosphate and/or difluorophosphoric acid salt " and the present invention 1 used in " mono-fluor phosphate and/or difluorophosphoric acid Salt " is identical.

<the mono- fluorophosphoric acid metal salt of 1-6-1., difluorophosphoric acid metal salt>

Mono-fluor phosphate, difluorophosphoric acid salt in the present invention 3 be single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion with it is specific When salt (being denoted as " single fluorophosphoric acid metal salt ", " difluorophosphoric acid metal salt " respectively) that metal ion is formed, with the feelings in the present invention 1 Condition is identical.

< 1-6-2. mono- fluorophosphoric acid seasonSalt, difluorophosphoric acid seasonSalt >

Mono-fluor phosphate, difluorophosphoric acid salt in the present invention 3 are single fluorophosphoric acid radical ion, difluorophosphoric acid radical ion and season The salt of formation (is denoted as " single fluorophosphoric acid season respectivelySalt ", " difluorophosphoric acid seasonSalt ") when, also with the present invention 1 the case where it is identical.

<1-6-3. content, detection (source contained), technical scope etc.>

In the nonaqueous electrolytic solution of the present invention 3, a kind of mono-fluor phosphate or difluorophosphoric acid salt can be used only, it can also be to appoint The combination of meaning and ratio are applied in combination mono-fluor phosphate and/or difluorophosphoric acid salt of more than two kinds, but from keeping nonaqueous electrolyte secondary , it is preferable to use a kind of mono-fluor phosphate or difluorophosphoric acid salt from the viewpoint of battery effectively works.

In addition, the molecular weight of mono-fluor phosphate and difluorophosphoric acid salt, preparation method, ratio in nonaqueous electrolytic solution etc., It is identical illustrated in the present invention 1.

In addition, the detection period (period contained) of mono-fluor phosphate or difluorophosphoric acid salt, the place initially contained first (source contained), the method contained are considered as detection place etc. in nonaqueous electrolytic solution containing (or having contained), also with It is identical illustrated in the present invention 1.

<1-7. additive>

In the range of not destroying the effect of the present invention 3 significantly, it can also contain in the nonaqueous electrolytic solution of the present invention 3 various Additive.Add additive carry out prepare processing when, can arbitrarily use known additive.It should be noted that Additive can be used alone, can also in any combination and two or more is applied in combination in ratio.

As the example of additive, overcharge preventing agent can be enumerated, for improving the capacity maintenance characteristics after High temperature storage And auxiliary agent of cycle characteristics etc..Wherein, as the auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics, It is preferred that addition has the carbonic ester of at least one of unsaturated bond and halogen atom (hereinafter, can be also simply referred to as " specific carbonic acid Ester ").

<the specific carbonic ester of 1-7-1.>

The specific example of specific carbonic ester is identical as the present invention 1.

<the other additives of 1-7-2.>

As the additive other than specific carbonic ester, overcharge preventing agent can be enumerated, for improving the appearance after High temperature storage Measure retention performance and the auxiliary agent of cycle characteristics etc..The specific example and its concentration of overcharge preventing agent, its effect and auxiliary agent Specific example is documented identical with the present invention 1.

<preparation method of 1-6. nonaqueous electrolytic solution>

The preparation method of nonaqueous electrolytic solution 3 is identical as the present invention 1.

[2. non-aqueous electrolyte secondary battery]

The non-aqueous electrolyte secondary battery of the present invention 3 has the nonaqueous electrolytic solution of aforementioned present invention 3 and can occlude and put Out ion anode and cathode and constitute.In addition, the non-aqueous electrolyte secondary battery of the present invention 3 can also have other structures.

Battery structure；Cathode；Carbonaceous material；Structure, physical property, the preparation method of carbonaceous cathode；Metal compound species material, And structure, physical property, the preparation method of the cathode using metal compound species material；Anode；Partition；Battery design etc., with this hair Situation documented by bright 1 is identical.As negative electrode active material, as long as the substance of lithium ion can electrochemically be occluded and be released , it is not particularly limited.It is sub as its concrete example, carbonaceous material, alloy material, the metal composite oxygen containing lithium can be enumerated Compound material etc..Carbonaceous material, alloy material, metal compound species material, metallic composite oxides material containing lithium Respective specific example；Using the cathode of a variety of materials structure, physical property, preparation method also with the present invention 1 documented by situation It is identical.

<processing of electrode>

In addition, from that can obtain the excellent battery of cycle characteristics and inhibit to examine in terms of electrode surface Consider, preferably the nonaqueous electrolytic solution of the present invention 3 is used in following non-aqueous electrolyte secondary battery, the nonaqueous electrolyte is secondary Battery has the processed positive or negative pole of compound represented by the above-mentioned general formula (1) and/or general formula (2) of the present invention 3.

Using in compound represented by compound and general formula (2) represented by the general formula (1) selected from the present invention 3 at least The method that a kind of compound handles positive or negative pole is not particularly limited, but preferably makes general formula (1) institute table of the present invention 3 The method that compound represented by the compound and/or general formula (2) shown is evenly distributed on electrode surface, in particular it is especially preferred that By compound represented by compound and/or general formula (2) represented by the general formula (1) of the present invention 3 be dissolved or dispersed in solvent or In decentralized medium, the method that obtained liquid is impregnated or coated the electrode is reused.

Furthermore it is also possible to handle positive active material or negative electrode active material, which is also contained in the present invention 3 " processing of positive or negative pole " concept among.At this point it is possible to be handled as follows: the general formula (1) of the present invention 3 is represented Compound or general formula (2) represented by compound be dissolved or dispersed in solvent or decentralized medium, then the liquid made with Positive active material or negative electrode active material mixing, are thus handled；It can also be made using treated active material Positive or negative pole.In addition, in order to make chemical combination represented by compound represented by the general formula (1) of the present invention 3 and/or general formula (2) Interaction between object and electrode or electrode active material is stronger, preferably carries out at overheat to the electrode after processing Reason.Overtemperature is preferably 45 DEG C~300 DEG C, more preferably 60 DEG C~200 DEG C.

<nonaqueous electrolytic solution 4, non-aqueous electrolyte secondary battery 4>

[1. nonaqueous electrolytic solution]

The nonaqueous electrolytic solution of the present invention 4 is identical as common nonaqueous electrolytic solution, containing electrolyte and dissolves the electrolyte Nonaqueous solvents.

<1-1>lithium salts

The lithium salts contained in the nonaqueous electrolytic solution of the present invention 4 is not particularly limited, and can arbitrarily use target nonaqueous electrolyte The well known lithium salts used in secondary cell as electrolyte.As the specific example of lithium salts, for example, can enumerate with the present invention 1 in As the identical lithium salts of lithium salts documented by electrolyte.

The type of electrolyte when for electrolyte is applied in combination, when being applied in combination lithium salts ratio, with conduct in the present invention 1 Lithium salts documented by electrolyte is identical.

In addition, lithium salt, preferred concentration etc. in the final composition of the nonaqueous electrolytic solution 4 of the present invention 4, non-with being documented in Situation in water electrolysis liquid 1 is identical.In addition, when deviateing numberical range there is a phenomenon where also be documented in nonaqueous electrolytic solution 1 The case where it is identical.

In particular, for nonaqueous electrolytic solution nonaqueous solvents with carbonic acid as alkylene carbonates or dialkyl carbonate It is the case where based on ester compounds, also identical as situation about being documented in nonaqueous electrolytic solution 1.It is sent out when in addition, deviateing numberical range Raw phenomenon is also identical as situation about being documented in nonaqueous electrolytic solution 1.

<1-2. nonaqueous solvents>

The nonaqueous electrolytic solution of nonaqueous solvents and the present invention 1 contained by the nonaqueous electrolytic solution of the present invention 4 contains non-aqueous Solvent described in agent is identical.

<1-3>additive

The nonaqueous electrolytic solution of the present invention 4 must be containing compound represented by the following general formula (1), preferably further containing single Fluorophosphate and/or difluorophosphoric acid salt, it is also preferable to contain the carbonic acid at least one of unsaturated bond and halogen atom Ester.That is, containing compound represented by the following general formula (1) and " single fluorine in the embodiment 4-1 of the present invention 4 Phosphate and/or difluorophosphoric acid salt " is used as additive.In addition, in the embodiment 4-2 of the present invention 4, containing relative to non-aqueous Electrolyte total amount is compound represented by the general formula (1) of 0.001 weight of weight %~5 %, and containing relative to non-water power It solves " carbonic ester at least one of unsaturated bond and halogen atom " that liquid total amount is 0.001 weight of weight %~5 %.

Compound represented by<1-3-1>general formula (3)

About the nonaqueous electrolytic solution of the present invention 4, either embodiment 4-1 or embodiment 4-2 contain following Compound represented by the general formula (3) of invention 4 is as essential component.

[chemical formula 9]

[in general formula (3), A and B indicate various substituent groups, and at least one therein is fluorine, and n indicates 3 or more nature Number.]

In the above-mentioned general formula (3) of the present invention 4, A and B indicate various substituent groups, and at least one therein is fluorine.Fluorine removal Substituent group in addition is not particularly limited, but in view of its reactivity, preferably unsubstituted or by fluorine-substituted alkyl or aryl.Separately Outside, it is bonded with ehter bond with P between the preferably described alkyl or aryl and P by oxygen atom.That is, further preferably in the alkyl Or the group of oxygen atom is bonded on aryl.

Abovementioned alkyl, aryl carbon atom number be not particularly limited, but work as substituent group basic bone represented by general formula (3) When shared structure/weight ratio increases in frame, relative to the additive amount of compound represented by general formula (3), decreased effectiveness, In addition side effect, therefore preferably 10 or less carbon atom number, the alkyl or aryl below of more preferable carbon atom number 6 be there may also be, only For alkyl, more preferable carbon atom number is 3 or less.

It as the concrete example of these alkyl, can enumerate: methyl, methyl fluoride, difluoromethyl, trifluoromethyl, ethyl, 1- fluorine second Base, 2- fluoro ethyl, 1,1- bis-fluoro ethyls, 1,2- bis-fluoro ethyls, 2,2- bis-fluoro ethyls, 1,1,2- trifluoroethyl, 1,2,2- trifluoro Ethyl, 2,2,2- trifluoroethyl, tetra- fluoro ethyl of 1,1,2,2-, tetra- fluoro ethyl of 1,2,2,2-, pentafluoroethyl group, propyl (n-propyl), 1- fluoropropyl, 2- fluoropropyl, 3- fluoropropyl, bis- fluoropropyl of 1,1-, bis- fluoropropyl of 1,2-, bis- fluoropropyl of 1,3-, 2,2- difluoro third Base, bis- fluoropropyl of 2,3-, bis- fluoropropyl of 3,3-, 1,1,2- trifluoro propyl, 1,2,2- trifluoro propyl, 1,1,3- trifluoro propyl, 1, 2,3- trifluoro propyl, 1,3,3- trifluoro propyl, 2,2,3- trifluoro propyl, 2,3,3- trifluoro propyl, 3,3,3- trifluoro propyl, 1,1, Tetra- fluoropropyl of 2,2-, tetra- fluoropropyl of 1,1,2,3-, tetra- fluoropropyl of 1,1,3,3-, tetra- fluoropropyl of 1,2,2,3-, 1,2,3,3- tetrafluoro Propyl, tetra- fluoropropyl of 2,2,3,3-, tetra- fluoropropyl of 2,3,3,3-, 1,1,2,2,3- pentafluoropropyl group, 1,2,2,3,3- pentafluoropropyl group, 1,1,3,3,3- pentafluoropropyl group, 1,2,3,3,3- pentafluoropropyl group, 2,2,3,3,3- pentafluoropropyl group, 1,1,2,2,3,3- hexafluoro third Base, 1,1,2,3,3,3- hexafluoro propyl, 1,2,2,3,3,3- hexafluoro propyl, heptafluoropropyl, 1- Methylethyl (isopropyl), 1- The fluoro- 1- Methylethyl of fluoro- 1- Methylethyl, 2-, the fluoro- 1- Methylethyl of 1,2- bis-, 1,2- bis- fluoro- 1- (methyl fluoride) ethyl, 1, The fluoro- 1- Methylethyl of 2,2- tri-, the fluoro- 1- Methylethyl of 2,2,2- tri-, 2,2 ,-two fluoro- 1- (methyl fluoride) ethyls, 1,2,2,2- tetra- Fluoro- 1- Methylethyl, 1,2,2- tri- fluoro- 1- (methyl fluoride) ethyl, 2,2,2- tri- fluoro- 1- (methyl fluoride) ethyl, the fluoro- 1- of 2,2- bis- (difluoromethyl) ethyl, 1,2,2,2- tetra- fluoro- 1- (methyl fluoride) ethyl, 1,2,2- tri- fluoro- 1- (difluoromethyl) ethyl, 2,2,2- Three fluoro- 1- (difluoromethyl) ethyls, 1,2,2,2- tetra- fluoro- 1- (difluoromethyl) ethyl, 2,2,2- tri- fluoro- 1- (trifluoromethyl) second Base, 1,2,2,2- tetra- fluoro- 1- (trifluoromethyl) ethyl etc..

Wherein, from the point of view of easy to manufacture, more preferable methyl, methyl fluoride, trifluoromethyl, ethyl, 2- fluoro ethyl, 2, 2,2- trifluoroethyl, pentafluoroethyl group, propyl, 3- fluoropropyl, 3,3,3- trifluoro propyl, heptafluoropropyl, 1- Methylethyl, 1- are fluoro- The fluoro- 1- Methylethyl of 1- Methylethyl, 2-, 2- fluoro- 1- (methyl fluoride) ethyl, 2,2,2- tri- fluoro- 1- (trifluoromethyl) ethyl, 1, 2,2,2- tetra- fluoro- 1- (trifluoromethyl) ethyls, particularly preferred methyl, trifluoromethyl, ethyl, 2,2,2- trifluoroethyls, propyl, 1- Methylethyl.

It is preferably unsubstituted or by fluorine-substituted phenyl as aryl, it specifically, can enumerate: phenyl, 2- fluorophenyl, 3- fluorine Phenyl, 4- fluorophenyl, 2,3- difluorophenyl, 2,4 difluorobenzene base, 2,5- difluorophenyl, 2,6- difluorophenyl, 3,4- difluorobenzene Base, 3,5- difluorophenyl, 2,3,4- trifluorophenyl, 2,3,5- trifluorophenyl, 2,3,6- trifluorophenyl, 2,4,5- trifluorophenyl, 2,4,6- trifluorophenyl, 3,4,5- trifluorophenyl, 2,3,4,5- tetrafluoro phenyl, 2,3,4,6- tetrafluoro phenyl, 2,3,5,6- tetrafluoro Phenyl, pentafluorophenyl group etc..

Wherein, more preferable phenyl, 2- fluorophenyl, 3- fluorophenyl, 4- fluorophenyl, 2,3- difluorophenyl, 2,4- difluorophenyl, 2,5- difluorophenyl, 2,6- difluorophenyl, 3,4- difluorophenyl, 3,5- difluorophenyl, 2,3,4- trifluorophenyl, 2,3,5- trifluoro Phenyl, 2,3,6- trifluorophenyls, 2,4,5- trifluorophenyls, 2,4,6- trifluorophenyls, 3,4,5- trifluorophenyls, particularly preferred benzene Base.

In n repetitive unit, A can be the same or different, but preferably identical.In addition, B can in n repetitive unit It can also be different with identical, but preferably identical.

A or B is that the ratio of fluorine atom is not particularly limited, from the point of view of easy performance said effect, preferably A or B It is optimal preferably its ratio be 1/3 or more, more preferably 1/2 or more, particularly preferably 2/3 or more for the high person of ratio of fluorine atom The case where choosing is all fluorine.

From structural stability, n is necessary for 3 or more, but upper limit value is not particularly limited.

Compound represented by general formula (1) as the present invention 4, specifically, it can be mentioned, for example following compounds.

[chemical formula 10]

(the three phosphonitrile class of ring that hydrogen atom is all replaced by fluorine atoms)

(the three phosphonitrile class of ring with the methyl connected by oxygen)

(the three phosphonitrile class of ring with the ethyl connected by oxygen)

(the three phosphonitrile class of ring with the propyl connected by oxygen)

(the three phosphonitrile class of ring with the isopropyl connected by oxygen)

(the ring tricyclic nitrile with the phenyl connected by oxygen)

[chemical formula 11]

(the three phosphonitrile class of ring with the trifluoromethyl connected by oxygen)

(the three phosphonitrile class of ring with the trifluoroethyl connected by oxygen)

(the four phosphonitrile class of ring that hydrogen atom is all replaced by fluorine atoms)

(the four phosphonitrile class of ring with the methyl connected by oxygen)

(the four phosphonitrile class of ring with the ethyl connected by oxygen)

[chemical formula 12]

(the four phosphonitrile class of ring with the propyl connected by oxygen)

(the four phosphonitrile class of ring with the isopropyl connected by oxygen)

(the four phosphonitrile class of ring with the phenyl connected by oxygen)

(the four phosphonitrile class of ring with the trifluorophenyl connected by oxygen)

(the four phosphonitrile class of ring with the trifluoroethyl connected by oxygen)

[chemical formula 13]

(the five phosphonitrile class of ring that hydrogen atom is all replaced by fluorine atoms)

(the five phosphonitrile class of ring with the methyl connected by oxygen)

(the five phosphonitrile class of ring with the ethyl connected by oxygen)

[chemical formula 14]

(the five phosphonitrile class of ring with the propyl connected by oxygen)

(the five phosphonitrile class of ring with the isopropyl connected by oxygen)

(the five phosphonitrile class of ring with the phenyl connected by oxygen)

[chemical formula 15]

(the five phosphonitrile class of ring with the trifluoromethyl connected by oxygen)

(the five phosphonitrile class of ring with the trifluoroethyl connected by oxygen)

(the six phosphonitrile class of ring that hydrogen atom is all replaced by fluorine atoms)

[chemical formula 16]

(the six phosphonitrile class of ring with the methyl connected by oxygen)

(the six phosphonitrile class of ring with the ethyl connected by oxygen)

[chemical formula 17]

(the six phosphonitrile class of ring with the propyl connected by oxygen)

(the six phosphonitrile class of ring with the isopropyl connected by oxygen)

[chemical formula 18]

(the six phosphonitrile class of ring with the phenyl connected by oxygen)

(the six phosphonitrile class of ring with the trifluorophenyl connected by oxygen)

[chemical formula 19]

(the six phosphonitrile class of ring with the trifluoroethyl connected by oxygen)

In embodiment 4-1, these contained in nonaqueous electrolytic solution are with chemical combination represented by the general formula (3) of the present invention 4 The ratio of object is not particularly limited, but the range of preferably 0.001 weight of weight %~2 %, more preferable 0.01 weight %~1.7 weight Measure the range of %, the range of the particularly preferred 0.05 weight weight of %~1.3 %, the further preferred 0.1 weight weight of %~1 % Range.Additionally, it is preferred that the range of 0.001 volume of volume %~1 %, the range of the more preferable 0.01 volume volume of %~0.8 %, spy The not preferably range of 0.05 volume of volume %~0.7 %, the range of the further preferred 0.1 volume volume of %~0.5 %.

