CN1722509A - Electrolyte for lithium ion rechargeable battery and lithium ion rechargeable battery including the same - Google Patents

Electrolyte for lithium ion rechargeable battery and lithium ion rechargeable battery including the same Download PDF

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CN1722509A
CN1722509A CNA2005100794261A CN200510079426A CN1722509A CN 1722509 A CN1722509 A CN 1722509A CN A2005100794261 A CNA2005100794261 A CN A2005100794261A CN 200510079426 A CN200510079426 A CN 200510079426A CN 1722509 A CN1722509 A CN 1722509A
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electrolyte
additive
carbonate
lithium ion
active material
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CN100423355C (en
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金真喜
金镇诚
金溶植
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Samsung SDI Co Ltd
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Samsung SDI Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention is an electrolyte for a lithium ion rechargeable battery and a lithium ion rechargeable battery that includes the same. More particularly, the present invention discloses an electrolyte for a lithium ion rechargeable battery that provides excellent cycle life characteristics and high-temperatures storage stability and prevents a drop in discharge capacity of a battery at low temperature, and a lithium ion rechargeable battery including the same. The lithium ion rechargeable battery including the electrolyte provides improved cycle life characteristics and prevents the problems of a drop in discharge capacity at low temperature and high-temperature swelling through the formation of a stable SEI film at the initial charge cycle.

Description

The electrolyte of rechargeable lithium ion batteries and comprise its rechargeable lithium ion batteries
The cross reference of related application
The application require korean patent application 2004-0046273 number submitted on June 21st, 2004 and submission on October 26th, 2004 the priority and the rights and interests of korean patent application 2004-0085692 number, it is incorporated herein by reference as being set forth in herein fully for any purpose.
Technical field
The present invention relates to a kind of electrolyte of rechargeable lithium ion batteries and comprise the rechargeable lithium ion batteries of this electrolyte.Particularly, the invention provides a kind of electrolyte of rechargeable lithium ion batteries, described rechargeable lithium ion batteries provides good cycle life characteristics and high-temperature storage stability, and described electrolyte prevents that also battery discharge capacity at low temperatures from reducing.The present invention also provides the rechargeable lithium ion batteries that comprises described electrolyte.
Background technology
Along with the electronics industry development, portable and wireless electron instrument are comprised that the technical research of phone, video camera and PC develops rapidly.Therefore, need in light weight day by day and little rechargeable battery with high-energy-density to give these instrument power.Particularly, contain nonaqueous electrolytic solution, and use contain lithium metal oxide as cathode active material, use can embed/carbonaceous material of removal lithium embedded satisfies these needs as anode active material with the rechargeable battery that about 4V voltage is provided.
The average discharge volt of rechargeable lithium ion batteries is about 3.6～3.7V, thereby compares with other alkaline battery, Ni-MH battery, Ni-Cd battery etc., and it can provide high relatively electrical power.Yet, in order to obtain the high driving voltage level, need be in the charging of 0～4.2V the electrolyte component of electrochemical stability.For this reason, for example common the use comprises the mixture of cyclic carbonate based solvent such as ethylene carbonate, propylene carbonate and butylene carbonate as electrolyte.
In the circulation of the initial charge of rechargeable lithium ion batteries, lithium ion is from being to discharge the lithium metal oxide of cathode active material, and moves to the carbon electrode that is anode, so that lithium ion can embed in the carbon.In this process, lithium can react with carbon electrode, generates Li 2CO 3, Li 2O, LiOH etc., thus on the surface of anode, form film.This film is called as solid electrolyte interface (SEI) film.
The SEI film is after initial charge circulation forms, and it is as the barrier that stops lithium ion and carbon anode or other material to react, and in charge/discharge cycle subsequently the formation ion channel.Described ion channel prevents that carbon anode from breaking, and this breaks is that dissolving lithium ion by being present in the HMW organic solvent in the electrolyte causes.It also prevents moving of lithium ion and solvent, moves to cause embedding in the carbon anode therefore, in case form the SEI film, just can prevent lithium ion and carbon anode secondary response or undesirably react with other material again.Thereby can keep the concentration of lithium ion constant.
