JP2014137878A - Nonaqueous electrolyte secondary battery - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a nonaqueous electrolyte secondary battery improved in battery performance as compared with conventional ones.SOLUTION: In a nonaqueous electrolyte secondary battery 100 including a positive electrode 220, a negative electrode 240 and a nonaqueous electrolyte 90, the nonaqueous electrolyte 90 contains a nonaqueous solvent, an oxalate complex compound and an aromatic carbonate compound. With respect to 100 pts.mass of other electrolyte composition excluding the oxalate complex compound and the aromatic carbonate compound, the content of the oxalate complex compound and the content of the aromatic carbonate compound are 0.5 pts.mass or more and 2 pts.mass or less, and 0.5 pts.mass or more and 4 pts.mass or less, respectively.

Description

  The present invention relates to a non-aqueous electrolyte secondary battery. Specifically, the present invention relates to a non-aqueous electrolyte secondary battery having an improved capacity retention rate and a resistance reduction effect.

  Lithium ion secondary batteries and other secondary batteries are smaller, lighter, and have higher energy density and superior output density than existing batteries. For this reason, in recent years, it has been preferably used as a so-called portable power source such as a personal computer or a portable terminal, or a vehicle driving power source such as a hybrid vehicle.

  As the solvent of the electrolyte solution provided in this type of secondary battery, when the electrolyte solution receives a voltage equal to or higher than the decomposition voltage of water, water cannot be used as the solvent. (Also referred to as an aprotic solvent). For example, as an electrolyte solution for lithium ion secondary batteries, chemical species (here lithium ions) that can serve as charge carriers can be supplied to carbonate solvents (non-aqueous solvents) such as ethylene carbonate, propylene carbonate, and diethyl carbonate. A nonaqueous electrolytic solution in which a simple electrolyte (supporting electrolyte, typically a lithium salt) is dissolved is used. For example, Patent Document 1 is disclosed as a conventional document related to a non-aqueous electrolyte. Patent Document 1 describes that a liquid organic solvent is added to an electrolytic solution in order to improve cycle characteristics. In the examples, methylphenyl carbonate is used as the liquid organic solvent.

JP 09-022722 A

  However, when methylphenyl carbonate is added to the electrolyte solution as in Patent Document 1, methylphenyl carbonate works as a resistance component of the battery, and therefore, if the amount added increases, battery performance is adversely affected (for example, capacity deterioration or resistance increase). It is not preferable. Therefore, there is a need for a technique that can improve cycle characteristics and avoid capacity deterioration and resistance increase.

  This invention is made | formed in view of this point, The place made into the objective is providing the non-aqueous-electrolyte secondary battery whose battery performance improved compared with the past.

  The present inventor has found that by adding a small amount of an oxalato complex compound and an aromatic carbonate compound to a non-aqueous electrolyte, the capacity retention rate and output characteristics of a battery equipped with the electrolyte can be greatly improved. Furthermore, according to the oxalato complex compound and the aromatic carbonate compound, it has been found that a higher improvement effect is realized by adding each in combination of capacity retention rate and output characteristic than by adding them individually. The present invention has been completed.

That is, according to the present invention, a non-aqueous electrolyte secondary battery including a positive electrode, a negative electrode, and a non-aqueous electrolyte is provided. The non-aqueous electrolyte includes a non-aqueous solvent, an oxalato complex compound, and an aromatic carbonate compound. The content of the oxalato complex compound is 0.5 parts by mass or more and 2 parts by mass or less (preferably 0.8 parts by mass) with respect to 100 parts by mass of the other electrolyte components except the oxalato complex compound and the aromatic carbonate compound. 5 parts by mass or more and 1.5 parts by mass or less), and the content of the aromatic carbonate compound is 0.5 parts by mass or more and 4 parts by mass or less (preferably more than 1 part by mass and less than 4 parts by mass, more preferably Is 2 parts by mass or more and 3 parts by mass or less).
In other words, the non-aqueous electrolyte is 0.5 wt% or more and 2 wt% or less (preferably 0.5 wt%), where the total mass of other electrolyte components excluding the oxalato complex compound and the aromatic carbonate compound is 100 wt%. % Of the oxalato complex compound corresponding to the mass of 0.5 wt% to 1.5 wt%, and 0.5 wt% to 4 wt% (preferably 1 wt% to 4 wt%, more preferably greater than 1 wt% to 4 wt% Less than that, more preferably 2 wt% or more and 3 wt% or less). In a preferred embodiment, the oxalato complex compound includes at least lithium bisoxalate borate. In a preferred embodiment, the aromatic carbonate compound contains at least methyl phenyl carbonate.

  According to such a non-aqueous electrolyte secondary battery, a non-aqueous electrolyte secondary battery (for example, a lithium secondary battery) constructed using the electrolyte solution by containing the oxalato complex compound and the aromatic carbonate compound in the above-described content. (Typically, a lithium ion secondary battery) capacity retention ratio and output characteristics can be improved. Typically, the rate of increase in resistance after high-temperature storage durability compared to a battery constructed using an electrolyte solution with a composition to which no oxalato complex compound and aromatic carbonate compound are added or to which they are added alone As a result, a larger capacity retention rate improvement effect is exhibited. This can effectively improve the durability of the battery.