In addition, these contained in nonaqueous electrolytic solution are represented by the general formula (3) of the present invention 4 in embodiment 4-2 The ratio of compound be necessary for the range of 0.001 weight of weight %~5 %, the range of the more preferable 0.01 weight weight of %~3 %, The range of the range of the particularly preferred 0.05 weight weight of %~2 %, the further preferred 0.1 weight weight of %~1 %.In addition, excellent Select the range of 0.001 volume of volume %~3 %, the range of the more preferable 0.01 volume volume of %~2 %, particularly preferred 0.05 body Range, the range of the further preferred 0.1 volume volume of %~0.5 % of the product volume of %~1 %.

Above-mentioned " volume % " compound represented by 4 general formula (3) is calculated in the density of room temperature according to the present invention.

No matter in embodiment 4-1 or in embodiment 4-2, these contained in nonaqueous electrolytic solution are with the present invention The ratio of compound represented by 4 general formula (3) is both preferably 0.001 weight % or more and 0.001 volume % or more, more preferably 0.01 weight % or more and 0.01 volume % or more, particularly preferred 0.05 weight % or more and 0.05 volume % or more, further It is preferred that 0.1 weight % or more and 0.1 volume % or more.Additionally, it is preferred that the upper limit is 2 weight % or less and 1 volume % or less.If this The concentration of compound represented by the general formula (3) of invention 4 is too low, then is sometimes difficult to obtain the improvement of discharge load characteristic, If opposite excessive concentration occasionally results in efficiency for charge-discharge reduction.It should be noted that the general formula containing two or more present invention 4 (3) when compound represented by, above-mentioned content refers to its total amount.

<1-4. mono-fluor phosphate, difluorophosphoric acid salt>

" mono-fluor phosphate and/or difluorophosphoric acid salt " used in the present invention 4 is identical as the present invention 1.Preferred range It is identical as invention 1.

<the mono- fluorophosphoric acid metal salt of 1-4-1., difluorophosphoric acid metal salt>

Mono-fluor phosphate, difluorophosphoric acid salt firstly, for the present invention 4 be single fluorophosphoric acid radical ion, difluorophosphoric acid root from The case where salt that son is formed with special metal ion, concrete example can be enumerated and 1 identical example of the invention.

< 1-4-2. mono- fluorophosphoric acid seasonSalt, difluorophosphoric acid seasonSalt >

Then, for the mono-fluor phosphate of the present invention 4, difluorophosphoric acid salt be single fluorophosphoric acid radical ion, difluorophosphoric acid root from Son and seasonIn the case where the salt of formation, concrete example can be enumerated and 1 identical example of the invention.

<1-4-3. content, detection (source contained), technical scope etc.>

In the nonaqueous electrolytic solution of the present invention 4, a kind of mono-fluor phosphate or difluorophosphoric acid salt can be used only, it can also be with Two or more mono-fluor phosphate and/or difluorophosphoric acid salt is applied in combination in any combination and ratio, from making non-aqueous electrolyte secondary battery , it is preferable to use a kind of mono-fluor phosphate or difluorophosphoric acid salt from the viewpoint of efficient operation.

In addition, mono-fluor phosphate, the molecular weight of difluorophosphoric acid salt, manufacturing method, ratio in nonaqueous electrolytic solution etc. are It is identical illustrated in the present invention 1.

In addition, the detection period (period contained) of mono-fluor phosphate or difluorophosphoric acid salt, the place initially contained first (source contained), the method contained are considered as detection place etc. in nonaqueous electrolytic solution containing (or having contained), also with It is identical illustrated in the present invention 1.

<1-5-1>specific carbonic ester

In embodiment 4-1, preferably addition have at least one of unsaturated bond and halogen atom carbonic ester (hereinafter, Sometimes referred to simply as " specific carbonic ester ") as compound, mono-fluor phosphate or difluoro represented by the general formula (1) except the present invention 4 Additive other than phosphate, and must then be added at least one of unsaturated bond and halogen atom in embodiment 4-2 Carbonic ester (hereinafter, sometimes referred to simply as " specific carbonic ester ") as compound, list represented by the general formula (1) except of the invention 4 Additive other than fluorophosphate or difluorophosphoric acid salt.When containing specific carbonic ester, have the effect of preventing overcharge, but also Capacity maintenance characteristics, cycle characteristics after High temperature storage can be improved etc..

Specific carbonic ester can only contain unsaturated bond, can also only contain halogen atom, can also containing unsaturated bond and Both halogen atoms.

Specific carbonic ester is identical as specific carbonic ester described in the present invention 1.

<1-5-2>other additives

In the range of not influencing the effect of the present invention 4, the nonaqueous electrolytic solution of the present invention 4 can also further contain overcharge " other additives " such as preventing agent, auxiliary agents for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics.As it Its additive can arbitrarily use known additive.The concrete example and its concentration of overcharge preventing agent, its effect etc. with It is documented identical in the present invention 1.

In addition, these overcharge preventing agents can be used alone a kind, two or more can also be applied in combination in any combination.Separately Outside, when two or more overcharge preventing agent being applied in combination in any combination, the change of the above-mentioned same category enumerated can be applied in combination Object is closed, the compound of different classifications can also be applied in combination.

The concrete example of the case where as the compound that different classifications are applied in combination can be enumerated and 1 identical example of the invention Son.

In addition, the specific example as the auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics, It in addition to auxiliary agent, can also enumerate: the phosphates such as trimethyl phosphate, triethyl phosphate, triphenyl phosphate cited by the present invention 1 Class；The phosphorous acid esters such as Trimethyl phosphite, triethyl phosphite, triphenyl phosphite；Trimethyl phosphine oxide, triethyl group oxidation Phosphorus-containing compounds such as the phosphinoxides such as phosphine, triphenylphosphine oxide etc..

These " other additives " are not particularly limited relative to the additive amount of the nonaqueous electrolytic solution of the present invention 4, as long as not The effect of the present invention 4 is significantly affected, can be arbitrary additive amount, it is usually uncommon relative to the nonaqueous electrolytic solution of the present invention 4 Hope the concentration containing 0.01 weight % or more, the concentration for preferably comprising 0.1 weight % or more, further preferably 0.3 weight % with On concentration, and it is generally desirable to containing 10 weight % concentration below, preferably comprise 5 weight % concentration below, more preferably contain There are 3 weight % concentration below, further preferably 2 weight % concentration below.

<preparation method of 1-6. nonaqueous electrolytic solution>

The preparation method of the nonaqueous electrolytic solution of the present invention 4 is identical as the present invention 1.

[2. non-aqueous electrolyte secondary battery]

The non-aqueous electrolyte secondary battery of the present invention 4 has the nonaqueous electrolytic solution of aforementioned present invention 4 and can occlude and put The cathode and anode of ion out.

Battery structure；Cathode；Carbonaceous material；Structure, physical property, the preparation method of carbonaceous cathode；Metal compound species material, And structure, physical property, the preparation method of the cathode using metal compound species material；Anode；Partition；Battery design etc. with this hair It is identical documented by bright 1.

By optimizing above structure, internal resistance can be minimized.In the battery used with high current, preferably It is 10 milliohms (m Ω) hereinafter, more preferably straight with the impedance (hreinafter referred to as " DC resistance component ") that 10kHz alternating current method measures Leakage resistance ingredient be 5 milliohms (m Ω) below.

When DC resistance component is 0.1 milliohm or less, high output characteristic is improved, but used current collecting material sometimes The shared ratio of material increases, and battery capacity is reduced.

The nonaqueous electrolytic solution of the present invention 4 is produced for reducing because (de- Inserted enters) is detached from and be inserted into electrode active material for lithium There is effect, this can be achieved on the major reason of good cryogenic discharging characteristic in terms of raw reaction resistance.But common It in battery of the D.C. resistance greater than 10 milliohms (m Ω), is influenced sometimes by D.C. resistance, the effect that reaction resistance reduces cannot 100% is reflected on cryogenic discharging characteristic.Therefore, the battery few by using DC resistance component, can improve such case, from And the effect of the nonaqueous electrolytic solution of the present invention 4 can be given full play to.

In addition, from the viewpoint for the battery of effect, production with high cryogenic discharging characteristic for giving full play to nonaqueous electrolytic solution Consider, particularly preferably meet above-mentioned condition and condition below simultaneously: 1 battery case for being accommodated in above-mentioned secondary cell is (outer Dress) in cell device (important document) possessed by capacitor (capacitor when battery to be discharged to by fully charged state to discharge condition) be It is more than 3 ampere-hours (Ah).

<nonaqueous electrolytic solution 5, non-aqueous electrolyte secondary battery 5>

[1. nonaqueous electrolytic solution]

The nonaqueous electrolytic solution of the present invention 5 is identical as common nonaqueous electrolytic solution, containing lithium salts and dissolves the room temperature of the lithium salts Fuse salt, and usually using them as main component.

<1-1>lithium salts

Lithium salts contained in nonaqueous electrolytic solution for the present invention 5 is not particularly limited, can be arbitrarily non-aqueous using target The known lithium salts used in electrolyte secondary battery as electrolyte.As the specific example of lithium salts, such as the present invention 1 can be enumerated It is middle to be used as lithium salts documented by electrolyte.

Type, the ratio of lithium salts at this time about electrolyte when lithium salts is applied in combination, and make in nonaqueous electrolytic solution 1 It is identical documented by electrolyte.

The concentration of lithium salts in nonaqueous electrolytic solution is not particularly limited, usually 0.1mol/L or more, preferably 0.2mol/L or more, more preferably 0.3mol/L or more.In addition, its upper limit be usually 3mol/L or less, preferably 2mol/L with Under, more preferably 1.8mol/L or less, particularly preferably 1.5mol/L or less.If the concentration of lithium salts is too low, sometimes non-aqueous The conductivity of electrolyte is insufficient, and on the other hand, if the excessive concentration of lithium salts, since viscosity increases, conductivity is reduced, electricity Pond performance is likely to decrease.

The nonaqueous electrolytic solution of the present invention 5 contains lithium salts and room temperature fuse salt.Also, contain in the nonaqueous electrolytic solution " being selected from least one of mono-fluor phosphate and difluorophosphoric acid salt compound ".

<1-2. room temperature fuse salt>

In the present invention 5 described " room temperature fuse salt " refer to 1 molecular structure by 1 or 1 or more cation and yin from The ionic substance (salt) that son is constituted, and some or all of the salt is the substance of liquid at 45 DEG C.In addition, even by The compound that the fusing point that heat analysis measures is 45 DEG C or more, as long as it was kept by the operation such as quenching at 45 DEG C steadily in the long term Cold state and exist in liquid form, can also be included in the present invention 5 room temperature fuse salt range.Even in addition, being at 45 DEG C The salt of solid state, when the salt can by with other ionic objects such as lithium salts, mono-fluor phosphate class or difluorophosphoric acid salt When matter mixes and becomes liquid condition at 45 DEG C, which can also be included in the range of the room temperature fuse salt of the present invention 5.

It is not particularly limited as room temperature fuse salt used in the present invention 5 as long as meeting above-mentioned condition, wherein It is the room temperature fuse salt of liquid condition more preferably at 15 DEG C, especially it is preferred that being the room temperature fuse salt of liquid condition at 25 DEG C It is preferred that being the room temperature fuse salt of liquid condition at 10 DEG C.

The cationic structural for forming room temperature fuse salt is not particularly limited, and the cationic structural formed by organic matter is at 45 DEG C Easily become liquid condition, therefore preferably.Containing selected from the tertiary sulfonium with structure shown in the following general formula (6) in the nonaqueous electrolytic solution Salt, the quaternary ammonium salt with structure shown in the following general formula (7) and the season with structure shown in the following general formula (8)At least 1 in salt When kind room temperature fuse salt, viscosity is low, therefore more preferably.

[chemical formula 20]

[in general formula (6), R_1r、R_2rAnd R_3rEach independently represent the organic group of carbon atom number 1~12.R_1r、R_2rWith R_3rIn 2 organic groups it is optionally mutually bonded and form ring structure.]

[chemical formula 21]

[in general formula (7), R_4r、R_5r、R_6rAnd R_7rEach independently represent the organic group of carbon atom number 1~12.R_4r、 R_5r、R_6rAnd R_7rIn 2~4 organic groups it is optionally mutually bonded and form ring structure or R_4r、R_5r、R_6rAnd R_7rIn 2 Organic group is actually 1 organic group, 1 organic group and " N⁺" connected with double bond between atom.]

[chemical formula 22]

[in general formula (8), R_8r、R_9r、R_10rAnd R_11rEach independently represent the organic group of carbon atom number 1~12.R_8r、 R_9r、R_10rAnd R_11rIn 2~4 organic groups it is optionally mutually bonded and form ring structure or R_8r、R_9r、R_10rAnd R_11rIn 2 organic groups are actually 1 organic group, 1 organic group and " P⁺" connected with double bond between atom.]

[compound represented by general formula (6)]

R in sulfonium cation structure represented by the above-mentioned general formula (6) of the present invention 5_1r、R_2rAnd R_3rIt is identical or different The organic group of carbon atom number 1~12, as R_1r、R_2rAnd R_3r, can enumerate: methyl, ethyl, n-propyl, isopropyl, butyl, different The chain-like alkyls such as butyl, sec-butyl, tert-butyl；The cyclic alkyls such as cyclohexyl, norborny；Vinyl, 1- acrylic, allyl The alkenyls such as base, cyclobutenyl, 1,3- butadienyl；The alkynyls such as acetenyl, propinyl, butynyl；Trifluoromethyl, trifluoroethyl, The halogenated alkyls such as hexafluoro propyl；Optionally there are the aryl such as the phenyl of substituent groups such as alkyl substituent；The aralkyls such as benzyl, phenylethyl Base；The trialkylsilkls such as trimethyl silyl；The alkyl containing carbonyl such as ethoxycarbonyl-ethyl；Methoxy ethyl, benzene Oxygroup methyl, ethoxyethyl group, allyloxy ethyl, methoxyethoxyethyl, ethoxyethoxyethyl etc. contain ether Alkyl；The alkyl etc. containing sulfonyl such as sulfonvlmethvl.

R in the sulfonium cation structure_1r、R_2rAnd R_3rIt is optionally mutually bonded and form ring structure, R_1r、R_2rAnd R_3rIt can be with The saturation or unsaturated bond formed on above-mentioned substituent group by miscellaneous member such as oxygen, nitrogen, sulphur, P elements is combined with substituent group.

In R_1r、R_2rAnd R_3rIn, alkyl, halogenated alkyl, allyl, the alkyl containing ether of carbon atom number 1~6 pass through Reduce the intermolecular interaction of the sulfonium salt, low-melting salt easy to form, therefore preferably.

Wherein, since viscosity is easily reduced, particularly preferred trimethylsulfonium, triethyl group sulfonium, dimethyl ethyl sulfonium, Methyl diethyl sulfonium, tripropyl sulfonium, dimethyl propyl sulfonium, methyl dipropyl sulfonium, diethylpropyl sulfonium, ethyl dipropyl sulfonium, first Base ethyl propyl sulfonium, tributyl sulfonium, dimethylbutyl sulfonium, methyl dibutyl sulfonium, diethyl butyl sulfonium, ethyl dibutyl sulfonium, two Butyl sulfonium, propyl dibutyl sulfonium, Methylethyl butyl sulfonium, methyl-propyl butyl sulfonium, ethyl propyl butyl sulfonium or these alkane 1 or more hydrogen atom in base is replaced by fluorine atoms and the compound that is formed；Dimethyl ethenyl sulfonium, dimethyl-allyl sulfonium, Dimethyl butyrate alkenyl sulfonium, diethyl vinyl sulfonium, diethyl allyl sulfonium, diethyl cyclobutenyl sulfonium, Methylethyl vinyl sulfonium, Methylethyl allyl sulfonium, Methylethyl cyclobutenyl sulfonium, dimethyl methoxy sulfonium, dimethyl methoxy ethyl sulfonium, diformazan Base oxethyl methyl sulfonium, dimethylethyloxy ethyl sulfonium, dimethyl methoxyethoxyethyl sulfonium, dimethylethoxy base oxethyl Ethyl sulfonium, diethyl ylmethoxymethyl sulfonium, diethyl methoxy ethyl sulfonium, diethyl ethoxy ethyl sulfonium, diethyl ylmethoxy Ethoxyethyl group sulfonium, diethyl ethoxy ethoxyethyl group sulfonium etc..