Yet along with charging and discharge cycles repeat, battery lead plate repeatedly expands and shrinks, and may apply local overvoltage.In these cases, As time goes on, passivation layer such as SEI film may progressively be degenerated, and may come out and undesirably react with on every side electrolyte in the surface of anode.In addition, produce gas, thereby the interior pressure of increase battery also reduces the cycle life characteristics of battery greatly by undesirable side reaction.According to the kind of employed carbonic ester in electrolyte and the type of anode active material, the gas of generation mainly comprises CO, CO 2, CH 4, C 2H 6Deng (J.Power Sources, 72 (1998) p.66-70).
In addition, a certain graphite-based anode active material may cause the decomposition of carbonate group electrolyte and separating of carbonaceous material, comprises capacitance, cycle life characteristics and storage characteristics thereby reduce battery behavior.Particularly, owing to use the battery of the electrolyte that comprises propylene carbonate, make that this problem is serious.In first charging cycle, propylene carbonate is in anodic decomposition, thereby significantly reduces initial capacity.
For the decomposition of cyclic carbonate and the separating of carbonaceous material that prevents to cause by the graphite-based anode active material, a kind of method has been proposed, in electrolyte, add crown ether (12-crown-4) (J.Electrochem.Soc. based on propylene carbonate and ethylene carbonate, Vol.140, No.6, L101 (1993)).Yet this method is problematic, because need a large amount of expensive crown ethers in case the degree that decomposes hope of stop ring shape carbonic ester, and the battery behavior that obtains by this method is not enough to practical application.
In addition, disclose for the flat 8-45545 of Japanese patent unexamined number a kind of to the method that adds vinylene carbonate based on the electrolyte of propylene carbonate and ethylene carbonate, to prevent the decomposition of described electrolyte.According to this method, in charging cycle, vinylene carbonate reduces on anode, thereby forms undissolved film on the surface of graphite (anode), thereby prevents the reduction of the ethylene carbonate of solvent such as propylene carbonate.
Yet, in first charging cycle, use this method of vinylene carbonate can not form complete SEI film separately.Because at room temperature recharge and discharge cycles, described film may break, and vinylene carbonate decomposes and consumes once more to compensate this part of breaking.Finally, can not obtain the stable cycle life characteristics of battery.And though by increasing the amount of vinylene carbonate, the cycle life characteristics of battery can improve, and this method still has problem, because the discharge capacity of battery reduces rapidly at low temperatures, and when it at high temperature stores, the battery swelling may take place.
Summary of the invention
The invention provides a kind of electrolyte of rechargeable lithium ion batteries, described rechargeable lithium ion batteries provides good cycle life characteristics and high-temperature storage stability, and also prevents the reduction of the discharge capacity of battery at low temperatures.
The present invention also provides a kind of rechargeable lithium ion batteries that comprises described electrolyte.
To in declaratives subsequently, illustrate supplementary features of the present invention, and from declaratives, will be in part apparent, perhaps can understand by enforcement of the present invention.
The invention discloses a kind of electrolyte that is used for chargeable lithium cell, described electrolyte comprises: lithium salts; Non-aqueous organic solvent; And first additive, when calculating by AM1 (the Austin model 1) method in Quantum chemical calculation, the lowest unoccupied molecular orbital (LUMO) of this first additive (LUMO) energy level is 0.3～0.5eV.Described electrolyte also comprises second additive, and when calculating by the AM1 method, the lumo energy of described second additive is-0.2～0.3eV or 0.5～1.0eV.