  In the present specification, the term “secondary battery” refers to a power storage device that can be repeatedly charged and discharged, and a so-called storage battery such as a lithium secondary battery, nickel hydride battery, or nickel cadmium battery, and a power storage element such as an electric double layer capacitor. It is a term encompassing. The “non-aqueous electrolyte secondary battery” refers to a secondary battery including a non-aqueous electrolyte (typically, an electrolyte containing a supporting salt (supporting electrolyte) in a non-aqueous solvent). The “lithium secondary battery” refers to a secondary battery that uses lithium ions as electrolyte ions and is charged and discharged by the movement of lithium ions between the positive and negative electrodes. A secondary battery generally referred to as a lithium ion battery is a typical example included in the lithium secondary battery in this specification. The electrode active material refers to a material that can reversibly occlude and release chemical species (lithium ions in a lithium ion secondary battery) as a single charge.

  The technique disclosed herein can be preferably applied to a nonaqueous electrolytic solution in which 50% by volume or more of the nonaqueous solvent is composed of one or two or more carbonate solvents. In the nonaqueous electrolytic solution having such a composition, it is particularly meaningful to contain an oxalato complex compound and an aromatic carbonate compound. For example, in a non-aqueous electrolyte secondary battery (typically a lithium ion secondary battery) constructed using the non-aqueous electrolyte, the durability performance of the battery (for example, resistance increase rate and capacity after high-temperature storage durability) Maintenance rate) can be effectively improved.

FIG. 1 is a diagram schematically showing a lithium ion secondary battery according to an embodiment of the present invention. FIG. 2 is a diagram schematically showing a wound electrode body incorporated in a lithium ion secondary battery. FIG. 3 is a graph showing the resistance increase rate of each example. FIG. 4 is a graph showing the capacity retention rate of each example. FIG. 5 is a graph showing the relationship between the added amount of MPhC and the resistance increase rate. FIG. 6 is a graph showing the relationship between the added amount of MPhC and the capacity retention rate. FIG. 7 is a diagram showing a vehicle equipped with a non-aqueous electrolyte secondary battery.

  Hereinafter, preferred embodiments of the present invention will be described. Note that matters other than matters specifically mentioned in the present specification and necessary for the implementation of the present invention can be grasped as design matters of those skilled in the art based on the prior art in this field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

  In the configuration of the non-aqueous electrolyte secondary battery disclosed herein, a positive electrode, a negative electrode, and a non-aqueous electrolyte are accommodated in a battery case, and the non-aqueous electrolyte includes a non-aqueous solvent, an oxalato complex compound, and an aroma. The present invention can be widely applied to various non-aqueous electrolyte secondary batteries including a group carbonate compound. Hereinafter, the case of a lithium ion secondary battery may be described in more detail as a typical example, but the application target of the present invention is not intended to be limited to such a battery.

<Non-aqueous electrolyte>
The nonaqueous electrolytic solution used in the secondary battery disclosed herein is characterized by including an oxalato complex compound and an aromatic carbonate compound in a nonaqueous solvent.

《Aromatic carbonate compound》
The aromatic carbonate compound is not particularly limited as long as it is a carbonate (carbonate ester) compound having at least an aromatic group, and one or two or more kinds can be appropriately used. For example, the aromatic carbonate compound may be any of a benzene aromatic carbonate compound, a heteroaromatic carbonate compound, and a non-benzene aromatic carbonate compound. In an aromatic ring (typically a benzene ring), hydrogen atoms bonded to atoms (for example, carbon atoms) constituting the aromatic ring are each independently an aliphatic alkyl group (straight chain having 1 to 10 carbon atoms). Or branched), an alicyclic alkyl group (saturated or unsaturated having 1 to 10 carbon atoms), an oxygen atom (which may be a hydroxyl group (OH)), a halogen atom (for example, F, Cl, Br), etc. The compound prepared may be used. A compound in which such an aromatic ring (including a heteroaromatic ring) is directly bonded to a carbonate group (OCOO) is preferable. For example, a compound in which the aromatic ring and an alkyl group having 1 to 4 carbon atoms (preferably 1 or 2) are directly bonded to a carbonate group can be suitably used. Specific examples of the aromatic carbonate compound preferable for the technique disclosed herein include alkylphenyl carbonate (ROCOOPh, where R represents an alkyl group and Ph represents a phenyl group). Such an alkylphenyl carbonate may have an alkyl group having 1 to 4 carbon atoms (preferably 1 or 2). Particularly preferred examples include methyl phenyl carbonate (MPhC) and ethyl phenyl carbonate. Of these, use of MPhC is preferable.

  In one embodiment of the non-aqueous electrolyte used in the secondary battery disclosed herein, the content X of the aromatic carbonate compound (when two or more aromatic carbonate compounds are included, the total amount thereof) is: The total amount of other electrolyte components is preferably 0.5 parts by mass or more and less than 4 parts by mass (that is, 0.5 ≦ X ≦ 4). For example, as in Examples described later, a reference electrolyte solution in which a supporting electrolyte is dissolved in a nonaqueous solvent at an appropriate concentration is prepared, and X parts by mass (here 0.5 ≦ X) per 100 parts by mass of the reference electrolyte solution. The non-aqueous electrolyte solution disclosed herein can be preferably prepared by adding the aromatic carbonate compound of ≦ 4) and mixing them uniformly. Usually, the content X of the aromatic carbonate compound with respect to 100 parts by mass of the other electrolyte components is suitably 0.5 parts by mass or more and 4 parts by mass or less (that is, 0.5 ≦ X ≦ 4). , Preferably more than 1 part by weight and less than 4 parts by weight (that is, 1 <X <4), more preferably 2 parts by weight to 3 parts by weight, and particularly preferably 2.2 parts by weight. It is not less than 2.8 parts by mass.