The anion of tertiary sulfonium salt as structure represented by the above-mentioned general formula (6) with the present invention 5, does not limit especially Fixed, the van der Waals radius of anion isAbove tertiary sulfonium salt easily becomes liquid condition at 45 DEG C or less, therefore excellent Choosing.Wherein, the anion structure that the element with negative electrical charge is formed in conjunction with electron-attracting substituent in form is at room temperature Liquid condition is easily become, therefore more preferably.

Wherein, from heat resistance and oxidative resistance it is good from the point of view of, particularly preferred electron-attracting substituent be fluorine atom； Cyano；Containing fluorine, cyano, alkyl, fluoro-alkyl, cyaniding alkyl, phenyl, difluorophenyl, the carbonyl with cyaniding phenyl, and Carboxyl, sulfonic group, sulfonyl；Phenyl, difluorophenyl, the phenyl containing fluoro-alkyl, cyano-phenyl；Phenoxy group, fluorobenzene oxygen Base, the phenyl containing fluoro-alkyl, cyaniding phenoxy group；The thio phenoxy group of thio phenoxy group, fluoro contains the thio of fluoro-alkyl Phenoxy group, the thio phenoxy group of cyaniding；Fluoroalkyl, cyaniding alkoxy；Fluoro thio alkoxy, cyaniding thio alkoxy.

In addition, BF₃Or AlF₃、PF₃、PF₅、SbF₅、AsF₅Equal Lewis Acidic compounds, by in anion structure Negative electrical charge position interacts and forms the strong anion of oxidative resistance, therefore identical as above-mentioned electron-attracting substituent group, It can be used as particularly preferred substituent group.

In above-mentioned substituent group, due to be suitable for nonaqueous electrolyte battery when ionic conductivity, viscosity, oxidation/ The balance of Reductive stability, efficiency for charge-discharge, High temperature storage stability etc. is good, therefore, most preferably BF₄ ^-、AlF₄ ^-、ClO₄ ^-、 PF₆ ^-、SbF₆ ^-、SiF₆ ^2-、AsF₆ ^-、WF₇ ^-、CO₃ ^2-、FSO₃ ^-、(FSO₂)₂N^-、(FSO₂)₃C^-、NO₃ ^-、PO₄ ^3-、PO₃F^-、PO₂F₂ ^-、 B₁₂F₁₂ ^2-Equal inorganic anions；(CN)₂N^-、(CNCO)₂N^-、(CNSO₂)₂N^-、(CF₃CO)₂N^-、(CF₃CF₂CO)₂N^-、(CF₃SO₂)₂N^-、(CF₃CO)(CF₃SO₂)N^-、(CF₃SO₂)(CF₃CF₂SO₂)N^-、(CF₃CF₂SO₂)₂N^-、(CF₃SO₂)(C₄F₉SO₂)N^-, ring-type 1, 2- perfluor second di-sulfonyl imides, the third di-sulfonyl imides of ring-type 1,3- perfluor, (CN)₃C^-、(CNCO)₃C^-、(CNSO₂)₃C^-、(FSO₂)₃C^-、(CF₃CO)₃C^-、(CF₃CF₂CO)₃C^-、(CF₃SO₂)₃C^-、CF₃BF₃ ^-、CF₃CF₂BF₃ ^-、CF₃CF₂CF₂BF₃ ^-、(CF₃CO)BF₃ ^-、 (CF₃SO₂)BF₃ ^-、(CF₃CF₂SO₂)BF₃ ^-、(CF₃)₂BF₂ ^-、(CF₃CF₂)₂BF₂ ^-、(CF₃SO₂)₂BF₂ ^-、(CF₃CF₂SO₂)₂BF₂ ^-、 (CF₃)₃BF^-、(CF₃CF₂)₃BF^-、(CF₃CO)₃BF^-、(CF₃SO₂)₃BF^-、(CF₃CF₂SO₂)₃BF^-、(CF₃)₄B^-、(CF₃CF₂)₄B^-、 (C₆F₅)₄B^-、(CF₃CO₂)₄B^-、(CF₃SO₃)₄B^-、(CF₃CF₂SO₃)₄B^-、((CF₃)₃CO)₄B^-、((CF₃)₂CHO)₄B^-、(Ph (CF₃)₂CO)₄B^-、(C₆F₅O)₄B^-、(CF₃CO)₄Al^-、(CF₃SO₂)₄Al^-、(CF₃CF₂SO₂)₄Al^-、((CF₃)₃CO)₄Al^-、 ((CF₃)₂CHO)₄Al^-、(Ph(CF₃)₂CO)₄Al^-、(C₆F₅O)₄Al^-、(CF₃)₂PF₄ ^-、(C₂F₅)₂PF₄ ^-、(CF₃SO₂)₂PF₄ ^-、 (C₂F₅SO₂)₂PF₄ ^-、(CF₃)₃PF₃ ^-、(C₂F₅)₃PF₃ ^-、(CF₃SO₂)₃PF₃ ^-、(C₂F₅SO₂)₃PF₃ ^-、(CF₃)₄PF₂ ^-、(C₂F₅)₄PF₂ ^-、(CF₃SO₂)₄PF₂ ^-、(C₂F₅SO₂)₄PF₂ ^-Equal organic anions；Two (oxalate conjunction) borates, three (oxalate conjunction) phosphoric acid Salt, difluoro oxalate root close the anion containing dicarboxyl acid complex such as borate.

[compound represented by general formula (7)]

R in quaternary ammonium salt cationic structure represented by the above-mentioned general formula (7) of the present invention 5_4r、R_5r、R_6rAnd R_7rBe it is identical or The organic group of different carbon atom numbers 1~12, as R_4r、R_5r、R_6rAnd R_7r, can enumerate and " the R in general formula (6)_1r、R_2rWith R_3r" identical chain-like alkyl；Cyclic alkyl；Alkenyl；Alkynyl；Halogenated alkyl；The virtues such as the phenyl optionally with alkyl substituent Base；Aralkyl；Trialkylsilkl；Alkyl containing carbonyl；Alkyl containing ether；Alkyl etc. containing sulfonyl.This Outside, preferred specific group also with the " R in above-mentioned general formula (6)_1r、R_2rAnd R₃" identical.

R_4r、R_5r、R_6rAnd R_7rIn 2~4 optionally mutually bonded and form ring structure, R_4r、R_5r、R_6rAnd R_7rIt can be with The saturation or unsaturated bond formed on above-mentioned substituent group by the miscellaneous element such as oxygen, nitrogen, sulphur, P elements is combined with substituent group.

In the quaternary ammonium salt cationic structure of above-mentioned shown general formula (7), in chain ammonium cation, as R_4r、R_5r、R_6r And R_7r, preferred alkyl, halogenated alkyl, allyl, the alkyl containing ether of carbon atom number 1~6, because they should by reducing The intermolecular interaction of ammonium salt and low-melting salt easy to form.

Wherein, from the point of view of being easy to reduction from viscosity, more preferable trimethylpropylammonium, trimethyl butyl ammonium, three Methyl amyl ammonium, trimethyl ammonium, dimethylethylpropylammonium, dimethyl ethyl butyl ammonium, dimethyl ethyl amyl ammonium, two Methylethyl hexyl ammonium, dimethyl dipropylammonium, dimethyl propyl butyl ammonium, dimethyl propyl amyl ammonium, dimethyl propyl oneself Base ammonium, dimethyl dibutyl ammonium, dimethylbutyl amyl ammonium, dimethylbutyl hexyl ammonium, dimethyl diamyl ammonium, dimethyl-penten Base hexyl ammonium, dimethyl dihexyl ammonium, methyl diethylpropyl ammonium, methyl diethyl butyl ammonium, methyl diethyl amyl group ammonium, first Base diethylhexyl ammonium, Methylethyl dipropylammonium, Methylethyl butyl ammonium, Methylethyl propylpentyl ammonium, methyl second Base propyl hexyl ammonium, Methylethyl dibutyl ammonium, Methylethyl butyl amyl ammonium, Methylethyl butyl hexyl ammonium, Methylethyl Diamyl ammonium, Methylethyl amyl hexyl ammonium, Methylethyl dihexyl ammonium, methyl tripropyl ammonium, methyl dipropyl butyl ammonium, first Base dipropyl amyl ammonium, methyl dipropyl hexyl ammonium, methyl-propyl dibutyl ammonium, methyl-propyl butyl amyl ammonium, methyl-propyl Butyl hexyl ammonium, methyl-propyl diamyl ammonium, methyl-propyl amyl hexyl ammonium, methyl-propyl dihexyl ammonium, methyltributylammoni,m, Methyl dibutyl amyl ammonium, methyl dibutyl hexyl ammonium, methyl butyl diamyl ammonium, methyl butyl amyl hexyl ammonium, methyl fourth Base dihexyl ammonium, three amyl ammonium of methyl, methyl diamyl hexyl ammonium, methyl amyl dihexyl ammonium, three hexyl ammonium of methyl, triethyl group Hydrogen atom in propyl ammonium, triethyl group butyl ammonium, triethyl group amyl ammonium, triethyl group hexyl ammonium etc. or these alkyl is by 1 or more Fluorine atom replaces and compound, the trimethyl allyl ammonium, trimethylbutene base ammonium, trimethyl methoxy methyl ammonium, three of formation Methyl methoxy base ethyl ammonium, trimethyl methoxy ethoxyethyl group ammonium etc..

Wherein, will not become excessive, unit volume number of ions (i.e. ion concentration) from cation size is not influence often Warm fuse salt feature it is appropriately sized, and with the balance of fusing point, viscosity it is good from the point of view of, particularly preferred trimethyl third Base ammonium, trimethyl butyl ammonium, tri-methyl-amyl ammonium, trimethyl ammonium, dimethylethylpropylammonium, dimethyl ethyl butyl Ammonium, dimethyl ethyl amyl ammonium, dimethyl ethyl hexyl ammonium, dimethyl propyl butyl ammonium, dimethyl propyl amyl ammonium, dimethyl Propyl hexyl ammonium, triethyl group propyl ammonium, triethyl group butyl ammonium, triethyl group amyl ammonium, triethyl group hexyl ammonium etc. and these alkyl In hydrogen atom by 1 or more fluorine atom replaces and is formed compound, trimethyl allyl ammonium, trimethylbutene base ammonium, three Methyl methoxy ylmethyl ammonium, trimethyl methoxy ethyl ammonium etc..

In the quaternary ammonium cation structure of above-mentioned general formula (7), R_4r、R_5r、R_6rAnd R_7rIn 2~4 it is optionally mutually bonded and Form ring structure, wherein general formula (9) below, general formula (10), saturated heterocyclic structure is easy to form low represented by general formula (11) The salt of fusing point, therefore preferably.In the following general formula (9), general formula (10) and general formula (11), R_12a、R_13a、R_12b、R_13b、R_12c、R_13c With " the R that can be mutually different in general formula (7)_4r、R_5r、R_6rAnd R_7r" identical.

[chemical formula 23]

[chemical formula 24]

[chemical formula 25]

The pyrrolidines shown in above-mentioned general formula (9)In cation, from the point of view of room temperature fuse salt easy to form, more It is preferred that dimethyl pyrrolidineEryptopyrrole alkaneDiethyl pyrrolidinesMethyl-propyl pyrrolidinesEthyl third Base pyrrolidinesDipropyl pyrrolidinesMethyl butyl pyrrolidinesEthyl-butyl pyrrolidinesButyl pyrrolidinesDibutyl pyrrolidinesOr the hydrogen atom in these alkyl is by 1 or more fluorine atom replaces and is formed compound, methyl Ethenyl pyrrolidoneEthyl vinyl pyrrolidinesPropyl ethylene base pyrrolidinesButyl vinyl pyrrolidinesFirst Base allylpyrrolidineAllyl ethyl pyrrolidinesAllyl pyrrolidinesButyl allylpyrrolidine Diallyl pyrrolidinesMethyl butene base pyrrolidinesEthyl cyclobutenyl pyrrolidinesPropyl cyclobutenyl pyrrolidines Butyl cyclobutenyl pyrrolidinesDibutene base pyrrolidinesMethyl methoxy ylmethylpyrrolidineMethyl methoxy base ethyl pyrrole Cough up alkaneMethyl ethoxy ethyl pyrrolidineMethyl methoxy base oxethyl ethyl pyrrolidineMethylethoxy base oxethyl Ethyl pyrrolidineEthyl methoxymethylpyrrolidineEthyl methoxy ethyl pyrrolidinesEthyl ethoxyethyl group pyrrole Cough up alkaneEthyl methoxyethoxyethyl pyrrolidinesEthyl ethoxyethoxyethyl pyrrolidinesPropylmethoxy CrassitudePropylmethoxy ethyl pyrrolidinePropyl ethoxyethyl group pyrrolidinesPropylmethoxy ethyoxyl Ethyl pyrrolidinePropyl ethoxyethoxyethyl pyrrolidinesButylmethoxy crassitudeButylmethoxy Ethyl pyrrolidineButyl ethoxyethyl group pyrrolidinesButylmethoxy ethoxyethyl group pyrrolidinesButyl ethyoxyl Ethoxyethyl group pyrrolidinesDeng.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred eryptopyrrole alkaneMethyl-propyl pyrrole Cough up alkaneEthyl propyl pyrrolidinesMethyl butyl pyrrolidinesEthyl-butyl pyrrolidinesOr the hydrogen in these alkyl Atom is by compound, the methacrylic pyrrolidines that 1 or more fluorine atom replaces and is formedAllyl ethyl pyrrolidines Allyl pyrrolidinesButyl allylpyrrolidineMethyl butene base pyrrolidinesEthyl cyclobutenyl pyrrolidinesPropyl cyclobutenyl pyrrolidinesButyl cyclobutenyl pyrrolidinesMethyl methoxy ylmethylpyrrolidineMethyl methoxy base Ethyl pyrrolidineEthyl methoxymethylpyrrolidineEthyl methoxy ethyl pyrrolidinesDeng.

The piperidines represented by above-mentioned general formula (10)In cation, from the point of view of room temperature fuse salt easy to form, More preferable lupetidineMethylethyl piperidinesDiethyl phenylpiperidinesMethyl-propyl piperidinesEthyl propyl piperidinesDipropyl phenylpiperidinesMethyl butyl piperidinesEthyl-butyl piperidinesButyl piperidinesDibutyl piperidines Or the hydrogen atom in these alkyl is by 1 or more fluorine atom replaces and is formed compound, ethylene methacrylic phenylpiperidinesEthyl second Alkenyl piperidinePropyl ethylene phenylpiperidinesButylethylene phenylpiperidinesMethallyl phenylpiperidinesAllyl ethyl piperazine PyridineAllyl piperidinesButyl allylpiperidinDiallyl piperidinesMethyl butene phenylpiperidinesEthyl Butylene phenylpiperidinesPropyl butylene phenylpiperidinesButyl butylene phenylpiperidinesDibutene phenylpiperidinesMethyl methoxy Ji Jia PhenylpiperidinesMethyl methoxy base ethyl piperidineMethyl ethoxy ethyl piperidineMethyl methoxy base oxethyl ethyl piperidineMethyl ethoxy ethoxyethyl group piperidinesEthyl methoxy methyl phenylpiperidinesEthyl methoxy ethyl piperidinesSecond Base oxethyl ethyl piperidineEthyl methoxyethoxyethyl piperidinesEthyl ethoxyethoxyethyl piperidinesThird Ylmethoxymethyl piperidinesPropylmethoxy ethyl piperidinePropyl ethoxyethyl group piperidinesPropylmethoxy ethoxy Base ethyl piperidinePropyl ethoxyethoxyethyl piperidinesButylmethoxy methyl piperidineButylmethoxy ethyl PiperidinesButyl ethoxyethyl group piperidinesButylmethoxy ethoxyethyl group piperidinesButyl ethoxyethoxyethyl PiperidinesDeng.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred Methylethyl piperidinesMethyl-propyl piperazine PyridineEthyl propyl piperidinesMethyl butyl piperidinesEthyl-butyl piperidinesOr the hydrogen atom in these alkyl is by 1 The above fluorine atom replaces and compound, the methallyl phenylpiperidines of formationAllyl phenylpiperidinesAllyl piperazine PyridineButyl allylpiperidinMethyl butene phenylpiperidinesEthyl butylene phenylpiperidinesPropyl butylene phenylpiperidinesFourth Base butylene phenylpiperidinesMethyl methoxy ylmethylpiperidineMethyl methoxy base ethyl piperidineEthyl methoxy methyl phenylpiperidinesEthyl methoxy ethyl piperidinesDeng.

The morpholine represented by above-mentioned general formula (11)It is molten from room temperature easy to form in (モ Le ホ リ ニ ウ system) cation From the point of view of melting salt, more preferable thebaineMethylethyl morpholineDiethyl morpholineMethyl-propyl morpholineEthyl propyl morpholineDipropyl morpholineMethyl butyl morpholineEthyl-butyl morpholineButyl morpholineDibutyl morpholineOr the hydrogen atom in these alkyl is by 1 or more fluorine atom replaces and is formed compound, methyl second Alkenyl morpholineEthyl vinyl morpholinePropyl ethylene base morpholineButyl vinyl morpholineMethacrylic QuinolineAllyl ethyl morpholineAllyl morpholineButyl allyl morpholineDiallyl morpholineMethyl Cyclobutenyl morpholineEthyl cyclobutenyl morpholinePropyl cyclobutenyl morpholineButyl cyclobutenyl morpholineDibutene base QuinolineMethyl methoxy ylmethyl morpholineMethyl methoxy base ethyl morpholineMethyl ethoxy ethyl morpholineMethyl first Oxygroup ethoxyethyl group morpholineMethyl ethoxy ethoxyethyl group morpholineEthyl methoxy morpholineEthyl first Oxygroup ethyl morpholineEthyl ethoxyethyl group morpholineEthyl methoxyethoxyethyl morpholineEthyl ethyoxyl second Oxygroup ethyl morpholinePropylmethoxy methyl morpholinePropylmethoxy ethyl morpholinePropyl ethoxyethyl group morpholinePropylmethoxy ethoxyethyl group morpholinePropyl ethoxyethoxyethyl morpholineButylmethoxy methyl morpholineButylmethoxy ethyl morpholineButyl ethoxyethyl group morpholineButylmethoxy ethoxyethyl group morpholineFourth Base oxethyl ethoxyethyl group morpholineDeng.