The invention also discloses a kind of electrolyte of chargeable lithium cell, described electrolyte comprises: lithium salts; Non-aqueous organic solvent; And first additive, when calculating by the AM1 method in Quantum chemical calculation, the lumo energy of described first additive is 0.3～0.5eV.Described electrolyte also comprises second additive, and when calculating by the AM1 method, the lumo energy of described second additive is 0.5～1.0eV; And the 3rd additive, when calculating by the AM1 method, the lumo energy of described the 3rd additive is-0.2～0.3eV.
The invention also discloses a kind of rechargeable lithium ion batteries, described rechargeable lithium ion batteries comprises above-mentioned electrolyte, comprises the negative electrode of cathode active material, comprises the anode of anode active material, and places the dividing plate between negative electrode and the anode.
Description of drawings
Comprise to provide the present invention is further understood and introduces the accompanying drawing that this specification constitutes the part of specification, the graphic extension embodiments of the present invention, and be used from declaratives one and explain principle of the present invention.
Fig. 1 is the schematic diagram of rechargeable lithium ion batteries structure according to the preferred embodiment of the present invention.
Embodiment
In order to form firm SEI film, need an additive, described additive can reduce and decompose before the non-aqueous organic solvent reduction.Use theoretical this additive of selecting of lowest unoccupied molecular orbital (LUMO) (LUMO).By using Austin model 1 (AM1) method, obtain joining the lumo energy of the compound in the electrolyte, described AM1 method is the semiempirical computational methods.
According to postulating and parameter, the semiempirical computational methods are divided into AM1, parametric method 3 (PM3), improved slightly differential overlapping (MNDO), complete neglect of differential overlap (CNDO), simple differential overlapping (INDO), the overlapping methods such as (MINDO) of improved simple differential.In 1985, improve the MNDO method by people such as Dewer by part and founded the AM1 method, be used for the calculating of hydrogen bond.Being used for the form that AM1 method of the present invention can the MOPAC computer package obtains.
LUMO represents not the molecular orbital of the lowest energy level track that occupied by electronics.When given molecule was accepted electronics, electronics occupied the lowest energy level track, and reducing degree depends on this energy level.Lumo energy is low more, and reducing degree is high more.On the other hand, higher lumo energy represents that resistance to reduction is high more.
Therefore, electrolyte according to the present invention comprises that its lumo energy is lower than the organic compound of present used non-aqueous organic solvent.This makes battery have stable cycle life characteristics.Particularly, the present invention includes a kind of organic compound, this organic compound is to be reduced before the carbonate group solvent of 1～2eV is reduced at lumo energy, and then forms stable film.
As indicated above, electrolyte according to the present invention comprises that lumo energy is first additive of 0.3～0.5eV, and lumo energy is second additive of-0.2～0.3eV or 0.5～1.0eV.If the lumo energy of additive is higher than 1.0eV or is lower than-0.2eV, then the carbonate group solvent forms unsettled film.
Be used for first and second additives of electrolyte of the present invention, all have the lumo energy that is lower than conventional non-aqueous organic solvent, wherein the potential energy of conventional lumo energy is about 1～2eV.In addition, the potential energy difference between the non-aqueous organic solvent and first and second additives is preferably 0.05～3eV, more preferably 0.1～2eV.
When not using additive, because forming, film needs low relatively irreversible capacity, battery can have good electrochemical charge/discharging efficiency.Yet, can not form stable SEI film, thereby in charging that repeats and discharge cycles, make battery quality worsen and reduce battery cycle life.
When independent use second additive, the cycle life of battery is improved, but should add with 3wt% or more concentration, so that it can form stable SEI film in the initial charge circulation.In this case, problem is that the discharge capacity of (20～0 ℃) battery at low temperatures reduces, and when its (85～90 ℃) storage at high temperature, battery may swelling.In addition,,, and may apply local overvoltage, thereby degrade SEI film and cause undesirable side reaction so battery lead plate repeatedly expands and shrinks because charging and discharge cycles repeat.This makes and is difficult to guarantee gratifying cycle life characteristics.