<Oxalato complex compound>
The oxalato complex compound is not particularly limited and can be used singly or in combination of two or more kinds prepared from known methods or obtained by purchasing commercially available products. For example, the oxalato complex compound preferably contains at least a boron atom (B) as a constituent atom. For example, the oxalato complex compound may contain at least lithium bisoxalate borate (LiBOB) represented by the following formula (I). Alternatively, as represented by the following formula (II) or (III), an oxalato complex compound having a structural portion in which at least one oxalate ion (C ₂ O ₄ ²⁻ ) is coordinated to a boron atom (B) ( B atom-containing oxalate salt).

Here, R ₁ and R ₂ in formula (II) are each independently a halogen atom (for example, F, Cl, Br, preferably F) and a carbon number of 1 to 10 (preferably 1 to 3). Selected from perfluoroalkyl groups. A ^{+ in} formulas (I) and (II) may be either an inorganic cation or an organic cation. Specific examples of inorganic cations include alkali metal cations such as Li, Na and K; alkali metal cations such as Li, Na and K; alkaline earth metal cations such as Be, Mg and Ca; Zn, Cu, Co, Fe, Ni, Mn, Ti, Pb, Cr, V, Ru, Y, metal cations such as lanthanoids, actinoids, protons, and the like. Specific examples of organic cations include tetraalkylammonium ions such as tetrabutylammonium ion, tetraethylammonium ion and tetramethylammonium ion; trialkylammonium ions such as triethylmethylammonium ion and triethylammonium ion; other pyridinium ions and imidazolium ions Ion, tetraethylphosphonium ion, tetramethylphosphonium ion, tetraphenylphosphonium ion, triphenylsulfonium ion, triethylsulfonium ion; and the like. Examples of preferred cations include Li ions, tetraalkylammonium ions and protons.

  As a preferred embodiment disclosed herein, a B atom-containing oxalate salt represented by the formula (III) (for example, lithium bis (oxalato) borate, lithium difluorooxalatoborate) is preferably used as the oxalato complex compound. Can do. Among them, a preferred example is LiBOB represented by the formula (I).

  In one embodiment of the nonaqueous electrolytic solution used in the secondary battery disclosed herein, the content Y of the oxalato complex compound (the total amount when two or more oxalato complex compounds are included) is other than It is preferable to set it to 0.5 mass part or more and 2 mass parts or less (namely, 0.5 <= Y <= 2) per 100 mass parts of electrolyte components total. For example, a reference electrolyte solution in which a supporting electrolyte is dissolved in a non-aqueous solvent at an appropriate concentration is prepared as in Examples described later, and Y parts by mass (where 0.5 ≦ Y By adding the oxalato complex compound of ≦ 2) and mixing uniformly, the non-aqueous electrolyte disclosed herein can be preferably prepared. Usually, it is appropriate that the content Y of the oxalato complex compound with respect to 100 parts by mass of other electrolyte components is 0.5 parts by mass or more and less than 2 parts by mass (that is, 0.5 ≦ Y <2). Preferably they are 0.5 mass part or more and 1.5 mass parts or less, More preferably, they are 0.8 mass part or more and 1.2 mass parts or less, for example, 0.5 mass part or more and 1 mass part or less.

  It is known that the nonaqueous solvent in the nonaqueous electrolytic solution used in the secondary battery disclosed herein can be generally used as a solvent for a nonaqueous electrolytic solution (for example, an electrolytic solution for a lithium ion secondary battery). Various aprotic solvents can be used. For example, various aprotic solvents such as carbonates, esters, ethers, nitriles, sulfones, and lactones can be used alone or in appropriate combination of two or more. Specific examples include ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), 1,2-dimethoxyethane, 1,2-diethoxyethane. , Tetrahydrofuran, 2-methyltetrahydrofuran, dioxane, 1,3-dioxolane, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether, acetonitrile, propionitrile, nitromethane, N, N-dimethylformamide, dimethyl sulfoxide, sulfolane, γ-butyrolactone, etc. . The non-aqueous solvent preferably exhibits a liquid state at room temperature (for example, 25 ° C.) as a whole (when a plurality of compounds are included, as a mixture thereof).

《Nonaqueous solvent》
As a suitable example of the non-aqueous solvent in the technology disclosed herein, a non-aqueous solvent containing one or more carbonates, and the total volume of these carbonates accounts for 50% by volume or more of the total volume of the non-aqueous solvent ( Carbonate-based solvents). For example, the total volume of carbonates is 60% by volume or more (more preferably 75% by volume or more, more preferably 90% by volume or more, and substantially 100% by volume) of the total volume of the nonaqueous solvent. ) Is preferred.

《Supporting electrolyte》
The nonaqueous electrolytic solution used for the secondary battery disclosed herein typically contains a supporting electrolyte (supporting salt) in addition to the nonaqueous solvent, the aromatic carbonate compound and the oxalato complex compound. Examples of the supporting electrolyte include LiPF ₆ , LiBF ₄ , LiN (SO ₂ CF ₃ ) ₂ , LiN (SO ₂ C ₂ F ₅ ) ₂ , LiCF ₃ SO ₃ , LiC ₄ F ₉ SO ₃ , LiC (SO ₂ CF _{3 3} ), LiClO ₄ or the like, one or more selected from various lithium salts known to be capable of functioning as a supporting electrolyte for lithium ion secondary batteries can be used. Of these, LiPF ₆ is preferable. The concentration of the supporting electrolyte is not particularly limited, and can be, for example, the same level as that of a conventional lithium ion secondary battery. Usually, it is appropriate that the concentration of the supporting electrolyte is about 0.1 mol / L to 5 mol / L (for example, about 0.8 mol / L to 1.5 mol / L).