From the point of view of being wherein easily reduced from viscosity, particularly preferred Methylethyl morpholineMethyl-propyl morpholineEthyl propyl morpholineMethyl butyl morpholineEthyl-butyl morpholineOr the hydrogen atom in these alkyl by 1 with Upper fluorine atom replaces and compound, the methacrylic morpholine of formationAllyl ethyl morpholineAllyl morpholineButyl allyl morpholineMethyl butene base morpholineEthyl cyclobutenyl morpholinePropyl cyclobutenyl morpholineFourth Base cyclobutenyl morpholineMethyl methoxy ylmethyl morpholineMethyl methoxy base ethyl morpholineEthyl methoxy morpholineEthyl methoxyethyl morpholineDeng.

The general formula (7) of the present invention 5 further includes following structures: in the quaternary ammonium cation structure of above-mentioned general formula (7), R_4r、 R_5r、R_6rAnd R_7rIn 2 organic groups be actually 1 organic group, 1 organic group and " N⁺" pass through between atom Double bond connection.That is, general formula (7) further includes R_4r、R_5r、R_6rAnd R_7rIn 2 the case where merging into alkylidene.In addition, also It is preferred that the alkylidene forms ring structure.In the structure, the salt of unsaturated heterocycle structure low melting point easy to form as shown below, Therefore preferably.

[chemical formula 26]

[chemical formula 27]

[chemical formula 28]

[chemical formula 29]

[chemical formula 30]

[chemical formula 31]

[chemical formula 32]

[chemical formula 33]

[chemical formula 34]

The pyridine represented by above-mentioned general formula (12)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₁₄Replaced and shape for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom At compound, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, second Oxygroup ethoxyethyl group etc., and R₁₅~R₁₉For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethylpyridine1- propyIpyridine 1- butyl-pyridinium1- pentyl pyridine1- hexyl pyridine1- allyl pyridine1- butylene yl pyridines1- methoxy Ylmethyl pyridine1- methoxy ethyl pyridineDeng.

The pyridazine represented by above-mentioned general formula (13)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₂₀Replaced and shape for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom At compound, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, second Oxygroup ethoxyethyl group etc., and R₂₁~R₂₄For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethyl pyridazine1- propyl pyridazine 1- butyl pyridazine1- amyl pyridazine1- hexyl pyridazine1- allyl radical pyridazine1- butylene radical pyridazine1- methoxy Ylmethyl pyridazine1- methoxy ethyl pyridazineDeng.

The pyrimidine represented by above-mentioned general formula (14)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₂₅Replaced and shape for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom At conjunction object, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, ethoxy Base oxethyl ethyl etc., and R₂₆~R₂₉For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethyl-pyrimidine1- propyl pyrimidine 1- butyl pyrimidine1- amyl pyrimidine1- hexyl pyrimidine1- allyl yl pyrimidines1- butylene yl pyrimidines1- methoxy Ylmethyl pyrimidine1- methoxy ethyl pyrimidineDeng.

The pyrazine represented by above-mentioned general formula (15)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₃₀Replaced and shape for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom At compound, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyethoxyethyl, second Oxygroup ethoxyethyl group etc., and R₃₁~R₃₄For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethyl pyrazine1- propyl pyrazine 1- butyl pyrazine1- amyl pyrazine1- hexyl pyrazine1- allyl pyrazine1- cyclobutenyl pyrazine1- methoxy Ylmethyl pyrazine1- methoxy ethyl pyrazineDeng.

The imidazoles represented by above-mentioned general formula (16)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₃₆And R₃₉Replaced for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom And compound, the vinyl, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxyl group second formed Oxygroup ethyl, ethoxyethoxyethyl etc., and R₃₅、R₃₇、R₃₈For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1,3- methylimidazole1- ethyl -3- Methylimidazole1- propyl -3- methylimidazole1- butyl -3- methylimidazole1- amyl -3- methylimidazole1- oneself Base -3- methylimidazole1,3- diethyl imidazolium1- ethyl -3- propyl imidazole1- ethyl -3- butyl imidazole1- Ethyl -3- amyl imidazoles1- ethyl -3- hexyl imidazolium1,3- dipropyl imidazoles1- propyl -3- butyl imidazole 1- propyl -3- amyl imidazoles1- hexyl -3- butyl imidazole1,2,3- tri-methylimidazolium1- ethyl -2,3- dimethyl Imidazoles1- propyl -2,3- methylimidazole1- butyl -2,3- methylimidazole1- amyl -2,3- methylimidazole1- hexyl -2,3- methylimidazole1,3- diethyl -2-methylimidazole1- propyl -2- methyl -3- ethyl imidazol(e)1- butyl -2- methyl -3- ethyl imidazol(e)1- amyl -2- methyl -3- ethyl imidazol(e)1- hexyl -2- methyl -3- second Base imidazoles1,2,3,4,5- pentamethyl imidazoles1- ethyl -2,3,4,5- tetramethyl imidazoles1- propyl -2,3,4,5- Tetramethyl imidazoles1- butyl -2,3,4,5- tetramethyl imidazoles1- amyl -2,3,4,5- tetramethyl imidazoles1- oneself Base -2,3,4,5- tetramethyl imidazolesAnd the hydrogen atom in these alkyl is by 1 or more fluorine atom replaces and is formed chemical combination Object, 1- allyl -3- methylimidazole1- allyl -3- ethyl imidazol(e)1- allyl -3- propyl imidazole1- allyl Base -3- butyl imidazole1- allyl -2,3- methylimidazole1- allyl -2,3,4,5- tetramethyl imidazoles1- fourth Alkenyl -3- methylimidazole1- cyclobutenyl -3- ethyl imidazol(e)1- cyclobutenyl -3- propyl imidazole1- cyclobutenyl -3- fourth Base imidazoles1- cyclobutenyl -2,3- methylimidazole1- cyclobutenyl -2,3,4,5- tetramethyl imidazoles1- methoxy methyl Base -3- methylimidazole1- methoxy -3- ethyl imidazol(e)1- methoxy -3- propyl imidazole1- methoxy Ylmethyl -3- butyl imidazole1- methoxy -2,3- methylimidazole1- methoxy -2,3,4,5- tetramethyl Base imidazoles1- methoxy ethyl -3- methylimidazole1- methoxy ethyl -3- ethyl imidazol(e)1- methoxy ethyl -3- Propyl imidazole1- methoxy ethyl -3- butyl imidazole1- methoxy ethyl -2,3- methylimidazole1- methoxyl group Ethyl -2,3,4,5- tetramethyl imidazolesDeng.

Represented by above-mentioned general formula (17)AzolesIn cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₄₁Replaced to be formed by 1 or more fluorine atom for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl Compound, vinyl, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxy ethoxy second Base, ethoxyethoxyethyl etc., and R₄₀、R₄₂、R₄₃For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethylAzoles1- propylAzoles1- butylAzoles1- amylAzoles1- hexylAzoles1- allylAzoles1- cyclobutenylAzoles1- methoxyAzoles1- methoxy ethylAzoles1- ethyl -2,4,5- trimethylAzoles1- third Base -2,4,5- trimethylAzoles1- butyl -2,4,5- trimethylAzoles1- amyl -2,4,5- trimethylAzoles1- hexyl -2,4,5- trimethylAzoles1- allyl -2,4,5- trimethylAzoles1- cyclobutenyl -2,4,5- three MethylAzoles1- methoxy -2,4,5- trimethylAzoles1- methoxy ethyl -2,4,5- trimethylAzolesDeng.

The thiazole represented by above-mentioned general formula (18)In (チ ア ゾ リ ウ system) cation, melted from room temperature easy to form From the point of view of salt, preferably R₄₅It is the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine Atom replace and formed compound, vinyl, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, Methoxyethoxyethyl, ethoxyethoxyethyl etc., and R₄₄、R₄₆、R₄₇For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethyl thiazole1- propyl thiazole 1- butyl thiazole1- amyl thiazole1- hexyl thiazole1- allyl thiazole1- cyclobutenyl thiazole1- methoxy Ylmethyl thiazole1- methoxy ethyl thiazole1- ethyl -2,4,5- trimethylthiazole1- propyl -2,4,5- front three Base thiazole1- butyl -2,4,5- trimethylthiazole1- amyl -2,4,5- trimethylthiazole1- hexyl -2,4,5- three Methylthiazol1- allyl -2,4,5- trimethylthiazole1- cyclobutenyl -2,4,5- trimethylthiazole1- methoxyl group Methyl -2,4,5- trimethylthiazole1- methoxy ethyl -2,4,5- trimethylthiazoleDeng.

The pyrazoles represented by above-mentioned general formula (19)In cation, from the point of view of room temperature fuse salt easy to form, It is preferred that R₄₉Replaced and shape for the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine atom At compound, vinyl, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, methoxy ethoxy Ethyl, ethoxyethoxyethyl etc., and R₄₈、R₅₀~R₅₂For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethylpyrazol1- propylpyrazol 1- butyl pyrazoles1- amyl pyrazoles1- hexyl pyrazoles1- allyl pyrazoles1- cyclobutenyl pyrazoles1- methoxy Ylmethyl pyrazoles1- methoxy ethyl pyrazoles1- ethyl -2,3,4,5- tetramethyl pyrazoles1- propyl -2,3,4,5- Tetramethyl pyrazoles1- butyl -2,3,4,5- tetramethyl pyrazoles1- amyl -2,3,4,5- tetramethyl pyrazoles1- hexyl- 2,3,4,5- tetramethyl pyrazoles1- allyl -2,3,4,5- tetramethyl pyrazoles1- cyclobutenyl -2,3,4,5- tetramethyl pyrrole Azoles1- methoxy -2,3,4,5- tetramethyl pyrazoles1- methoxy ethyl -2,3,4,5- tetramethyl pyrazolesDeng.

The triazole represented by above-mentioned general formula (20)In (ト リ ア ゾ リ ウ system) cation, melted from room temperature easy to form From the point of view of salt, preferably R₅₄It is the hydrogen atom in ethyl, propyl, butyl, amyl, hexyl and these alkyl by 1 or more fluorine Atom replace and formed compound, vinyl, allyl, cyclobutenyl, methoxy, methoxy ethyl, ethoxyethyl group, Methoxyethoxyethyl, ethoxyethoxyethyl etc., and R₅₃、R₅₅、R₅₆For hydrogen atom or methyl.

Wherein, from the point of view of being easily reduced from viscosity, particularly preferred 1- ethyl triazole1- propyl triazole 1- triazbutil1- amyl triazole1- hexyl triazole1- allyl triazole1- cyclobutenyl triazole1- methoxy Ylmethyl triazole1- methoxy ethyl triazole1- ethyl -2,3,4,5- tetramethyl triazole1- propyl -2,3,4,5- Tetramethyl triazole1- butyl -2,3,4,5- tetramethyl triazole1- amyl -2,3,4,5- tetramethyl triazole1- hexyl- 2,3,4,5- tetramethyl triazole1- allyl -2,3,4,5- tetramethyl triazole1- cyclobutenyl -2,3,4,5- tetramethyl three Azoles1- methoxy -2,3,4,5- tetramethyl triazole1- methoxy ethyl -2,3,4,5- tetramethyl triazoleDeng.

The anion of the quaternary ammonium salt with structure represented by above-mentioned general formula (7) in the present invention 5 is not limited especially It is fixed, it can enumerate and the anion of above-mentioned lithium salts or have the anion of tertiary sulfonium salt of structure represented by above-mentioned general formula (6) identical Anion as preferred example.

[compound represented by general formula (8)]

Season represented by the above-mentioned general formula (8) of the present invention 5R in cationic structural_8r、R_9r、R_10rAnd R_11rIt is identical Or the organic group of different carbon atom numbers 1~12, as R_8r、R_9r、R_10rAnd R_11r, the general formula (6) with the present invention 5 can be enumerated In " R_1r、R_2rAnd R_3r" identical chain-like alkyl；Cyclic alkyl；Alkenyl；Alkynyl；Halogenated alkyl；Optionally there is alkyl to replace The aryl such as the phenyl of base；Aralkyl；Trialkylsilkl；Alkyl containing carbonyl；Alkyl containing ether；Contain sulfonyl Alkyl etc..Additionally, it is preferred that specific group also with the " R in above-mentioned general formula (6)_1r、R_2rAnd R₃" identical.

R_8r、R_9r、R_10rAnd R_11rIn 2~4 optionally mutually bonded and form ring structure, R_8r、R_9r、R_10rAnd R_11rMay be used also It is substituted to be combined and the saturation or unsaturated bond formed by the miscellaneous element such as oxygen, nitrogen, sulphur, P elements on above-mentioned substituent group Base.

In addition, the above-mentioned general formula (8) in the present invention 5 further includes following structures: in the season of the above-mentioned general formula (8) of the present invention 5In cationic structural, R_8r、R_9r、R_10rAnd R_11rIn 2 organic groups be actually 1 organic group, this 1 is organic Group and " P⁺" connected with double bond between atom.That is, the above-mentioned general formula (8) in the present invention 5 further includes R_8r、R_9r、R_10rWith R_11rIn 2 groups the case where merging into alkylidene.

In R_8r~R_10rIn, preferred alkyl, halogenated alkyl, allyl, the alkyl containing ether of carbon atom number 1~10, because To be somebody's turn to do by reducingThe intermolecular interaction of salt and the salt of low melting point easy to form.

Wherein, from the point of view of being easily reduced viscosity, more preferable triethyl group butylTriethyl group amylThree EthylhexylTriethyl group heptylTriethyl group octylDiethylpropyl butylDiethylpropyl amylDiethyl Propyl hexylDiethylpropyl heptylDiethylpropyl octylDiethyl butyl amylDiethyl butyl hexylDiethyl butyl heptylDiethyl butyl octylDiethyl amyl group hexylDiethyl amyl group heptylDiethyl Amyl octylDiethylhexyl heptylDiethylhexyl octylDiethyl heptyl octylDiethyl dioctyl Ethyl dipropyl butylEthyl dipropyl amylEthyl dipropyl hexylEthyl dipropyl heptylEthyl dipropyl Base octylEthyl propyl dibutylEthyl propyl butyl amylEthyl propyl butyl hexylEthyl propyl butyl HeptylEthyl propyl butyl octylEthyl propyl diamylEthyl propyl amyl hexylEthyl propyl amyl heptan BaseEthyl propyl amyl octylEthyl propyl dihexylEthyl propyl hexyl heptylEthyl propyl hexyl octylEthyl propyl diheptylEthyl propyl heptyl octylEthyl propyl dioctylEthyl tributylTwo fourth of ethyl Base amylEthyl dibutyl hexylEthyl dibutyl heptylEthyl dibutyl octylEthyl-butyl diamyl Ethyl-butyl amyl hexylEthyl-butyl amyl heptylEthyl-butyl amyl octylEthyl-butyl dihexylSecond Base butyl hexyl heptylEthyl-butyl hexyl octylEthyl-butyl heptyl octylEthyl-butyl dioctylEthyl Three amylsEthyl diamyl hexylEthyl diamyl heptylEthyl diamyl octylEthylpentyl dihexyl Ethylpentyl hexyl heptylEthylpentyl hexyl octylEthylpentyl diheptylEthylpentyl heptyl octylSecond Base amyl dioctylThree hexyl of ethylEthyl dihexyl heptylEthyl dihexyl octylEthylhexyl diheptylEthylhexyl heptyl octylEthylhexyl dioctylThree heptyl of ethylEthyl diheptyl octylEthylheptyl DioctylEthyl trioctylphosphineTripropyl butylTripropyl amylTripropyl hexylTripropyl heptylThree Propyl octylDipropyl dibutylDipropyl butyl amylDipropyl butyl hexylDipropyl butyl heptyl Dipropyl butyl octylDipropyl diamylDipropyl amyl hexylDipropyl amyl heptylDipropyl amyl OctylDipropyl dihexylDipropyl hexyl heptylDipropyl hexyl octylDipropyl diheptylDipropyl Heptyl octylDipropyl dioctylPropyl tributylPropyl dibutyl amylPropyl dibutyl hexylPropyl Dibutyl heptylPropyl dibutyl octylButyl diamylButyl amyl hexylButyl penta Base heptylButyl amyl octylButyl diheptylButyl heptyl octylButyl two is pungent BaseThree amyl of propylPropyl diamyl hexylPropyl diamyl heptylPropyl diamyl octylPropylpentyl Hexyl heptylPropylpentyl hexyl octylPropylpentyl diheptylPropylpentyl heptyl octylPropylpentyl two OctylThree hexyl of propylPropyl dihexyl heptylPropyl dihexyl octylPropyl hexyl diheptylPropyl oneself Base heptyl octylPropyl hexyl dioctylThree heptyl of propylPropyl diheptyl octylPropylheptyl dioctyl Propyl trioctylphosphineThe tetrabutylTributyl amylTributyl hexylTributyl heptylTributyl octylFour AmylThree amyl hexylsThree amyl heptylThree amyl octylsFour hexylsThree hexyl heptylThree hexyls are pungent BaseFour heptylThree heptyl octylsFour octylsDeng or these alkyl in hydrogen atom replaced by 1 or more fluorine atom And compound, the triethyl group allyl formedTriethyl group cyclobutenylTripropyl allylTripropyl cyclobutenylThree Butyl allylTributyl cyclobutenylTriethyl group methoxy ethylTriethyl group methoxyethoxyethyl3 third Ylmethoxy ethylTripropyl methoxyethoxyethylTributyl methoxy ethylTributyl methoxy ethoxy EthylDeng.