First additive can comprise trimethyl silyl phosphate and LiBF4 (LiBF 4).Second additive can comprise vinylene carbonate and carbonic acid fluoroethyl.
In the initial charge circulation, electrolyte of the present invention can form stable SEI film, described electrolyte comprises first additive and second additive with suitable mixed, thereby can guarantee the high-temperature stability of battery, good cycle life characteristics and stable low temperature discharge capacity.
Particularly, electrolyte according to the present invention uses first additive, thereby forms stable SEI film in the initial charge circulation.Therefore, even the concentration of second additive reduces, first additive still can keep the cycle life characteristics of battery and guarantee low temperature discharge capacity and the high-temperature stability that battery is stable.Finally, may obtain all above-mentioned characteristics simultaneously, be different from the situation of independent use second additive.
Based on the total weight of electrolyte, electrolyte according to the present invention comprises that the concentration of first additive is preferably 0.01～3wt%, more preferably 0.2～0.5wt%.
When the concentration of first additive is lower than 0.01wt%, can not form stable SEI film.When the amount of first additive during greater than 3wt%, at high temperature store for a long time, battery may serious swelling.In addition, low temperature discharge capacity and initial capacity reduce.Because consume the first a large amount of additives, form thick film.And when battery at high temperature stored, remaining unreacted excessive first additive may decompose, or serves as resistance in the discharge cycles at low temperatures, causes the deterioration of battery quality.
Based on the total weight of electrolyte, electrolyte according to the present invention comprises that the concentration of second additive is preferably 0.01～20wt%, and more preferably 0.01～10wt% most preferably is 0.1～5wt%.
When the concentration of second additive is lower than 0.01wt%, can not form stable SEI film.When the amount of second additive during greater than 20wt%, the low temperature discharge capacity of battery reduces greatly, and when at high temperature storing, battery may swelling, and may shorten its cycle life.
The weight ratio of first additive and second additive is preferably 0.1: 1～and 1: 1, more preferably 0.2: 1～0.5: 1.When the weight ratio of first additive and second additive was lower than 0.1, the cycle life of battery reduced.When the weight ratio of first additive and second additive greater than 1.0 the time, the low temperature discharge capacity of battery and initial capacity reduce, it is swelling widely at high temperature.
Except top additive, electrolyte according to the present invention comprises non-aqueous organic solvent and lithium salts.Non-aqueous organic solvent serves as medium, can move by the ion that participates in chemical reaction in this medium battery.Non-aqueous organic solvent can include but not limited to: cyclic carbonate, non-annularity carbonic ester, alphatic carboxylic acid ester, acyclic ether, cyclic ethers, alkyl phosphate and fluoride thereof or comprise two or more mixture in them.
The example of cyclic carbonate can include but not limited to: ethylene carbonate, propylene carbonate, butylene carbonate, vinylene carbonate.The example of non-annularity carbonic ester comprises for example dimethyl carbonate, diethyl carbonate, ethylene methyl esters, carbonic acid first propyl ester, ethyl propyl carbonic acid ester, dipropyl carbonate and methyl ethyl carbonate.And the example of alphatic carboxylic acid ester can include but not limited to for example methyl formate, methyl acetate, methyl propionate and ethyl propionate.
In addition, the example of acyclic ether can comprise gamma lactone, 1,2-dimethoxy-ethane, 1,2-diethoxyethane and ethyoxyl methoxy base ethane.The example of cyclic ethers can comprise for example oxolane and 2-methyltetrahydrofuran.The example of alkyl phosphate comprises methyl-sulfoxide, 1,2-dioxolanes, trimethyl phosphate, triethyl phosphate and trioctyl phosphate.