  The non-aqueous electrolyte used for the secondary battery disclosed herein can further contain other components as necessary. As an example of such an optional component, a polymer precursor (which may be a monomer, an oligomer, a mixture thereof, or the like) for gelling the non-aqueous electrolyte, an initiator for initiating or accelerating the gelation reaction, A crosslinking agent is mentioned. As another example, a moisture removing agent that reacts with moisture present in the electrolyte solution or moisture that can be mixed into the electrolyte solution to eliminate the moisture. On the other hand, it may be a non-aqueous electrolyte substantially composed of a non-aqueous solvent (typically a carbonate-based solvent), a non-aqueous electrolyte, an aromatic carbonate compound, and an oxalato complex compound.

  The non-aqueous electrolyte disclosed herein can be widely applied to lithium ion secondary batteries and other various non-aqueous secondary batteries, and can be useful for improving the performance of the battery. For example, the increase in resistance and the capacity deterioration after high-temperature storage durability of the battery can be effectively improved. In carrying out the technology disclosed herein, it is not necessary to clarify the reason why such an effect is obtained, but the following may be considered, for example. That is, the aromatic carbonate compound and the oxalato complex compound are decomposed together with the electrolytic solution components (non-aqueous solvent, supporting salt, etc.) at the time of initial charging, etc., and a mixed film consisting of these decomposition products, that is, the aromatic carbonate compound and By covering the surface of the electrode (positive electrode and / or negative electrode) with the mixed film with the oxalato complex compound, further decomposition of the electrolyte component can be suppressed, which can contribute to the improvement of battery characteristics. Such a mixed film is strong and hard to break as compared with a film formed when an aromatic carbonate compound or an oxalato complex compound is used alone, so that the film can be maintained well (for example, with charge / discharge) Even if the electrode active material expands and contracts or is kept at a high temperature for a long time, the film is difficult to peel off from the electrode surface). Therefore, it is considered that the increase in resistance and the capacity deterioration after the endurance of the battery are effectively improved.

  In addition, even if the nonaqueous electrolyte solution disclosed here is a composition containing an aromatic carbonate compound and an oxalato complex compound at the time of construction (assembly) of the battery, as described above, initial charge / discharge or A part or all of the aromatic carbonate compound and the oxalato complex compound can be decomposed by charging and discharging. In the battery in such a state, the aromatic carbonate compound and the oxalato complex compound were contained in the nonaqueous electrolytic solution used at the time of battery construction, for example, the NMR (Nuclear Magnetic Resonance: nuclear magnetic resonance) of the electrolytic solution or the electrode. ) Analysis and mass spectrometry (for example, MALDI-MS (Matrix Assisted Laser Desorption / Ionization-Mass Spectrometry), TOF-SIMS (Time of Flight Secondary Ion Mass Spectrometry) Mass spectrometry) mass spectrometry using an instrument). Furthermore, as a method of grasping each amount of MPhC and LiBOB contained in the non-aqueous electrolyte used at the time of battery construction from the battery after initial charge / discharge (or after further charge / discharge), for example, Examples include NMR analysis, mass spectrometry, IR analysis, and the like of battery components (electrolyte, electrode, etc.).

  Although not intended to be particularly limited, as a schematic configuration of the nonaqueous electrolyte secondary battery according to one embodiment of the present invention, a wound-type electrode body (hereinafter referred to as “wound electrode body”) and non-winding type. A lithium ion secondary battery (unit cell) in a form in which a water electrolyte is housed in a rectangular (here, rectangular parallelepiped box-shaped) case is shown as an example, and FIGS. The battery structure is not limited to the illustrated example, and is not particularly limited to a prismatic battery.

  FIG. 1 is a cross-sectional view of a lithium ion secondary battery 100 according to an embodiment of the present invention. FIG. 2 is a view showing a wound electrode body 200 housed in the lithium ion secondary battery 100.

  A lithium ion secondary battery 100 according to an embodiment of the present invention is configured in a flat rectangular battery case (that is, an exterior container) 300 as shown in FIG. As shown in FIG. 2, in the lithium ion secondary battery 100, a flat wound electrode body 200 is housed in a battery case 300 together with a non-aqueous electrolyte 90.

<Battery case 300>
The battery case 300 has a box-shaped (that is, bottomed rectangular parallelepiped) case main body 320 having an opening at one end (corresponding to the upper end in a normal use state of the battery 100), and is attached to the opening. It is comprised from the sealing board (lid body) 340 which consists of a rectangular-shaped plate member which block | closes an opening part.

  The material of the battery case 300 may be the same as that used in the conventional sealed battery, and there is no particular limitation. A battery case 300 mainly composed of a lightweight metal material having good thermal conductivity is preferable. Examples of such a metal material include aluminum, stainless steel, nickel-plated steel, and the like. The battery case 300 (the case main body 320 and the sealing plate 340) according to the present embodiment is made of aluminum or an alloy mainly composed of aluminum.

  As shown in FIG. 1, a positive electrode terminal 420 and a negative electrode terminal 440 for external connection are formed on the sealing plate 340. Between the terminals 420 and 440 of the sealing plate 340, when the internal pressure of the battery case 300 rises to a predetermined level (for example, a set valve opening pressure of about 0.3 to 1.0 MPa), the internal pressure is released. A configured thin safety valve 360 and a liquid injection hole 350 are formed. In FIG. 1, the liquid injection hole 350 is sealed with a sealing material 352 after liquid injection.

<< Wound electrode body 200 (electrode body) >>
As shown in FIG. 2, the wound electrode body 200 includes a long sheet-like positive electrode (positive electrode sheet 220) and a long sheet-like negative electrode (negative electrode sheet 240) similar to the positive electrode sheet 220 in total of two sheets. Long sheet separators (separators 262 and 264).