It wherein, is do not damage room temperature fuse salt feature suitable big from the number of ions (i.e. ion concentration) in unit volume It is small, and with the balance of fusing point, viscosity it is good from the point of view of, particularly preferred triethyl group butylTriethyl group amylThree EthylhexylTriethyl group heptylTriethyl group octylTripropyl butylTripropyl amylTripropyl hexyl Tripropyl heptylTripropyl octylThe tetrabutylTributyl amylTributyl hexylTributyl heptylThree Butyl octylFour pentylThree amyl hexylsThree amyl heptylThree amyl octylsFour hexylsThree hexyl heptan BaseThree hexyl octylsFour heptylThree heptyl octylsFour octylsDeng and these alkyl in hydrogen atom by 1 The above fluorine atom replaces and compound, the triethyl group allyl of formationTriethyl group cyclobutenylTripropyl allylThree Propyl cyclobutenylTributyl allylTributyl cyclobutenylTriethyl group methoxy ethylTriethyl group methoxyl group second Oxygroup ethylTripropyl methoxy ethylTripropyl methoxyethoxyethylTributyl methoxy ethylThree Butylmethoxy ethoxyethyl groupDeng.

Season with structure represented by general formula (8) in the present invention 5The anion of salt is not particularly limited, as preferred Example can enumerate the anion of the tertiary sulfonium salt with the anion of above-mentioned lithium salts, with structure represented by above-mentioned general formula (6) or have The identical anion of anion of the quaternary ammonium salt of structure represented by above-mentioned general formula (7).

In the range of not damaging the effect of the present invention 5, the nonaqueous solvents in the nonaqueous electrolytic solution of the present invention 5 can also contain There is solvent well known to the previous solvent as nonaqueous electrolytic solution.At this point it is possible to from the solvent of well known nonaqueous electrolytic solution into The appropriate selection of row uses.As preferred example, such as the combination based on following solvents: room temperature fuse salt and chain can be enumerated Carbonates, room temperature fuse salt and cyclic carbonates, room temperature fuse salt and cyclic annular esters, room temperature fuse salt and cyclic sulfones class, Room temperature fuse salt and fluoro chain ethers, room temperature fuse salt and fluorinated chain carbonate class, room temperature fuse salt and molecular weight 500~ Polyethers, room temperature fuse salt and the phosphoric acid of 700~3000 degree of 3000 or so polysiloxane-based, room temperature fuse salt and molecular weight Esters etc..

It is excellent relative to the nonaqueous electrolytic solution ingredient other than lithium salts and aftermentioned " mono-fluor phosphate, difluorophosphoric acid salt " Select the room temperature fuse salt containing 0.01 weight of weight %~100 %." lithium salts and ' mono-fluor phosphate, difluorophosphoric acid are removed about described Salt ' other than nonaqueous electrolytic solution ingredient ", such as can enumerate: chain or cyclic carbonates, chain or cyclic annular esters, chain or Cyclic sulfones class, chain or ring-type ethers, the fluorides of these compounds, polysiloxane-based, polyethers etc. " high boiling solvent or Noninflammability solvent " etc..Aftermentioned nonaqueous solvents can also be enumerated.

Relative to the total amount of mentioned component, the content of more preferable room temperature fuse salt is 50 weight of weight %~100 %, especially Preferably 60 weight of weight %~95 %, further preferably 70 weight of weight %~90 %.In the very few feelings of room temperature fuse salt Under condition, for nonaqueous electrolytic solution, it is unable to get the security impacts such as noninflammability, high thermal stability sometimes, on the other hand, in room temperature In the case that fuse salt is excessive, the structure of room temperature fuse salt causes viscosity excessively high, ionic conductivity reduction sometimes, the non-aqueous solution electrolysis Liquid is difficult to infiltrate through in partition or anode/cathode.

The present invention 5 in, the preferred combination of the nonaqueous solvents containing room temperature fuse salt first is that with room temperature fuse salt and ring Combination based on shape carbonates.Wherein, ratio shared by room temperature fuse salt is 50 weight % or more, preferably in nonaqueous solvents For 60 weight % or more, more preferably 70 weight % or more, and usually 95 weight % or less, preferably 90 weight % or less, More preferably 85 weight % or less.Using the nonaqueous solvents combination when, and room temperature fuse salt is used only as nonaqueous electrolytic solution It is compared when solvent, the viscosity of nonaqueous electrolytic solution reduces, and is formed well in negative terminal surface since cyclic carbonate has Envelope effect, it is special using the battery charge/discharge capacity at higher current densities and circulation of the combination production of the nonaqueous solvents Property it is excellent, therefore preferably.

Preferred combined concrete example as room temperature fuse salt and " cyclic carbonates or cyclic annular esters, cyclic sulfones class " Son, such as can enumerate: room temperature fuse salt and ethylene carbonate, room temperature fuse salt and propylene carbonate, room temperature fuse salt and fluorine carbon Sour ethyl, room temperature fuse salt and butylene carbonate, room temperature fuse salt and gamma-butyrolacton, room temperature fuse salt and gamma-valerolactone, Room temperature fuse salt and sulfolane, room temperature fuse salt and fluoro sulfolane etc..

In addition, other preferred combinations first is that combination based on room temperature fuse salt and fluoro chain ethers.Wherein, non- Ratio shared by room temperature fuse salt is 50 weight % or more, preferably 60 weight % or more, more preferably 70 weights in aqueous solvent % or more is measured, and usually 95 weight % or less, preferably 90 weight % or less, more preferably 85 weight % or less.Due to making When with the combination of the nonaqueous solvents, noninflammability possessed by room temperature fuse salt will not be damaged, and room temperature fuse salt conduct is used only Compared when the solvent of nonaqueous electrolytic solution, the viscosity of nonaqueous electrolytic solution reduces, and nonaqueous electrolytic solution it is readily permeable enter anode or In the pore of cathode, the charge/discharge capacity of the battery made using the combination of the nonaqueous solvents at higher current densities is improved, because This is preferably.

It as the preferred combined specific example of room temperature fuse salt and fluoro chain ethers, such as can enumerate: room temperature melting Salt and nona-fluoro butyl group methyl ether, room temperature fuse salt and nona-fluoro butyl group ethylether, room temperature fuse salt and trifluoro ethoxy (ethoxymethyl) Alkane, room temperature fuse salt and trifluoro ethoxy Ethoxyethane, room temperature fuse salt and hexafluoro ethoxy ethoxy methylmethane, room temperature melting Salt and hexafluoro ethoxy ethoxy ethane etc..

As the preferred combined specific example of room temperature fuse salt and phosphoric acid ester, such as can enumerate: room temperature fuse salt and Trimethyl phosphate, room temperature fuse salt and triethyl phosphate, room temperature fuse salt and phosphoric acid dimethyl ethyl ester, room temperature fuse salt and phosphorus Acid methyl diethyl ester, room temperature fuse salt and tricresyl phosphate (trifluoroethyl) ester, room temperature fuse salt and methylethylene phosphate, often Warm fuse salt and ethylethylene residue phosphate, room temperature fuse salt and tri hexyl phosphate, room temperature fuse salt and trioctyl phosphate etc..

<1-3. mono-fluor phosphate, difluorophosphoric acid salt>

In addition to above-mentioned lithium salts and room temperature fuse salt, the nonaqueous electrolytic solution of the present invention 5 also contains " mono-fluor phosphate and/or two Fluorophosphate ".

The counter cation of mono-fluor phosphate and difluorophosphoric acid salt is not particularly limited, and removes Li, Na, K, Mg, Ca, Fe, Cu Other than equal metallic elements, quaternary ammonium represented by tertiary sulfonium represented by general formula (6), general formula (7), general formula (8) institute table can also be enumerated The season shownWherein, contend with sun used in counter cation represented by general formula (6)~(8) and above-mentioned room temperature fuse salt Ionic structure is identical.

In these counter cations, when from for nonaqueous electrolyte battery from the aspect of the characteristic of battery, preferably lithium, Sodium, potassium, magnesium, calcium or tertiary sulfonium, quaternary ammonium, seasonParticularly preferred lithium.

In addition, in mono-fluor phosphate, difluorophosphoric acid salt, examined from the cycle characteristics of battery, High temperature storage characteristic etc. Consider, preferably difluorophosphoric acid salt, particularly preferred difluorophosphate.In addition, these compounds can substantially be directly used in it is non-aqueous It is synthesized in solvent, the compound after can also being separated by other synthesis and substantially is added in nonaqueous solvents or non-aqueous In electrolyte.

Relative to the nonaqueous electrolytic solution total amount of the present invention 5, the additive amount of " mono-fluor phosphate and/or difluorophosphoric acid salt " does not have Limitation can be any amount as long as not significantly affecting the effect of the present invention 5, and the nonaqueous electrolytic solution relative to the present invention 5 is total Amount, always contain concentration be usually 0.001 weight % or more, preferably 0.01 weight % or more, more preferably 0.1 weight % with On, and usually 20 weight % or less, preferably 10 weight % or less, more preferably 5 weight % or less.In too high levels, Mono-fluor phosphate and/or difluorophosphoric acid salt are precipitated in low temperature, occasionally result in battery behavior reduction, and when mono-fluor phosphate and/or When difluorophosphoric acid salt content is too low, the improvement effect of cycle characteristics, High temperature storage characteristic etc. is substantially reduced sometimes.In single fluorophosphoric acid In the case that salt and/or difluorophosphoric acid salt double as room temperature fuse salt, the concentration of contained mono-fluor phosphate and/or difluorophosphoric acid salt Usually 0.001 weight % or more, preferably 0.01 weight % or more, more preferably 0.1 weight % or more, and usually 100 Weight % or less, preferably 95 weight % or less, more preferably 90 weight % or less, particularly preferably 85 weight % or less.When When the too high levels of mono-fluor phosphate and/or difluorophosphoric acid salt, the viscosity of nonaqueous electrolytic solution increases, and ionic conductivity drops sometimes It is low, be not easy to infiltrate through in partition or anode/cathode.On the other hand, when mono-fluor phosphate and/or difluorophosphoric acid salt content are too low When, same as described above, the improvement effect of low-temperature characteristics, cycle characteristics, High temperature storage characteristic etc. is substantially reduced sometimes.

In addition, about the molecular weight of mono-fluor phosphate or difluorophosphoric acid salt, preparation method etc., also with it is described in the present invention 1 Bright is identical.

In addition, the detection period (period contained) of mono-fluor phosphate or difluorophosphoric acid salt, the place initially contained first (source contained), the method contained are considered as detection place etc. in nonaqueous electrolytic solution containing (or having contained), also with It is identical illustrated in the present invention 1.

<the other compounds of 1-4.>

In the range of not damaging the effect of the present invention 5, the nonaqueous electrolytic solution of the present invention 5 can contain " other chemical combination Object ".As " other compounds ", known cathode envelope forming agent can be enumerated, positive protective agent, overcharge prevent The various compounds such as agent, auxiliary agent.

<1-4-1. cathode envelope forming agent>

By containing cathode envelope forming agent, the reaction invertibity of the lithium ion of cathode can be improved, so as to improve Charge/discharge capacity, efficiency for charge-discharge, cycle characteristics.As cathode envelope forming agent, preferably such as vinylene carbonate, vinyl Ethylene carbonate, fluorine ethylene carbonate etc..These cathode envelope forming agents can be used alone a kind, can also be by two or more with any Combination and ratio are applied in combination.

The content ratio of these cathode envelope forming agents in nonaqueous electrolytic solution is not particularly limited, relative to non-aqueous solution electrolysis Liquid total amount, respectively 0.01 weight % or more, preferably 0.1 weight % or more, more preferably 0.2 weight % or more, the upper limit For 12 weight % or less, preferably 10 weight % or less, more preferably 8 weight % or less.

<1-4-2. anode protective agent>

By the way that containing positive protective agent, the capacity after High temperature storage can be improved is kept and cycle characteristics.It is protected as anode Protect agent, preferably glycol sulfite, sulfurous acid Asia propyl ester, propane sultone, butyl sultone, methyl mesylate, two methanesulfonic acids Butyl ester etc..Two or more can be applied in combination these positive protective agents.

These protectant content ratios of anode in nonaqueous electrolytic solution are not particularly limited, total relative to nonaqueous electrolytic solution Amount, respectively 0.01 weight % or more, preferably 0.1 weight % or more, more preferably 0.2 weight % or more, the upper limit are 5 weights Measure % or less, preferably 3 weight % or less, more preferably 2 weight % or less.

<1-4-3. overcharge preventing agent>

By containing overcharge preventing agent, rupture, the kindling of battery when overcharge can be inhibited.

As the specific example of overcharge preventing agent, such as documented overcharge preventing agent in the present invention 1 can be enumerated.It is non- The ratio of overcharge preventing agent in water electrolysis liquid relative to nonaqueous electrolytic solution total amount be usually 0.1 weight % or more, preferably It 0.2 weight % or more, particularly preferably 0.3 weight % or more, is most preferably 0.5 weight % or more, the upper limit is usually 5 weight % It below, is preferably 3 weight % or less, particularly preferably 2 weight % or less.When concentration is lower than the lower limit, it cannot play substantially The effect for the preventing agent that charges.Conversely, the battery behaviors such as High temperature storage characteristic have the tendency that reduction if excessive concentration.

<1-4-4. auxiliary agent>

As the specific example of auxiliary agent, such as auxiliary agent cited in the present invention 1 can be enumerated.Two or more can be helped these Agent is applied in combination.Wherein, it as the auxiliary agent for improving the capacity maintenance characteristics after High temperature storage and cycle characteristics, preferably adds Carbonic ester containing at least one of unsaturated bond and halogen atom (hereinafter, sometimes referred to simply as " specific carbonic ester ").Particular carbon The specific example of acid esters is identical as the present invention 1.

In nonaqueous electrolytic solution the ratio of these auxiliary agents relative to nonaqueous electrolytic solution total amount be usually 0.01 weight % or more, it is excellent It is selected as 0.1 weight % or more, particularly preferably 0.2 weight % or more, the upper limit is usually 5 weight % or less, preferably 3 weight % Below, it is particularly preferably 1 weight % or less.Capacity maintenance characteristics by adding these auxiliary agents, after High temperature storage can be improved And cycle characteristics.When concentration is lower than the lower limit, the effect of auxiliary agent cannot be played substantially.Conversely, if excessive concentration, high load is put The battery behaviors such as electrical characteristics have the tendency that reduction.

<preparation of 1-5. nonaqueous electrolytic solution>

The nonaqueous electrolytic solution of the present invention 5 can be prepared by following methods: by lithium salts, room temperature fuse salt, mono-fluor phosphate class Or difluorophosphoric acid salt and " other compounds " used as needed are mutually dissolved.When preparing nonaqueous electrolytic solution, in order to subtract Moisture when nonaqueous electrolytic solution is made less, is preferably in advance dehydrated each raw material.Usually can by raw material dehydration to 50ppm with Under, preferably dehydration to 30ppm or less, particularly preferably dehydration be to 10ppm or less.Alternatively, it is also possible to after preparing nonaqueous electrolytic solution Be dehydrated, depickling processing etc..

The nonaqueous electrolytic solution of the present invention 5 is preferably as (such as the secondary electricity of lithium of the secondary cell in nonaqueous electrolyte battery Pond use) electrolyte use.Hereinafter, being just illustrated using the nonaqueous electrolyte battery of the nonaqueous electrolytic solution of the present invention 5.

<preparation method of 1-6. nonaqueous electrolytic solution>

The preparation method of the nonaqueous electrolytic solution of the present invention 5 is identical as the present invention 1.

[2. non-aqueous electrolyte secondary battery]

The non-aqueous electrolyte secondary battery of the present invention 5 has the nonaqueous electrolytic solution of aforementioned present invention 5 and can occlude and put The cathode and anode of ion out.

Battery structure；Cathode；Carbonaceous material；Structure, physical property, the preparation method of carbonaceous cathode；Metal compound species material, And structure, physical property, the preparation method of the cathode using metal compound species material；Anode；Partition；Battery design etc. with this hair It is identical illustrated by bright 1.

[current collecting]

Current collecting is not particularly limited, in order to which height brought by the nonaqueous electrolytic solution of the present invention 5 is better achieved in effect The raising of the charge-discharge characteristic of current density is preferably made the structure for reducing the resistance of wiring portion and bonding part.In this way Reduction internal resistance in the case where, can especially give full play to using the present invention 5 nonaqueous electrolytic solution effect.

In the case where electrode group is above-mentioned laminar structure, it is preferred to use following structures: by the metal core of each electrode layer Divide the structure for tying together that simultaneously welding is formed on terminal.Since when increasing the area of 1 piece of electrode, internal resistance increases therewith Add, thus it is also preferred that dropping low-resistance method using multiple terminals are arranged in electrode.It is above-mentioned winding-structure in electrode group In the case where, multiple pin configurations can be respectively set on anode and cathode, and be bundled on terminal to reduce internal resistance.

By optimizing above structure, internal resistance can be reduced as far as possible.In the battery used with high current, preferably use The impedance (hreinafter referred to as " DC resistance component ") of 10kHz alternating current method measurement is 10 milliohms (m Ω) hereinafter, more preferable direct current Resistance components are 5m Ω or less.When DC resistance component is 0.1m Ω or less, although output characteristics enhances, the collection used sometimes Ratio shared by electric structural material increases, and battery capacity is reduced.