<< Positive electrode sheet 220 >>
The positive electrode sheet 220 includes a strip-shaped positive electrode current collector 221 and a positive electrode active material layer 223. For the positive electrode current collector 221, for example, a metal foil suitable for the positive electrode can be suitably used. In this embodiment, a strip-shaped aluminum foil having a thickness of about 15 μm is used as the positive electrode current collector 221. An uncoated portion 222 is set along the edge on one side in the width direction of the positive electrode current collector 221. In the illustrated example, the positive electrode active material layer 223 is held on both surfaces of the positive electrode current collector 221 except for the uncoated portion 222 set on the positive electrode current collector 221. The positive electrode active material layer 223 contains a positive electrode active material.

≪Positive electrode active material≫
As the positive electrode active material, one type or two or more types of materials conventionally used in lithium ion secondary batteries can be used without any particular limitation. Examples of the positive electrode active material disclosed herein include LiNiCoMnO ₂ (lithium nickel cobalt manganese composite oxide), LiNiO ₂ (lithium nickelate), LiCoO ₂ (lithium cobaltate), LiMn ₂ O ₄ (lithium manganate). And lithium transition metal oxide particles such as LiFePO ₄ (lithium iron phosphate). Here, LiMn ₂ O ₄ has, for example, a spinel structure. LiNiO ₂ or LiCoO ₂ has a layered rock salt structure. LiFePO ₄ has, for example, an olivine structure. Moreover, LiFePO _{4 having} an olivine structure can be further covered with a carbon film.

  The positive electrode active material layer 223 may contain, in addition to the positive electrode active material, one or more materials that can be used as a constituent component of the positive electrode active material layer 223 in a general lithium ion secondary battery as necessary. it can. An example of such a material is a conductive material. Examples of the conductive material include carbon materials such as carbon powder and carbon fiber. One kind selected from such conductive material particles may be used alone, or two or more kinds may be used in combination. As the carbon powder, various carbon blacks (for example, acetylene black, oil furnace black, graphitized carbon black, carbon black, graphite, ketjen black, channel black, furnace black), carbon powder such as graphite powder may be used. it can. Alternatively, conductive metal powder such as nickel powder may be used. In addition, examples of the material that can be used as a component of the positive electrode active material layer include various polymer materials (for example, polyvinylidene fluoride (PVDF)) that can function as a binder for the positive electrode active material.

  The proportion of the positive electrode active material in the entire positive electrode active material layer is suitably about 50% by mass or more (typically 50 to 95% by mass), and usually about 70 to 95% by mass. preferable. When the conductive agent is used, the ratio of the conductive material in the entire positive electrode active material layer can be, for example, about 2 to 20% by mass, and preferably about 2 to 15% by mass. When using a binder, the ratio of the binder to the whole positive electrode active material layer can be, for example, about 1 to 10% by mass, and usually about 2 to 5% by mass is appropriate.

  As a method of forming the positive electrode active material layer 223, a positive electrode active material (typically granular) and other positive electrode active material layer forming components are used in an appropriate solvent (for example, a nonaqueous solvent such as N-methylpyrrolidone (NMP)). A method in which the paste-like composition for forming a positive electrode active material layer dispersed in is applied in a strip shape on one side or both sides (here, both sides) of the positive electrode current collector 221 and dried can be preferably employed. After drying the composition for forming a positive electrode active material layer, an appropriate rolling process (for example, various conventionally known press methods such as a roll press method and a flat plate press method can be employed) is performed, thereby producing a positive electrode active material. The thickness and density of the layer 223 can be adjusted.

<< Negative Electrode Sheet 240 >>
As shown in FIG. 2, the negative electrode sheet 240 includes a strip-shaped negative electrode current collector 241 and a negative electrode active material layer 243. For the negative electrode current collector 241, for example, a metal foil suitable for the negative electrode can be suitably used. In this embodiment, a strip-shaped copper foil having a thickness of about 10 μm is used for the negative electrode current collector 241. On one side in the width direction of the negative electrode current collector 241, an uncoated part 242 is set along the edge. The negative electrode active material layer 243 is held on both surfaces of the negative electrode current collector 241 except for the uncoated portion 242 set on the negative electrode current collector 241. The negative electrode active material layer 243 contains a negative electrode active material.

<Negative electrode active material>
A graphite material is used as the negative electrode active material. Examples of the graphite material include graphite (graphite), non-graphitizable carbon (hard carbon), graphitizable carbon (soft carbon), natural graphite, and a material obtained by applying amorphous carbon coating on the surface of natural graphite. Is included. In particular, application to a negative electrode active material (typically, a negative electrode active material substantially composed of natural graphite or artificial graphite) having natural graphite or artificial graphite as a main component is preferable. Such graphite can be flat scaly graphite. Alternatively, spheroidized graphite obtained by spheroidizing the flaky graphite may be used.

  The negative electrode active material layer 243 may contain, in addition to the negative electrode active material, one or more materials that can be used as a constituent component of the negative electrode active material layer 243 in a general lithium ion secondary battery as necessary. it can. Examples of such materials are polymer materials that can function as a binder for the negative electrode active material (for example, styrene-butadiene rubber (SBR)), and function as a thickener for the composition for forming the negative electrode active material layer. Examples thereof include a polymer material to be obtained (for example, carboxymethyl cellulose (CMC)).

  Although not particularly limited, the ratio of the negative electrode active material (graphite) to the entire negative electrode active material layer 243 can be approximately 80% by mass or more (for example, 80 to 99% by mass), and approximately 90% by mass or more ( For example, it is preferable that it is 90-99 mass%, More preferably, it is 95-99 mass%. In the composition using the binder, the proportion of the binder in the entire negative electrode active material layer 243 can be, for example, approximately 0.5 to 10% by mass, and is preferably approximately 1 to 5% by mass.

<< Separators 262, 264 >>
As shown in FIG. 2, the separators 262 and 264 are members that separate the positive electrode sheet 220 and the negative electrode sheet 240. In this example, the separators 262 and 264 are made of a strip-shaped sheet material having a predetermined width and having a plurality of minute holes. As the separators 262 and 264, for example, a single layer structure separator or a multilayer structure separator made of a porous polyolefin resin can be used. In this example, as shown in FIG. 2, the width b1 of the negative electrode active material layer 243 is slightly wider than the width a1 of the positive electrode active material layer 223. Furthermore, the widths c1 and c2 of the separators 262 and 264 are slightly wider than the width b1 of the negative electrode active material layer 243 (c1, c2>b1> a1).

  In the example illustrated in FIG. 2, the separators 262 and 264 are configured by sheet-like members. The separators 262 and 264 may be members that insulate the positive electrode active material layer 223 and the negative electrode active material layer 243 and allow the electrolyte to move. Therefore, it is not limited to a sheet-like member. The separators 262 and 264 may be formed of a layer of insulating particles formed on the surface of the positive electrode active material layer 223 or the negative electrode active material layer 243, for example, instead of the sheet-like member. Here, as the particles having insulating properties, inorganic fillers having insulating properties (for example, fillers such as metal oxides and metal hydroxides) or resin particles having insulating properties (for example, particles such as polyethylene and polypropylene). ).

<< Attachment of wound electrode body 200 >>
In this embodiment, the wound electrode body 200 is flatly bent in one direction orthogonal to the winding axis WL, as shown in FIG. In the example shown in FIG. 2, the uncoated portion 222 of the positive electrode current collector 221 and the uncoated portion 242 of the negative electrode current collector 241 are spirally exposed on both sides of the separators 262 and 264, respectively. In this embodiment, as shown in FIG. 1, the middle part of the uncoated part 222 (242) is gathered and collected by the electrode terminals 420 and 440 (internal terminals) arranged inside the battery case 300. Welded to tabs 420a, 440a.

  The lithium ion secondary battery 100 having such a configuration is provided on the sealing plate 340 after the electrode body 200 is accommodated inside the opening of the case 300 and the sealing plate 340 is attached to the opening of the case 300, for example. The electrolytic solution 90 is injected from the injection hole 350. The electrolytic solution 90 enters the wound electrode body 200 from the axial direction of the wound shaft WL. Next, the lithium ion secondary battery 100 can be constructed by closing the liquid injection hole 350.

  Several examples relating to the present invention will be described below, but the present invention is not intended to be limited to the specific examples.

(Test Example 1)
<Example 1>
A solution containing LiPF ₆ at a concentration of 1 mol / L in a mixed solvent of EC, DMC and EMC (volume ratio 3: 4: 3) was used as the reference electrolyte NA, and this was used as the electrolyte sample of Example 1.

<Example 2 to Example 6>
MPhC was added and dissolved in the reference electrolyte NA. The content of MPhC is different by setting the amount of MPhC added to 100 parts by mass of the reference electrolyte NA to 5 levels of 0.5 parts by mass, 1 part by mass, 2 parts by mass, 3 parts by mass and 4 parts by mass. Five types of electrolyte samples were prepared. Hereinafter, these electrolyte samples are expressed as Example 2 to Example 6 in order from the one with the smallest MPhC content.

<Example 7>
1 part by mass of LiBOB was added and dissolved in 100 parts by mass of the standard electrolyte NA, and this was used as the electrolyte sample of Example 7.

<Example 8 to Example 12>
LiBOB and MPhC were added and dissolved in the reference electrolyte NA. The amount of LiBOB added to 100 parts by mass of the reference electrolyte NA was 1 part by mass. Moreover, content of MPhC is made by making the addition amount of MPhC with respect to 100 mass parts reference | standard electrolyte solution NA into 5 levels of 0.5 mass part, 1 mass part, 2 mass parts, 3 mass parts, and 4 mass parts. Five types of electrolyte samples with different values were prepared. Hereinafter, these electrolytic solution samples are expressed as Example 8 to Example 12 in order from the one with the smallest MPhC content.

<Example 13 and Example 14>
Propane sultone (PS) was added and dissolved in the reference electrolyte NA. Two types of electrolyte samples with different PS contents were prepared by setting the amount of PS added to 100 parts by mass of the reference electrolyte NA to two levels of 0.3 parts by mass and 0.5 parts by mass. Hereinafter, these electrolyte samples are referred to as Example 13 and Example 14 in order from the one with the smallest PS content.

<Example 15 and Example 16>
MPhC and PS were added and dissolved in the reference electrolyte NA. The amount of MPhC added to 100 parts by mass of the reference electrolyte NA was 3 parts by mass. Moreover, two types of electrolyte samples with different PS contents are prepared by setting the amount of PS added to 100 parts by mass of the reference electrolyte NA to two levels of 0.3 parts by mass and 0.5 parts by mass. did. Hereinafter, these electrolyte samples are referred to as Example 15 and Example 16 in order from the one with the smallest PS content.

<Example 17, Example 18>
MPhC and PS were added and dissolved in the reference electrolyte NA. The amount of MPhC added to 100 parts by mass of the reference electrolyte NA was 4 parts by mass. Moreover, two types of electrolyte samples with different PS contents are prepared by setting the amount of PS added to 100 parts by mass of the reference electrolyte NA to two levels of 0.3 parts by mass and 0.5 parts by mass. did. Hereinafter, these electrolytic solution samples are referred to as Example 17 and Example 18 in order from the one with the smallest PS content.

  Table 1 shows the amount of additive added to the electrolyte solution sample in each example. “%” In Table 1 indicates the addition amount (wt%) of each additive when the reference electrolyte NA is 100 wt%.