[effect]

With regard to the present invention 5 for, using in the nonaqueous electrolytic solution of room temperature fuse salt contain " mono-fluor phosphate class or difluorophosphoric acid There is the reducing effect of interface resistance, charge and discharge cycles to improve effect for salt ", " mono-fluor phosphate class or the difluorophosphoric acid salt " Fruit etc..The present invention 5 play said effect action principles do not know, it is believed that its action principle is as follows, but the present invention 5 not by The limitation of following effects principle.That is, mono-fluor phosphate class or difluorophosphoric acid salt are excellent in the compound for constituting nonaqueous electrolytic solution Electrode is first acted on, concentration or adsorption occurs in electrode interface.Following function may be implemented in this way: preventing positive electrode active material Dissolution of the matter into nonaqueous electrolytic solution, inhibit electrode active material with charge and discharge because caused by volume change electronics conduct The shortcoming of access, or in the case where single lithium fluophosphate or difluorophosphate improve electrode surface lithium concentration, thus it is speculated that exactly this The effect that a little functions impart and reduce interface resistance, improve charge and discharge cycles.In addition, mono-fluor phosphate class, difluorophosphoric acid salt For inorganic matter, imflammable gas will not be generated because of its decomposition.

In addition, single lithium fluophosphate or difluorophosphate are with chains such as the cyclic carbonates such as ethylene carbonate and dimethyl carbonates Shape carbonic ester is that the dissolubility in the widely used nonaqueous electrolytic solution of main composition is very low, and in above-mentioned organic solvent It is compared in electrolyte, single lithium fluophosphate or difluorophosphate can largely dissolve in room temperature fuse salt.Moreover, single fluorophosphoric acid root yin Ion or difluorophosphoric acid root anion are also used as the counter anion of room temperature fuse salt.In this way, by by mono-fluor phosphate Or difluorophosphoric acid salt is combined with room temperature fuse salt, more can significantly and synergistically play reduces interface resistance, improves charge and discharge cycles The effect of characteristic.

Embodiment

More specific description is carried out to the present invention hereinafter, enumerating embodiment and comparative example, but as long as without departing from its purport, this Invention is not limited to these embodiments restrictions.

[about the present invention 1]

[positive manufacture]

By 92 parts by weight cobalt acid lithium (LiCoO₂), 4 parts by weight Kynoar (hreinafter referred to as " PVdF ") and 4 weight Part acetylene black mixing, and N-Methyl pyrrolidone is added thereto, slurry is made, which is coated on the two of aluminum collector Face, and it is dry, obtain anode.

[manufacture of cathode]

92 parts by weight of graphite powder and 8 parts by weight PVdF are mixed, and N-Methyl pyrrolidone is added thereto, slurry is made Material, which is coated on a face of copper collector, and dry, obtains cathode.

[manufacture of non-aqueous electrolyte secondary battery]

Above-mentioned anode, cathode and polyethylene partition are subjected to layer according to the sequence of cathode, partition, anode, partition, cathode Pressure.Thus obtained cell device is wrapped up with tubular aluminium stack membrane, after injecting aftermentioned electrolyte, carries out vacuum sealing, Make the non-aqueous electrolyte secondary battery of sheet.In addition, clipping sheet electricity with glass plate to improve interelectrode adaptation It pressurizes in pond.

[capacity evaluation]

In 25 DEG C of thermostat, sheet non-aqueous electrolyte secondary battery is subjected to constant current-constant voltage with 0.2C It charges (hereinafter appropriately referred to as " CCCV charging ") until 4.4V, then carries out electric discharge with 0.2C until 3.0V.Repeat the circulation 3 It is secondary, it is adjusted.Then, CCCV charging is carried out with 0.7C until 4.4V, carries out electric discharge with 1C until 3.0V, finds out initial stage again Discharge capacity.Cut-off current when charging is 0.05C.It should be noted that 1C is referred to the total of battery in 1 hour Current value when capacity discharges.

[cycle characteristics evaluation]

Battery after overcapacity evaluation test is put into 25 DEG C of thermostat, following charge and discharge cycles 50 are repeated It is secondary: CCCV charging being carried out with 0.7C until 4.4V, carries out constant current electric discharge until 3V with 1C.It is found out and is followed by following calculating formulas Capacity retention ratio after ring 50 times, in the hope of value carry out cycle characteristics evaluation.The numerical value is bigger, shows that the circulation of battery is bad Change lower.

Capacity retention ratio (%) after circulation 50 times

=[discharge capacity (mAh/g) of the 50th discharge capacity (mAh/g)/1st time] × 100

The embodiment 1 of the present invention 1

It will be in the mixed solvent (mixed volume ratio 2:8) of ethylene carbonate (EC) and methyl ethyl carbonate (EMC) with 1mol/ The ratio of L is dissolved with electrolyte LiPF₆Electrolyte as basic electrolyte (I), to difluoro is added in the basic electrolyte (I) Lithium phosphate (LiPO₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II) (Ni (PF₆)₂), make them relative to non-water power The concentration for solving liquid is respectively 0.5 weight % and 20ppm (with the densimeter of Ni element, being equivalent to 3.4ppm), and non-aqueous solution electrolysis is made Liquid.Non-aqueous electrolyte secondary battery is made according to the method described above using obtained nonaqueous electrolytic solution, and is carried out capacity evaluation and followed Ring property evaluation.The results are shown in Table 1.

The embodiment 2 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 50ppm (with the dense of Ni element Degree meter, is equivalent to 8.4ppm), nonaqueous electrolytic solution is made, makes nonaqueous electrolyte according to the method described above using the nonaqueous electrolytic solution Secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 3 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 100ppm (with Ni element Densimeter is equivalent to 16.8ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 4 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 200ppm (with Ni element Densimeter is equivalent to 33.7ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 5 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 300ppm (with Ni element Densimeter is equivalent to 50.5ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 6 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 1000ppm (with Ni element Densimeter is equivalent to 168ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 7 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 3500ppm (with Ni element Densimeter is equivalent to 589ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 8 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid nickel (II)(Ni(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 10000ppm (with Ni element Densimeter, be equivalent to 1684ppm), nonaqueous electrolytic solution is made, makes non-water power according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell is solved, and carries out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 9 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid cobalt (II)(Co(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 50ppm (with the dense of Co element Degree meter, is equivalent to 8.4ppm), nonaqueous electrolytic solution is made, makes nonaqueous electrolyte according to the method described above using the nonaqueous electrolytic solution Secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The embodiment 10 of the present invention 1

To addition difluorophosphate (LiPO in basic electrolyte (I)₂F₂) and as iron group compound hexafluorophosphoric acid cobalt (II)(Co(PF₆)₂), make them relative to the concentration of nonaqueous electrolytic solution be respectively 0.5 weight % and 100ppm (with Co element Densimeter is equivalent to 16.9ppm), nonaqueous electrolytic solution is made, makes non-aqueous solution electrolysis according to the method described above using the nonaqueous electrolytic solution Electrolitc secondary cell, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The comparative example 1 of the present invention 1

Difluorophosphate (LiPO is only added in basic electrolyte (I)₂F₂), make its concentration relative to nonaqueous electrolytic solution For 0.5 weight %, nonaqueous electrolytic solution is made, makes the secondary electricity of nonaqueous electrolyte according to the method described above using the nonaqueous electrolytic solution Pond, and carry out capacity evaluation and cycle characteristics evaluation.The results are shown in Table 1.

The comparative example 2 of the present invention 1

Hexafluorophosphoric acid nickel (II) (Ni (PF as iron group compound is only added in basic electrolyte (I)₆)₂), make its phase Concentration for nonaqueous electrolytic solution is 100ppm (with the densimeter of Ni element, being equivalent to 16.8ppm), and nonaqueous electrolytic solution is made, Non-aqueous electrolyte secondary battery is made according to the method described above using the nonaqueous electrolytic solution, and is carried out capacity evaluation and commented with cycle characteristics Valence.The results are shown in Table 1.

[table 1]

As shown in Table 1, just used the present invention's 1 to contain iron family element and " mono-fluor phosphate and/or difluorophosphoric acid salt " Nonaqueous electrolytic solution the present invention 1 1~embodiment of embodiment 10 non-aqueous electrolyte secondary battery for, and only contain difluoro Phosphate (comparative example 1 of the present invention 1) or the secondary electricity of nonaqueous electrolyte for only containing iron family element (comparative example 2 of the present invention 1) Pond is compared, and cycle characteristics (capacity retention ratio after circulation) is improved.

[about the present invention 2]

The embodiment 1 of the present invention 2

<production of non-aqueous electrolyte secondary battery>

[production of positive active material]

Use composition formula LiMn_0.33Ni_0.33Co_0.33O₂Represented lithium-transition metal composite oxide is as positive-active Substance.The positive active material synthesizes by the following method.Weigh the Mn as manganese raw material₃O₄, as nickel raw material NiO, make For the Co (OH) of cobalt raw material₂, make their molar ratio Mn:Ni:Co=1:1:1, pure water be added thereto, slurry, side stirring is made Solid component in slurry is carried out case of wet attrition with circulating medium-stirring wet-type ball mill by side, makes its median particle diameter 0.2μm。

Slurry is spray-dried with spray dryer, obtains the only partial size made of manganese raw material, nickel raw material, cobalt raw material About 5 μm, granulated particles substantially spherical in shape.The LiOH powder that median particle diameter is 3 μm is added into obtained granulated particles, makes Li The ratio between total mole number of the molal quantity relative to Mn, Ni and Co be 1.05 times, mixed with super mixer, obtain nickel original Material, cobalt raw material, the granulated particles of manganese raw material and the mixed-powder of lithium raw material.By the mixed-powder under air circulation, at 950 DEG C It calcines (5 DEG C/min of warming and cooling rate) 12 hours, then crushes, by 45 μm of sieve of width of mesh, obtain positive electrode active material Matter.

[positive production]

The conduct that the above-mentioned positive active material, 5 weight % of 90 weight % are mixed in N-Methyl pyrrolidone solvent is led The Kynoar (PVdF) of the acetylene black of electric material and 5 weight % as binder, is made slurry.The slurry that will be obtained It is coated on a face of 15 μm of thickness of aluminium foil, and is dried, after being rolled into 80 μm of thickness with press, after handling in this way Aluminium foil strike out the discoid of diameter 12.5mm with pierce punch, production anode.By a part of the anode, as to electrode Lithium metal plate, using at EC (ethylene carbonate): DMC (dimethyl carbonate): EMC (methyl ethyl carbonate)=3:3:4 (volume Than) solvent in 1mol/L concentration be dissolved with LiPF₆Electrolyte and 25 μm of thickness of porous polyethylene as partition Film assembles Coin-shaped battery.

0.2mA/cm is carried out to obtained Coin-shaped battery²Constant-current constant-voltage charging, i.e., be in upper voltage limit The reaction that lithium ion is released by anode is carried out under conditions of 4.2V.Then it is limited to carry out 0.2mA/ under conditions of 3.0V under voltage cm²Constant current electric discharge, when lithium ion namely being made to be occluded in the reaction on anode, at this point, per unit weight anode is living The initial stage charging capacity of property substance is set as Qs (C) [mAh/g], initial stage discharge capacity is set as to Qs (D) [mAh/g].

[production of cathode]

The addition in 98 parts by weight artificial graphite powder KS-44 (manufacture of Timcal (テ ィ system カ Le) company, trade name) 100 parts by weight as the sodium carboxymethylcellulose of thickener aqueous liquid dispersion (concentration of sodium carboxymethylcellulose be 1 weight Measure %), 2 parts by weight as the SBR styrene butadiene rubbers of adhesive aqueous liquid dispersion (SBR styrene butadiene rubbers it is dense Degree is 50 weight %), it is mixed with disperser, slurry is made.Slurry obtained is coated on to the two of 10 μm of thickness of copper foil Treated in this way copper foil after being rolled into 75 μm of thickness with press, is struck out diameter with pierce punch by face, and being dried 12.5mm's is discoid, makes cathode.

In addition, using lithium metal as to electrode, assembled battery unit is used by a part of the cathode as test pole 0.2mA/cm²The constant current of -3mV-constant voltage process (cut-off current 0.05mA) is limited to carry out under conditions of 0V under voltage So that lithium ion is occluded in the test on cathode, is set as at this point, the initial stage of per unit weight negative electrode active material is occluded capacity Qf[mAh/g]。

[nonaqueous electrolytic solution]

Under dry argon atmospher, ethylene carbonate, dimethyl carbonate, methyl ethyl carbonate mixture (volume ratio 3: LiPF fully dried is mixed with the ratio of 1mol/L in 3:4)₆.Make in the mixed solution containing relative to nonaqueous electrolytic solution Total amount is the heptane (compound of the compound group selected from the present invention 2) of 2 weight % ratios, then dissolves difluorophosphoric acid wherein Lithium makes its 0.2 weight % of concentration relative to nonaqueous electrolytic solution total amount, desired electrolyte is made.

[assembling of battery]

Anode, the cathode for combining above-mentioned production assemble testing battery using Coin-shaped battery (U イ Application セ Le), to it Battery performance is evaluated.That is, the above-mentioned anode of production is placed on the positive tank (positive narrow-necked earthen jar) of Coin-shaped battery, then It is provided as 25 μm of thickness of porous polyethylene membrane of partition on it, after being compressed with polypropylene washer, by above-mentioned non-water power It solves liquid to be added in tank, keeps nonaqueous electrolytic solution fully penetrated into after partition, place above-mentioned cathode, then put cathode pot and sealed Mouthful, thus make Coin shape lithium secondary battery.It should be noted that at this time to positive active material weight and negative electrode active material The balance of weight is set, it is made to substantially meet following formula.

(negative electrode active material weight [g] × Qf [mAh/g])/(positive active material weight [g] × Qs (C) [mAh/g]) =1.2

<battery behavior test>

In order to measure the low temperature load characteristic for the battery being achieved in that, 1 hour rate (1 time of battery is set according to the following formula Rate) current value, that is, 1C, carry out following tests.

1C [mA]=Qs (D) × positive active material weight [g]/h

Firstly, carrying out the constant current 0.2C charge and discharge of 1 circulation in room temperature, 2 following circulations are then carried out: carrying out permanent After constant-current constant-voltage 1/3C charging, constant current 1/3C electric discharge is carried out.It should be noted that charging upper limit therein is 4.1V, lower voltage limit 3.0V.

(output test)

Then, in the environment of 25 DEG C, to the coin that depth of charge is adjusted to 50% by 1/3C constant current charging Type battery carries out output measurement test.With 0.3C, 1.0C, 3.0C, 10.0C progress 10 seconds electric discharge (stop 15 minutes after electric discharge, Then charged with each corresponding capacitance of electric discharge, stop 15 minutes, then carry out next discharge test again), The 10th second voltage is measured respectively.Using the 3 angular areas that current-voltage straight line and lower voltage limit (3V) are surrounded as just Phase output power (W), the results are shown in Table 2.

(cyclic test)

Cyclic test is carried out under 60 DEG C of the hot environment of actual use ceiling temperature for being considered as lithium secondary battery. It is recycled following charge and discharge cycles as 1, the circulation is repeated 100 times, the charge and discharge cycles are as follows: with the constant electricity of 2C Stream constant voltage process carry out charging until charging upper limit voltage be 4.1V, then with the constant current of 2C discharge until electric discharge Final voltage is 3.0V.Battery after under 25 DEG C of environment to cyclic test carries out the charge and discharge of the 1/3C of 3 circulations, into Row output test identical with initial stage.Using the value measured as the output power after circulation, the results are shown in Table 2.

The embodiment 2 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the amount of heptane is changed to 0.5 weight % by 2 weight %, in addition to this, according to Method identical with the embodiment 1 of the present invention 2 makes non-aqueous electrolyte secondary battery, carries out battery behavior test.As a result such as table 2 It is shown.

The embodiment 3 of the present invention 2

In the preparation of nonaqueous electrolytic solution, in addition to this pressed using the hexamethylene of 2 weight % instead of the heptane of 2 weight % Non-aqueous electrolyte secondary battery is made according to method identical with the embodiment 1 of the present invention 2, carries out battery behavior test.As a result such as Shown in table 2.

The embodiment 4 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the amount of hexamethylene is changed to 0.5 weight % by 2 weight % and is in addition to this pressed Non-aqueous electrolyte secondary battery is made according to method identical with the embodiment 3 of the present invention 2, carries out battery behavior test.As a result such as Shown in table 2.

The embodiment 5 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the heptane of 2 weight % is replaced using the fluorobenzene of 2 weight %, in addition to this, according to Method identical with the embodiment 1 of the present invention 2 makes non-aqueous electrolyte secondary battery, carries out battery behavior test.As a result such as table 2 It is shown.

The embodiment 6 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the amount of fluorobenzene is changed to 0.5 weight % by 2 weight %, in addition to this, according to Method identical with the embodiment 5 of the present invention 2 makes non-aqueous electrolyte secondary battery, carries out battery behavior test.As a result such as table 2 It is shown.

The embodiment 7 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the heptane of 2 weight % is replaced using the nona-fluoro butyl group ethylether of 2 weight %, is removed Except this, non-aqueous electrolyte secondary battery is made according to method identical with the embodiment 1 of the present invention 2, carries out battery behavior examination It tests.The results are shown in Table 2.

The embodiment 8 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the amount of nona-fluoro butyl group ethylether is changed to 0.5 weight % by 2 weight %, is removed Except this, non-aqueous electrolyte secondary battery is made according to method identical with the embodiment 7 of the present invention 2, carries out battery behavior examination It tests.The results are shown in Table 2.

The embodiment 9 of the present invention 2

In the preparation of nonaqueous electrolytic solution, the difluorophosphoric acid of 0.2 weight % is replaced using the difluorophosphoric acid sodium of 0.2 weight % In addition to this lithium makes non-aqueous electrolyte secondary battery according to method identical with the embodiment 3 of the present invention 2, it is special to carry out battery Property test.The results are shown in Table 2.

The comparative example 1 of the present invention 2

In the preparation of nonaqueous electrolytic solution, without using the compound and difluorophosphate of the compound group of the present invention 2, this is removed Except, non-aqueous electrolyte secondary battery is made according to method identical with the embodiment 1 of the present invention 2, carries out battery behavior test. The results are shown in Table 2.