≪Production of lithium ion secondary battery≫
A lithium ion secondary battery for evaluation was produced as follows using each electrolytic solution produced in Examples 1 to 18.
The positive electrode for this lithium ion secondary battery was produced as follows. That is, LiNi _1/3 Co _1/3 Mn _1/3 O ₂ as a positive electrode active material, acetylene black (AB) as a conductive material, and PVDF as a binder have a mass ratio of these materials. A composition for forming a positive electrode active material layer was prepared by mixing in NMP so as to be 90: 8: 2. By applying this composition to an aluminum foil (positive electrode current collector) having a thickness of 15 μm and applying a coating amount of 25 mg / cm ² per side and drying, a positive electrode sheet having a positive electrode active material layer formed on both surfaces of the positive electrode current collector was obtained. Obtained.

The negative electrode for the lithium ion secondary battery was produced as follows. That is, natural graphite as a negative electrode active material, SBR as a binder, and CMC as a thickener are mixed in water so that the mass ratio of these materials is 98: 1: 1. An active material layer forming composition was prepared. A negative electrode sheet in which a negative electrode active material layer is formed on both surfaces of a negative electrode current collector by applying this composition to one side of a 10 μm thick copper foil (negative electrode current collector) at a coating amount of 15 mg / cm ² and drying. Got.

  The positive electrode sheet and the negative electrode sheet are wound through two separator sheets (a single-layer structure made of porous polyethylene having a thickness of 10 μm is used), and flattened by crushing the wound body from the side surface direction. A spiral wound electrode body was produced. The wound electrode body thus obtained was housed in a metal box-type battery case together with the non-aqueous electrolyte of each example, and the opening of the battery case was hermetically sealed. In this way, a lithium ion secondary battery for evaluation test was assembled.

  Next, the conditioning process, rated capacity measurement, SOC adjustment, and initial resistance measurement performed for the evaluation test lithium ion secondary battery constructed as described above will be described in order.

<< conditioning >>
Each evaluation cell is charged with a constant current (CC) for 3 hours at a rate of 1 / 10C (1C is a current value that can be fully charged and discharged in 1 hour), and then 4 at a rate of 1 / 3C. The conditioning process was performed by repeating the operation of charging to 1 V and the operation of discharging to 3 V at a rate of 1/3 C three times.

≪Measurement of rated capacity≫
Each evaluation cell after conditioning is initially charged to a voltage between both positive and negative terminals of 4.1 V, and CC discharge is performed at a temperature of 25 ° C. until the voltage between both terminals reaches 3 V at a rate of 1 C. A constant voltage (CV) discharge was performed for 2 hours. After 10 minutes of rest, CC charging was performed at a rate of 0.33 C until the voltage between both terminals reached 4.1 V, and then CV charging was performed for 2.5 hours at the same voltage. After a 10-minute pause, CC discharge was performed at a rate of 0.33 C until the voltage between both terminals reached 3 V, then CV discharge was performed for 2 hours at the same voltage, and the total discharge capacity measured at the time of this CCCV discharge was used as the initial capacity. .

≪SOC adjustment≫
The SOC adjustment was performed by the following procedures 1 and 2 in a temperature environment of 25 ° C. after the conditioning process and the rated capacity measurement.
Procedure 1: Charging at a constant current of 3V to 1C to obtain a charging state (SOC 60%) of about 40% of the initial capacity. Here, “SOC” means State of Charge.
Procedure 2: When adjusting to SOC of 40% or more, after Procedure 1, charge at a constant voltage until a desired state of charge is reached.

≪Measurement of initial resistance≫
The battery for evaluation adjusted to SOC 40% (charged state of about 40% of the rated capacity) was put in a thermostatic bath, cooled to −30 ° C., and AC impedance measurement was performed. Then, the diameter of the semicircle was read from the obtained impedance Cole-Cole plot (also referred to as a Nyquist plot), and was defined as the initial reaction resistance (initial resistance) (Ω). As the apparatus, “1287 type potentio / galvanostat” manufactured by Solartron and “Frequency Response Analyzer (FRA)” manufactured by Toyo Technica Co., Ltd. were used. The measurement frequency was 0.001 to 100,000 Hz.

≪High temperature storage durability test≫
A battery of SOC 90% (charged state of about 90% of the rated capacity) was stored in an environment of 60 ° C. for 30 days. The reaction resistance of the battery after storage (resistance after durability) was measured in the same manner as the initial resistance. Then, the resistance increase rate was calculated by the following formula: (resistance after durability / initial resistance); Moreover, the battery capacity after storage (capacity after endurance) was measured in the same manner as the rated capacity. The capacity retention rate (%) was calculated according to the following formula: (capacity after endurance / rated capacity) × 100; The resistance increase rate and the capacity retention rate obtained for the evaluation batteries according to Examples 1 to 14 are shown in FIGS.

  As shown in FIGS. 3 and 4, according to the batteries using the non-aqueous electrolytes of Examples 8 to 12 to which both LiBOB and MPhC were added, the resistance increase rate after the high temperature storage test stored at 60 ° C. for 30 days All were excellent at 0.6 or less (both capacity retention rates were 92.5% or more), and showed extremely high durability performance. On the other hand, in the battery using the non-aqueous electrolyte of Examples 1 to 6 with no additive added or MPhC added alone, the resistance increase rate after the high-temperature storage test exceeded 1.0 (capacity maintenance) The rate was less than 92%) and lacked durability. Moreover, in the battery using the non-aqueous electrolyte of Example 7 to which LiBOB was added alone, although the resistance increase rate in the high-temperature storage test showed a tendency to decrease (capacity retention rate increased), the batteries of Examples 8 to 12 The improvement effect was not recognized as much as the battery using the non-aqueous electrolyte. From this, it was confirmed that a higher improvement effect is realized by using a combination of LiBOB and MPhC than when using them alone. In other words, it can be said that by using LiBOB and MPhC in combination, a lithium secondary battery with greatly improved durability can be obtained as a synergistic effect of such combination. From the viewpoint of improving the durability performance, it is appropriate that the MPhC content X is 0.5 ≦ X ≦ 4 (Examples 8 to 12), preferably 1 part by mass or more and 4 parts by mass or less ( Examples 9 to 12), more preferably 2 parts by mass or more and 3 parts by mass or less (Examples 10 and 11).