The comparative example 2 of the present invention 2

In the preparation of nonaqueous electrolytic solution, difluorophosphate is not used, in addition to this, according to the embodiment 1 with the present invention 2 Identical method makes non-aqueous electrolyte secondary battery, carries out battery behavior test.The results are shown in Table 2.

The comparative example 3 of the present invention 2

In the preparation of nonaqueous electrolytic solution, difluorophosphate is not used, in addition to this, according to the embodiment 3 with the present invention 2 Identical method makes non-aqueous electrolyte secondary battery, carries out battery behavior test.The results are shown in Table 2.

The comparative example 4 of the present invention 2

In the preparation of nonaqueous electrolytic solution, difluorophosphate is not used, in addition to this, according to the embodiment 5 with the present invention 2 Identical method makes non-aqueous electrolyte secondary battery, carries out battery behavior test.The results are shown in Table 2.

The comparative example 5 of the present invention 2

In the preparation of nonaqueous electrolytic solution, difluorophosphate is not used, in addition to this, according to the embodiment 7 with the present invention 2 Identical method makes non-aqueous electrolyte secondary battery, carries out battery behavior test.The results are shown in Table 2.

The comparative example 6 of the present invention 2

In the preparation of nonaqueous electrolytic solution, without using the present invention 2 compound group compound, in addition to this, according to The identical method of embodiment 7 of the present invention 2 makes non-aqueous electrolyte secondary battery, carries out battery behavior test.As a result such as 2 institute of table Show.

Table 2 is shown is with output power after the initial stage output power of the battery of the comparative example 1 of the present invention 2 and circulation The ratio of the initial stage output power of each battery and output power after circulation when 100%.

[table 2]

As shown in Table 2, the non-aqueous electrolyte secondary battery of 1~embodiment of embodiment 9 of the present invention 2 has used contains simultaneously Belong to the compound of the compound group of the present invention 2 and the nonaqueous electrolytic solution of difluorophosphoric acid salt；The present invention 2 comparative example 1 it is non-aqueous Electrolyte secondary battery, which does not contain, to be belonged in the compound of compound group and the nonaqueous electrolytic solution of difluorophosphoric acid salt of the present invention 2 Any one；The non-aqueous electrolyte secondary battery of the comparative example 6 of the present invention 2 only contains difluorophosphate, compared with the present invention 2 The non-aqueous electrolyte secondary battery of example 1, the non-aqueous electrolyte secondary battery of the comparative example 6 of the present invention 2 are compared, the reality of the present invention 2 The non-aqueous electrolyte secondary battery for applying 1~embodiment of example 9 shows high output characteristics.Moreover, being followed even if comparing by high temperature Output power after ring, the present invention 2 1~embodiment of embodiment 9 battery relative to the present invention 2 comparative example 1 output work The climbing of rate is also bigger.

On the other hand, it is known that the non-aqueous electrolyte secondary battery of 2~comparative example of comparative example 5 of the present invention 2 is (containing belonging to this Invent the compound of 2 compound group but do not contain difluorophosphoric acid salt) it is secondary with the nonaqueous electrolyte of the comparative example 1 of the present invention 2 Battery (any one of compound and the nonaqueous electrolytic solution of difluorophosphoric acid salt without containing the compound group for belonging to the present invention 2) It compares, it may be said that output power absolutely not changes.Thus result can confirm the serviceability of the present invention 2, i.e., made by combination With the compound and difluorophosphate of the compound group for belonging to the present invention 2, output characteristics is improved.

[about the present invention 3]

The embodiment 1 of the present invention 3

<production of secondary cell>

[positive production]

Cobalt acid lithium (the LiCoO of 94 weight % as a positive electrode active material is mixed in N-Methyl pyrrolidone solvent₂)、3 Acetylene black and 3 weight %s Kynoar (PVdF) as adhesive of the weight % as conductive material, is made slurry.It will Obtained slurry is coated on the two sides of 14 μm of thickness of aluminium foil, and is dried, and is rolled into 85 μm of thickness with press, then will in this way Treated, and aluminium foil strikes out diameter 12.5mm circle, as anode.

[production of cathode]

Using 18 μm of thickness of electrolytic copper foil as current collection structure base board, uses Si as target electrode material, use DC sputtering device (" HSM-52 " of the manufacture of company, Shimadzu Seisakusho Ltd.), with power density 4.7W/cm², stackeding speed (film forming speed) about 1.8nm/ Sec carries out the film forming of Si film, obtains Si film cathode.

[nonaqueous electrolytic solution]

Under dry argon atmospher, the dissolution point in the mixture (volume ratio 3:7) of ethylene carbonate and diethyl carbonate LiPF not fully dried₆With difluorophosphoric acid salt, make LiPF₆Concentration with difluorophosphoric acid salt is respectively 1mol/L, 1 weight %, Desired nonaqueous electrolytic solution is made.

[processing of electrode]

Cathode obtained above is handled by the following method.3- methyl-prop is dissolved in diethyl carbonate (DEC) Alkene acyl propyl-triethoxysilicane makes its 1 weight % of concentration relative to diethyl carbonate (DEC), prepares cathode treatment fluid. The electrode is immersed in the cathode treatment fluid, then carries out heating for 1 hour at 110 DEG C.Then subtract at 60 DEG C It is used after pressing dry dry 11 hours.In addition, anode uses after being dried under reduced pressure 11 hours at 80 DEG C without above-mentioned processing.

[production of non-aqueous electrolyte secondary battery]

Anode is encased in the stainless steel tank as cathode conductor, on it by being saturated with the poly- of electrolyte Ethylene partition places cathode.It is sealed by the tank body and as the hush panel of negative electrode conductor by insulation washer etc., Make Coin-shaped battery.

<evaluation of battery>

Above-mentioned battery is subjected to 5 following circulations, makes battery the operation is stable, the circulation are as follows: at 25 DEG C to be equivalent to The constant current charging of 0.2C to end of charge voltage 4.2V, be discharged to final discharging voltage 2.5V again；6th circulation are as follows: with The electric current for being equivalent to 0.2C charges to end of charge voltage 4.2V, then carries out charging to charging current value being to be equivalent to 0.02C's After the 4.2V- constant-current constant-voltage charging (CCCV charging) (0.02C cutting) of current value, to be equivalent to the constant electricity of 0.5C Flow valuve carries out 2.5V electric discharge；7th circulation are as follows: carry out the charging of 4.2V- constant-current constant-voltage to be equivalent to the electric current of 0.2C After (CCCV charging) (0.02C cutting), 2.5V electric discharge is carried out to be equivalent to the constant current value of 1.0C.Then, in following conditions It is lower circulation 92 times, the condition are as follows: be equivalent to 0.5C electric current carry out the charging of 4.2V- constant-current constant-voltage (CCCV fills Electricity) (0.05C cutting), 2.5V electric discharge is then carried out with the constant current value for being equivalent to 0.5C；100th circulation are as follows: with suitable The charging of 4.2V- constant-current constant-voltage (CCCV charging) (0.02C cutting) is carried out in the electric current of 0.2C, then to be equivalent to The constant current value of 0.2C carries out 2.5V electric discharge.1C mentioned here indicates the current value that can reach full charge in 1 hour.

Embodiment 2~present invention 3 embodiment 4 of the present invention 3

According to method production anode same as the embodiment 1 of the present invention 3, cathode and prepare nonaqueous electrolytic solution.Then divide Not carry out electrode processing.That is, diethyl carbonate (DEC) or pure water are used respectively, respectively at it according to described in table 3 Middle dissolution or dispersion 3- methacryl propyl-triethoxysilicane or 3- aminopropyl triethoxysilane, make 3- methacryl Propyl-triethoxysilicane or 3- aminopropyl triethoxysilane are 1 weight relative to the concentration of diethyl carbonate (DEC) or pure water % is measured, cathode treatment fluid is prepared, cathode is handled according to method same as the embodiment 1 of the present invention 3.With the present invention 3 Embodiment 1 it is identical, also without anode processing.Non-aqueous solution electrolysis is made according to method identical with the embodiment 1 of the present invention 3 Then electrolitc secondary cell carries out the evaluation of battery according to method identical with the embodiment 1 of the present invention 3.As a result it is shown in table together 3。

The comparative example 1 of the present invention 3

It is non-aqueous according to being prepared according to method identical with the embodiment 1 of the present invention 3 other than without using difluorophosphate Electrolyte.In addition, according to method production anode identical with the embodiment 1 of the present invention 3 and cathode.Then, only right at 60 DEG C Cathode be dried under reduced pressure within 11 hours.The processing of anode is also equally carried out with the embodiment 1 of the present invention 3.According to the present invention's 3 After the identical method of embodiment 1 makes non-aqueous electrolyte secondary battery, according to the identical method of embodiment 1 of the present invention 3 into The evaluation of row battery.As a result it is shown in table 3 together.

2~comparative example of comparative example 5 of the present invention 3

Other than without using difluorophosphate, non-aqueous solution electrolysis is prepared according to method identical with the embodiment 1 of the present invention 3 Liquid.In addition, according to method production anode identical with the embodiment 1 of the present invention 3 and cathode.Then, without the processing of electrode. That is, as described in Table 3, using diethyl carbonate (DEC) or pure water respectively, 3- methyl-prop is dissolved or dispersed wherein respectively Alkene acyl propyl-triethoxysilicane or 3- aminopropyl triethoxysilane, make 3- methacryl propyl-triethoxysilicane or 3- Aminopropyl triethoxysilane is 1 weight % relative to the concentration of diethyl carbonate (DEC) or pure water, prepares cathode treatment fluid, Cathode is handled according to method same as the embodiment 1 of the present invention 3.Anode handles the also embodiment 1 with the present invention 3 It is same to carry out.Make non-aqueous electrolyte secondary battery according to the identical method of embodiment 1 with the present invention 3, then according to this The identical method of embodiment 1 of invention 3 carries out the evaluation of battery.As a result it is shown in table 3 together.

The comparative example 6 of the present invention 3

According to method same as the embodiment 1 of the present invention 3, production anode, cathode simultaneously prepare nonaqueous electrolytic solution.Then, Only cathode be dried under reduced pressure within 11 hours at 60 DEG C.Anode is carried out according to method identical with the embodiment 1 of the present invention 3 Processing.Make non-aqueous electrolyte secondary battery according to the identical method of embodiment 1 with the present invention 3, then according to the present invention 3 The identical method of embodiment 1 carry out battery evaluation.As a result it is shown in table 3 together.

It is confirmed by gas chromatograph, in the ratio of the embodiment 2, of the invention 3 of the embodiment 1, of the invention 3 of the present invention 3 Compared in the nonaqueous electrolytic solution after the production of the non-aqueous electrolyte secondary battery of example 2 and comparative example 3, contain relative to the nonaqueous electrolytic solution Total amount is the 3- methacryl propyl-triethoxysilicane of 0.06 weight %.In addition, being confirmed by gas chromatograph, at this Embodiment 3, the embodiment 4 of the present invention 3,3 comparative example 4 of the invention and the non-aqueous electrolyte secondary battery of comparative example 5 of invention 3 In nonaqueous electrolytic solution after production, contain the 3- aminopropyl-triethoxy for being 0.13 weight % relative to the nonaqueous electrolytic solution total amount Silane.

As a result, the comparative example 1 of the discharge capacity and the present invention 3 that are recycled with 50 times in each example is (at cathode Difluorophosphoric acid salt is not used in reason) the ratio between the discharge capacities of 50 circulations be shown in table 3 as " 50 cyclic discharge capacity ratios " In.That is, " 50 cyclic discharge capacity ratios " indicate are as follows: (50 cyclic discharge capacity ratios)=(50 times circulation Discharge capacity)/(discharge capacity of the comparative example 1 of the present invention 3 of 50 circulations).

[table 3]

As shown in Table 3, meet the nonaqueous electrolyte two of the nonaqueous electrolytic solution production using the present invention 3 of condition 1 and condition 2 Primary cell and one only met in condition 1 or condition 2 are both unsatisfactory for condition 1 or are unsatisfactory for the nonaqueous electrolyte two of condition 2 Primary cell is compared, and the discharge capacity after 50 circulations shows bigger value, is being inhibited the deterioration with battery charging and discharging, is being extended It succeeds in terms of battery life, the condition 1 is that the compound shown in general formula (1) or general formula (2) handles cathode, institute Stating condition 2 is in nonaqueous electrolytic solution containing the difluorophosphate as " mono-fluor phosphate and/or difluorophosphoric acid salt ".

Specifically, at the same meet condition 1,1~embodiment of embodiment 4 of the present invention 3 of condition 2 is inhibited with charge and discharge Battery behavior deterioration.In contrast, it is known that be unsatisfactory for the discharge capacity of the comparative example 1 of the present invention 3 of any one condition Conservation rate is small, and deterioration of battery is significant.Moreover, only meeting the comparative example 2 of one present invention 3 in condition 1 or condition 2~compare Example 6 all shows bigger discharge capacity compared with the comparative example 1 of the present invention 3, and determining has the effect of inhibiting deterioration of battery, But it compared with the non-aqueous electrolyte secondary battery of the present invention 3 (1~embodiment of embodiment 4 of the present invention 3), has little effect.It needs It is noted that although the record of condition 1, condition 2 has been carried out, but as long as being content described in claim, and unlimited It is set to the content of the embodiment of the present invention 3.

[about the present invention 4]

[preparation of electrolyte]

By the ethylene carbonate/dimethyl carbonate/ethyl methyl carbonate purified under dry argon atmospher respectively according to 381.6g/310.0g/391.5g the amount of (about 290mL/290mL/385mL) mixes, dissolved in the solvent being obtained by mixing 151.9g lithium hexafluoro phosphate (LiPF fully dried₆).The specific gravity of the solution is 1.22.In the above solution according to 4 institute of table Additive is added in the amount shown, and is allowed to dissolve.

[table 4]

In table 4, " embodiment 1 " expression " embodiment 4-1 ", " embodiment 2 " expression " embodiment 4-2 ".It is " logical Compound represented by formula (3) " expression " compound represented by 4 formula ofs (3) of the invention ".

[chemical formula 35]

[production of secondary cell]

<production of " secondary cell 1 ">

(positive production)

Cobalt acid lithium (the LiCoO of 90 weight % as a positive electrode active material is mixed in N-Methyl pyrrolidone solvent₂)、5 Acetylene black, 5 weight %s Kynoar (hreinafter referred to as " PVDF ") as binder of the weight % as conductive material, Prepare slurry.Obtained slurry is coated on to the two sides of 15 μm of aluminium foil, and is dried, is rolled into 80 μm of thickness with press, By treated in this way, aluminium foil is cut into the size of active material layer as width 100mm, long 100mm, and uncoated with width 30mm Partial shape, as anode.

(production of cathode)

100 parts by weight conducts are added in 98 parts by weight artificial graphite powder KS-44 (manufacture of Timcal company, trade name) The aqueous liquid dispersion (concentration of sodium carboxymethylcellulose is 1 weight %) of the sodium carboxymethylcellulose of thickener, 2 parts by weight conducts The aqueous liquid dispersion (concentration of SBR styrene butadiene rubbers be 50 weight %) of the SBR styrene butadiene rubbers of adhesive, with point Scattered device is mixed, and slurry is made.

Obtained slurry is coated on to the two sides of the copper foil of 10 μ m-thicks, and is dried, 75 μm are rolled into press, by this The size of sample treated copper foil is cut into active material layer is width 104mm, long 104mm, and has the uncoated portion of width 30mm Shape, as cathode.

(assembling of battery)

By anode, cathode, overlapping under conditions of contacting anode and cathode directly is crimped with polyethylene partition, system At electrode body.It is loaded into battery can, so that the terminal of anode and cathode is exposed to outside.Then, 5mL is injected thereto Aftermentioned electrolyte carries out caulk molding (か め forming), 18650 type cylinder batteries is made, as " secondary cell 1”。

<production of " secondary cell 2 ">

With nickel manganese cobalt acid lithium (LiNi_1/3Mn_1/3Co_1/3O₂) replacing cobalt acid lithium as a positive electrode active material, charging voltage is In addition to this 4.25V makes battery according to method identical with secondary cell 1, as " secondary cell 2 ".

<production of " secondary cell 3 ">

With LiFePO4 (LiFePO₄) replace cobalt acid lithium as a positive electrode active material, charging voltage 4.25V, except this it Outside, battery is made according to method identical with secondary cell 1, as " secondary cell 3 ".

<production of " secondary cell 4 ">

Use 73.2 parts by weight as non-carbon material silicon, 8.1 parts by weight copper and 12.2 parts by weight artificial graphite powder (Timcal corporation trade name " KS-6 ") is used as negative electrode active material, and the N- methyl containing 12 weight %PVDF is added thereto 54.2 parts by weight of pyrrolidone solution and 50 parts by weight N-Methyl pyrrolidones, are mixed with disperser, make slurry.

Obtained slurry is uniformly coated on the copper foil as 18 μm of thickness of negative electrode collector, after natural drying, most Diel is dried under reduced pressure at 85 DEG C eventually.Then carrying out compacting makes electrode density 1.5gcm^-3Left and right, strikes out diameter 12.5mm's is discoid, as cathode (silicon alloy cathode), in addition to this, makes electricity according to method identical with secondary cell 1 Pond, as " secondary cell 4 ".

<production of " secondary cell 5 ">

90 weight % negative electrode active material (Li are mixed in N-Methyl pyrrolidone solvent_4/3Ti_5/3O₄), 5 weight % make For the Kynoar (PVdF) as adhesive of acetylene black, 5 weight % of conductive material, slurry is made.

Obtained slurry is coated on a face of the rolled copper foil of 10 μ m-thicks, and is dried, is rolled into press 90 μm, by treated in this way, copper foil is cut into the size of active material layer as width 104mm, long 104mm, and has width 30mm not In addition to this shape of coated portion, makes battery according to method identical with secondary cell 1 as cathode, as " secondary cell 5 ".

The embodiment 1~14 of the present invention 4 and the comparative example 1~8 of the present invention 4

It is each of the invention 4 embodiment, every as the embodiment 1~14 of the present invention 4 and the comparative example 1~8 of the present invention 4 A of the invention 4 comparative example is according to experimental condition documented by following table 5, table 6 (type of electrolyte and secondary cell) Combination is tested, and obtains result for following assessment items.Its result is as shown in following table 5, table 6.

[evaluation of secondary cell]

The evaluation of secondary cell evaluates each battery according to following conditions.

<evaluation of secondary cell 1>

(initial capacity)

It carries out charging to 4.2V with the constant-current constant-voltage mise-a-la-masse method of 0.2C at 25 DEG C, then with the constant of 0.2C Electric current carries out being discharged to 3.0V.The circulation is carried out 5 times, battery is stablized.It is with the discharge capacity that the 5th at this time recycles " initial capacity ".It should be noted that the current value that will enable rated capacity to discharge in 1 hour is as 1C.

(circulation conservation rate)

Carry out 500 following charge and discharge cycles, the charge and discharge are as follows: the battery after initial stage charge and discharge will be implemented at 60 DEG C It is lower to carry out charging to 4.2V with the constant-current constant-voltage method of 1C, 3.0V is then discharged to the constant current of 1C.It will at this time The 500th cyclic discharge capacity account for the ratio of the 1st cyclic discharge capacity as " circulation conservation rate ".

(initial stage low temperature discharge rate)

The battery after initial stage charge and discharge will be implemented to be charged at 25 DEG C with the constant-current constant-voltage method of 0.2C Then 4.2V implements the constant-current discharge of 0.2C at -30 DEG C.It, will be first using discharge capacity at this time as initial stage low temperature capacity The ratio that phase low temperature capacity accounts for initial capacity is used as " initial stage low temperature discharge rate ".

(low temperature discharge rate after circulation)

Battery after cyclic test is charged into 4.2V at 25 DEG C with the constant-current constant-voltage mise-a-la-masse method of 0.2C, so 3.0V is discharged to the constant current of 0.2C afterwards.The circulation is carried out 3 times, after the discharge capacity that the 3rd is recycled is as circulation Capacity.Then, same battery is charged into 4.2V with the constant-current constant-voltage mise-a-la-masse method of 0.2C at 25 DEG C, then- Implement the constant current electric discharge of 0.2C at 30 DEG C.Using discharge capacity at this time as low temperature capacity after circulation, by low temperature after circulation Capacity accounts for the ratio conduct " low temperature discharge rate after circulation " of capacity after circulation.

<evaluation of secondary cell 2>

The charging voltage of each test is changed to 4.25V by 4.2V, in addition to this, for the evaluation phase with secondary cell 1 Same project, is carried out similarly evaluation.

<evaluation of secondary cell 3>

The charging voltage of each test is changed to 3.8V by 4.2V and discharge voltage is changed to 2.5V by 3.0V, removes this Except, for project identical with the evaluation of secondary cell 1, it is carried out similarly evaluation.

<evaluation of secondary cell 4>

The discharge voltage of each test is changed to 2.5V by 3.0V, in addition to this, for identical as the evaluation of secondary cell 1 Project, be carried out similarly evaluation.

<evaluation of secondary cell 5>

The charging voltage of each test is changed to 2.7V by 4.2V and discharge voltage is changed to 1.9V by 3.0V, removes this Except, for project identical with the evaluation of secondary cell 1, it is carried out similarly evaluation.

It is put using the initial capacity of the embodiment 1~16 of the present invention 4 of electrolyte 1~12, circulation conservation rate, initial stage low temperature Low temperature discharge rate is good after electric rate and circulation, and uses at least one of the comparative example 1~8 of the present invention 4 of electrolyte A~D It is very poor.

[table 5]

" table 61

[about the present invention 5]

Battery obtained in following embodiments and comparative example it is each evaluation method is as follows described.

[discharge capacity evaluation]

Nonaqueous electrolyte battery is equivalent to the constant current charging of 0.1C to 4.2V, then with 0.1C's at 60 DEG C Constant current is discharged to 3V.By the circulation carry out 20 times, find out with initial stage discharge capacity be 100 when through 20 times circulation after electric discharge Capacity (%), as " discharge capacity (%) after circulation ".1C mentioned here indicates to hold the benchmark of battery in 1 hour The current value of electric discharge is measured, 0.1C indicates its 1/10 current value.

The embodiment 1 of the present invention 5

[manufacture of nonaqueous electrolytic solution]

Under dry argon atmospher, in N- butyl-N- crassitudeImines is (hreinafter referred to as two (trifluoro methylsulfonyls) " BMPTFSI ") in dissolution two (trifluoro methylsulfonyl) imidization lithium (hreinafter referred to as " LiTFSI ") fully dried, make it Ratio is 0.4mol/L.Dissolve thereto again relative to 98 parts by weight BMPTFSI and LiTFSI mixture be 2 parts by weight warp Sufficiently dry difluorophosphate is (hereinafter, sometimes referred to simply as " LiPO₂F₂"), nonaqueous electrolytic solution is made.

[manufacture of nonaqueous electrolyte battery]

Cobalt acid lithium (the LiCoO of 90 weight % as a positive electrode active material is mixed in N-Methyl pyrrolidone solvent₂)、5 Acetylene black and 5 weight %s Kynoar (PVdF) as adhesive of the weight % as conductive material, makes slurry. Obtained slurry is coated on a face of 15 μm of thickness of aluminium foil, and is dried, is rolled into 80 μm of thickness with press, it will Treated in this way, and aluminium foil strikes out active material layer size as the discoid of diameter 12.5mm, makes electrode, as work electricity Pole (effect pole), across being saturated with nonaqueous electrolyte electricity of the dummy plate of nonaqueous electrolytic solution as Coin shape lithium secondary battery Pond, the battery are evaluated using lithium foil as to electrode.The ingredient of nonaqueous electrolytic solution is as shown in table 7, evaluation result such as table 8 It is shown.

The embodiment 2 of the present invention 5

In the nonaqueous electrolytic solution of the embodiment 1 of the present invention 5, two (trifluoro methylsulphur of N- butyl-N, N, N- trimethyl ammonium is used Acyl) imines (hreinafter referred to as " BTMATFSI ") is instead of BMPTFSI, in addition to this, according to identical as the embodiment 1 of the present invention 5 Method make Coin shape lithium secondary battery, and evaluated.The ingredient of nonaqueous electrolytic solution is as shown in table 7, evaluation result such as table 8 It is shown.

The embodiment 3 of the present invention 5

In the nonaqueous electrolytic solution of the embodiment 1 of the present invention 5, N, N- dimethyl-N-methyl-N-methoxy ethyl ammonium are used Two (trifluoro methylsulfonyl) imines (hreinafter referred to as " DEMETFSI ") replace BMPTFSI, in addition to this, according to the present invention's 5 The identical method of embodiment 1 makes Coin shape lithium secondary battery, and is evaluated.The ingredient of nonaqueous electrolytic solution is as shown in table 7, comments The results are shown in Table 8 for valence.

The comparative example 1 of the present invention 5

LiTFSI fully dried is dissolved in BMPTFSI, makes to prepare nonaqueous electrolytic solution its ratio be 0.4mol/L, And the nonaqueous electrolytic solution is used, it is in addition to this, secondary according to method production Coin shape lithium identical with the embodiment 1 of the present invention 5 Battery, and evaluated.The ingredient of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.

The comparative example 2 of the present invention 5

LiTFSI fully dried is dissolved in BTMATFSI, makes to prepare nonaqueous electrolytic solution its ratio be 0.4mol/L, And the nonaqueous electrolytic solution is used, it is in addition to this, secondary according to method production Coin shape lithium identical with the embodiment 1 of the present invention 5 Battery, and evaluated.The ingredient of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.

The comparative example 3 of the present invention 5

LiTFSI fully dried is dissolved in DEMETFSI, makes to prepare nonaqueous electrolytic solution its ratio be 0.4mol/L, And the nonaqueous electrolytic solution is used, it is in addition to this, secondary according to method production Coin shape lithium identical with the embodiment 1 of the present invention 5 Battery, and evaluated.The ingredient of nonaqueous electrolytic solution is as shown in table 7, and evaluation result is as shown in table 8.

[table 7]

No.	Lithium salts	Room temperature fuse salt	LiPO2F2
				Embodiment 1	LiTFSI	BMPTFSI	2 weight %
Embodiment 2	LiTFSI	BTMATFSI	2 weight %
				Embodiment 3	LiTFSI	DEMETFSI	2 weight %
Comparative example 1	LiTFSI	BMPTFSI	-
				Comparative example 2	LiTFSI	BTMATFSI	-
Comparative example 3	LiTFSI	DEMETFSI	-

[table 8]

No.	It discharges after circulation
		Embodiment 1	91.2
Embodiment 2	90.8
		Embodiment 3	92.5
Comparative example 1	32.4
		Comparative example 2	65.9
Comparative example 3	69.5

As shown in Table 8, using the battery (present invention 5 Examples 1 to 3) of the nonaqueous electrolytic solution of the present invention 5, Charge-discharge characteristic is high.In contrast, the battery (comparative example 1~3 of the present invention 5) of the nonaqueous electrolytic solution of the present invention 5 is not used Charge-discharge characteristic is poor.

Industrial applicibility

The secondary electricity of nonaqueous electrolyte that capacity is high, cycle characteristics is excellent can be manufactured using the nonaqueous electrolytic solution of the present invention 1 Pond, therefore any field of electronic equipment preferably for using non-aqueous electrolyte secondary battery etc..

The nonaqueous electrolytic solution of the present invention 1 and the purposes of non-aqueous electrolyte secondary battery are not particularly limited, and can be used for known Various uses.It as concrete example, can enumerate, laptop, pen control type PC, pocket pc, electronics Book player, mobile phone, portable facsimile printer, portable copier, portable printer, stereophone, video camera, liquid crystal electricity Depending on, portable type cleaner, portable CD, minidisk, portable wireless walkie-talkie, electronic notebook, calculator, storage Card, portable recorder, radio, backup power source, motor, automobile, motorcycle, electric bicycle, bicycle, luminaire, Toy, game machine, table, lathe, flash lamp, camera etc..

Good output characteristics, High temperature storage characteristic and cycle characteristics can be made using the nonaqueous electrolytic solution of the present invention 2 Excellent non-aqueous electrolyte secondary battery, therefore times of electronic equipment preferably for using non-aqueous electrolyte secondary battery etc. What field.

The nonaqueous electrolytic solution of the present invention 2 and the purposes of non-aqueous electrolyte secondary battery are not particularly limited, and can be used for known Various uses.As specific purposes, purposes described in the present invention 1 can be enumerated.

Using the nonaqueous electrolytic solution of the present invention 3, the good nonaqueous electrolytic solution of cycle characteristics and nonaqueous electrolyte can be provided Secondary cell.Therefore any field of electronic equipment preferably for using non-aqueous electrolyte secondary battery etc..

The non-aqueous electrolyte for secondary battery of the present invention 3 and the purposes of non-aqueous electrolyte secondary battery are not particularly limited, It can be used for well known various uses.As specific purposes, purposes described in the present invention 1 can be enumerated.

It is good using the lithium secondary battery cryogenic discharging characteristic of the nonaqueous electrolytic solution of the present invention 4, heavy-current discharge characteristic, and High temperature storage characteristic, cycle characteristics are excellent, therefore any field of electronic equipment preferably for using secondary cell etc..Make For specific purposes, purposes described in the present invention 1 can be enumerated.

High capacity can be kept using the nonaqueous electrolyte battery of the nonaqueous electrolytic solution of the present invention 5 and safety etc. is good, It can be used for well known various uses.As specific purposes, purposes described in the present invention 1 can be enumerated.

The application is hereby incorporated the full content of following applications based on following Japanese patent applications, is incorporated into this In the content of description of the invention.

1: Japanese Patent Application 2007-111918 (applying date: on April 20th, 2007) of the invention

2: Japanese Patent Application 2007-111976 (applying date: on April 20th, 2007) of the invention

3: Japanese Patent Application 2007-116448 (applying date: on April 26th, 2007) of the invention

4: Japanese Patent Application 2007-272163 (applying date: on October 19th, 2007) of the invention

5: Japanese Patent Application 2007-116444 (applying date: on April 26th, 2007) of the invention

Claims (13)

1. a kind of nonaqueous electrolytic solution, which contains electrolyte and dissolves the nonaqueous solvents of the electrolyte, wherein described Nonaqueous electrolytic solution contains difluorophosphoric acid salt, also contains the iron family element for being 1~100ppm relative to nonaqueous electrolytic solution total amount, and institute Stating iron family element is cobalt element and/or nickel element.

2. nonaqueous electrolytic solution according to claim 1, wherein the total amount of the difluorophosphoric acid salt contained is that nonaqueous electrolytic solution is total 0.001 weight of weight %~5 % of amount.

3. nonaqueous electrolytic solution described according to claim 1~any one of 2, the nonaqueous electrolytic solution is secondary for nonaqueous electrolyte Battery, the non-aqueous electrolyte secondary battery have used active material in cathode, and the active material includes carbonaceous material.

4. nonaqueous electrolytic solution described according to claim 1~any one of 2, the nonaqueous electrolytic solution is secondary for nonaqueous electrolyte Battery, the non-aqueous electrolyte secondary battery have used active material in cathode, the active material have selected from Al atom, At least one kind of atom in Si atom, Sn atom, Pb atom and Ti atom.

5. nonaqueous electrolytic solution according to claim 3, which is used for non-aqueous electrolyte secondary battery, described non- Water-Electrolyte secondary cell has used active material in cathode, and the active material has former selected from Al atom, Si atom, Sn At least one kind of atom in son, Pb atom and Ti atom.

6. a kind of non-aqueous electrolyte for secondary battery, which is used for non-aqueous electrolyte secondary battery, the non-water power Solution electrolitc secondary cell has nonaqueous electrolytic solution and can occlude and release the cathode and anode of ion, wherein the non-aqueous solution electrolysis Liquid contains electrolyte and nonaqueous solvents, also contain mono-fluor phosphate and/or difluorophosphoric acid salt, and containing the following general formula (1) and/ Or compound represented by the following general formula (2), compound represented by the following general formula (1) and/or the following general formula (2) containing than Example is the 0.001 weight % of weight %~10 of the nonaqueous electrolytic solution total amount,

In formula, R¹、R²、R³、R⁴It is respectively independent, it is organic group or halogen atom, R¹、R²、R³、R⁴In at least one group in, with The atom of X Direct Bonding is hetero atom, R¹、R²、R³、R⁴Identical or different, X is the atom other than carbon atom；

In formula, R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, R⁵、R⁶、R⁷In at least one group in, it is direct with Y The atom of bonding is hetero atom, R⁵、R⁶、R⁷Identical or different, Y is the atom other than carbon atom.

7. a kind of non-aqueous electrolyte for secondary battery, which is used for non-aqueous electrolyte secondary battery, the non-water power Solution electrolitc secondary cell has nonaqueous electrolytic solution and can occlude and release the cathode and anode of ion, wherein the non-aqueous solution electrolysis Liquid contains mono-fluor phosphate and/or difluorophosphoric acid salt, also, the change represented by the following general formula (1) and/or the following general formula (2) Object is closed to handle anode and cathode,

In formula, R¹、R²、R³、R⁴It is respectively independent, it is organic group or halogen atom, R¹、R²、R³、R⁴In at least one group in, with The atom of X Direct Bonding is hetero atom, R¹、R²、R³、R⁴Identical or different, X is the atom other than carbon atom；

In formula, R⁵、R⁶、R⁷It is respectively independent, it is organic group or halogen atom, R⁵、R⁶、R⁷In at least one group in, it is direct with Y The atom of bonding is hetero atom, R⁵、R⁶、R⁷Identical or different, Y is the atom other than carbon atom.

8. a kind of nonaqueous electrolytic solution, which contains lithium salts and dissolves the nonaqueous solvents of the lithium salts, wherein described non-aqueous Electrolyte contains compound represented by the following general formula (1), and contains mono-fluor phosphate and/or difluorophosphoric acid salt,

In general formula (1), A and B indicate various substituent groups, and at least one therein is fluorine, and n indicates 3 or more natural number.

9. a kind of nonaqueous electrolytic solution, which contains lithium salts and dissolves the nonaqueous solvents of the lithium salts, wherein described non-aqueous Electrolyte contains relative to chemical combination represented by the following general formula (1) that nonaqueous electrolytic solution total amount is 0.001 weight of weight %~5 % Object, and contain the having in unsaturated bond and halogen atom for 0.001 weight of weight %~5 % relative to nonaqueous electrolytic solution total amount At least one of carbonic ester,

In general formula (1), A and B indicate various substituent groups, and at least one therein is fluorine, and n indicates 3 or more natural number.

10. a kind of non-aqueous electrolyte secondary battery, wherein used non-aqueous solution electrolysis according to any one of claims 1 to 9 Liquid.

11. a kind of non-aqueous electrolyte secondary battery, the non-aqueous electrolyte secondary battery include nonaqueous electrolytic solution and can occlude and Release the cathode and anode of lithium ion, wherein the nonaqueous electrolytic solution is non-water power according to any one of claims 1 to 9 Solve liquid.

12. a kind of nonaqueous electrolytic solution, which contains lithium salts and room temperature fuse salt, wherein in the nonaqueous electrolytic solution Contain mono-fluor phosphate and/or difluorophosphoric acid salt.

13. a kind of nonaqueous electrolyte battery, which at least has nonaqueous electrolytic solution and can occlude and release The cathode and anode of lithium ion, wherein the nonaqueous electrolytic solution is nonaqueous electrolytic solution described in claim 12.