  The batteries using the non-aqueous electrolytes of Examples 13 and 14 to which PS was added alone were improved in the resistance increase rate and the capacity maintenance rate as compared with the battery using the non-aqueous electrolyte of Example 1 without addition. However, the batteries using the non-aqueous electrolytes of Examples 15 to 18 to which both PS and MPhC were added had a resistance increase rate of 1.0 or more (capacity maintenance rate of less than 92%), No further improvement effect was observed when combined with MPhC. From this, the durability improvement effect by using the non-aqueous electrolyte solution to which both LiBOB and MPhC are added is the same effect when the non-aqueous electrolyte solution to which both PS and MPhC are added is used. It was confirmed that it was not possible. In other words, it is not possible to expect further improvement effect by simply combining additives having durability improvement effect, and a lithium secondary battery with greatly improved durability performance can be obtained as a synergistic effect by the combination of LiBOB and MPhC. It can be said.

(Test Example 2)
An electrolyte sample was prepared in the same manner as Example 7, Example 10, and Example 11 except that the amount of LiBOB added to 100 parts by mass of the reference electrolyte NA was changed to two levels of 0.5 parts by mass and 2 parts by mass. Then, a lithium secondary battery for test was constructed. And the high temperature preservation | save durability test was done and the resistance increase rate and capacity | capacitance maintenance factor after durability were computed. The results are shown in FIG. 5 and FIG. FIG. 5 is a graph showing the relationship between the added amount of MPhC and the resistance increase rate. FIG. 6 is a graph showing the relationship between the added amount of MPhC and the capacity retention rate.

  As shown in FIGS. 5 and 6, regardless of the amount of LiBOB added, the battery using the non-aqueous electrolyte to which both LiBOB and MPhC are added is the battery using the non-aqueous electrolyte to which LiBOB is added alone. It was confirmed that the resistance increase rate and the capacity retention rate after the high temperature storage test were improved as compared with. Moreover, when the addition amount of MPhC was the same, it turned out that the higher durability improvement effect is acquired, so that the addition amount of LiBOB approaches 1%. From the viewpoint of improving the durability performance, the LiBOB content Y is suitably 0.5 ≦ Y ≦ 2, preferably 0.5 ≦ Y ≦ 1.5, more preferably 0.8. ≦ Y ≦ 1.2.

  As mentioned above, although the specific example of this invention was demonstrated in detail, these are only illustrations and do not limit a claim. The technology described in the claims includes various modifications and changes of the specific examples illustrated above.

  Any of the nonaqueous electrolyte secondary batteries disclosed herein has good capacity and output performance after high-temperature storage. For example, high capacity and low resistance can be maintained relatively well even after endurance. Since such high performance can be exhibited, for example, as shown in FIG. 7, it is suitable as a power source 1000 mounted on the vehicle 1. Therefore, the non-aqueous electrolyte secondary battery disclosed here (typically, a battery pack in which a plurality of the batteries (single cells) are connected in series) is an electric motor such as a hybrid vehicle or an electric vehicle. It can be suitably used as a power source (typically a driving power source) for a motor mounted on the vehicle 1 provided.

90 Non-aqueous electrolyte 100 Lithium ion secondary battery 200 Winding electrode body 220 Positive electrode sheet 240 Negative electrode sheet 262, 264 Separator 300 Battery case 350 Injection hole

Claims (7)

A non-aqueous electrolyte secondary battery comprising a positive electrode, a negative electrode, and a non-aqueous electrolyte,
The non-aqueous electrolyte includes a non-aqueous solvent, an oxalato complex compound, and an aromatic carbonate compound,
For 100 parts by mass of other electrolyte components except the oxalato complex compound and the aromatic carbonate compound,
The content of the oxalato complex compound is 0.5 parts by mass or more and 2 parts by mass or less,
Content of the said aromatic carbonate compound is a nonaqueous electrolyte secondary battery which is 0.5 mass part or more and 4 mass parts or less.   2. The water electrolyte secondary battery according to claim 1, wherein the content of the oxalato complex compound is 0.5 parts by mass or more and 1.5 parts by mass or less with respect to 100 parts by mass of the other electrolyte solution constituents. .   The non-aqueous electrolyte secondary battery according to claim 1 or 2, wherein the content of the aromatic carbonate compound is 2 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the other electrolyte component. .   The nonaqueous electrolyte secondary battery according to any one of claims 1 to 3, comprising at least lithium bisoxalate borate as the oxalato complex compound.   The non-aqueous electrolyte secondary battery according to any one of claims 1 to 4, comprising at least methyl phenyl carbonate as the aromatic carbonate compound.   The non-aqueous electrolyte secondary battery according to claim 1, wherein 50% by volume or more of the non-aqueous solvent is composed of one or two or more carbonate-based solvents. The nonaqueous electrolyte secondary battery according to claim 1, which is constructed as a lithium secondary battery containing a lithium-containing compound in the nonaqueous solvent.

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