Described lithium salts provides lithium ion in battery, and makes rechargeable lithium ion batteries can realize basic function.Operable lithium salts can include, but are not limited to: LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiCF 3SO 3, LiSbF 6, LiN (SO 2CF 3) 2, LiC 4F 9SO 3, LiAlF 4, LiAlCl 4, LiN (SO 2C 2F 5) 2, LiN (C xF 2x+1SO 2) (C yF 2y+1SO 2) (in the formula, x and y are integer), LiCl and LiI, or comprise two or more mixture in them.
In yet another embodiment of the present invention, electrolyte comprises first additive, and when calculating by the AM1 method, the lumo energy of described first additive is 0.3～0.5eV; Second additive, when calculating by the AM1 method, the lumo energy of described second additive is 0.5～1.0eV; And the 3rd additive, when calculating by the AM1 method, the lumo energy of described the 3rd additive is-0.2～0.3eV.
The chargeable lithium cell of described electrolyte used according to the invention comprises negative electrode, anode and dividing plate.Negative electrode comprises and can reversibly embed/cathode active material of removal lithium embedded ion.This cathode active material can comprise the insert type oxide that contains lithium.
Anode comprises and can embed/anode active material of removal lithium embedded ion.This anode active material can include, but are not limited to: organic polymer compounds, carbon fiber, tin ash compound, lithium metal and the lithium alloy of crystalline carbon setting carbon, the carbon anode active material that derives from carbon composite (carbon of thermal decomposition, coke, graphite), coking.
Preferably, anode active material is a crystalline carbon.More preferably, anode active material is crystalline carbon or graphite, and its Lc is 150 or bigger, is in particular 150～3000 , and d (002) is 3.35～3.38 , and real density is 2.2g/cm 3Or bigger, be in particular 2.2～2.3g/cm 3, the BET specific area is 0.5～50m 2/ g, average particulate diameter (D50) are 1～30 μ m.In addition, in the superincumbent anode active material, the strength ratio that the I in Raman spectrum (1360) surface is surperficial with I (1590), i.e. I (1360cm -1)/I (1590cm -1) be preferably 0.05 or bigger, more preferably 0.05～0.5.And, the peak intensity ratio on the I in X-ray diffractogram (110) surface and I (002) surface, promptly X (I (110)/I (002)) preferably is lower than 0.2, and more preferably 0.006～0.2.
The slurry that will comprise cathode active material or anode active material is applied on the collector body that is formed by metal forming.In addition, also active material itself can be filmed.
Prevent from the dividing plate that is short-circuited between negative electrode in the chargeable lithium cell and the anode from can comprise any material known to those skilled in the art.For example, dividing plate can comprise: polymer film, and as polyolefin, polypropylene or polyethylene film, its multilayer film, microporous membrane, mesh grid and non-mesh grid.
Aforesaid chargeable lithium cell also can form the element cell with cathode/separator/anode structure, has the double cell of cathode/separator/anode/separator structure, or the lamination battery of the structure repeated several times of element cell wherein.
Hereinafter, preferred implementation of the present invention will be described with reference to the drawings.
Fig. 1 represents the structure of rechargeable lithium ion batteries according to the preferred embodiment of the present invention.As shown in Figure 1, by in jar 10, forming electrode assemblie 12, described electrode assemblie 12 comprise negative electrode 13, anode 15 and place negative electrode 13 and anode 15 between dividing plate 14, obtain chargeable lithium cell.In addition, battery comprises the cap assemblies 20 at the top of electrolyte and hermetically sealed can.Described cap assemblies 20 comprises cover plate 40, insulation board 50, end plate 60 and electrode terminal 30.In addition, cap assemblies 20 and insulation shell 70 combination seal jars 10.
With electrode terminal 30 be inserted in cover plate 40 in the through hole 41 that is formed centrally.When electrode terminal 30 is inserted through hole 41, the outer surface of liner 46 with electrode terminal 30 combined, so that insulation between electrode terminal 30 and the cover plate 40.Thereby this liner is inserted in the through hole 41 with electrode terminal 30.After cap assemblies being installed in jars 10 top, 42 inject the electrolyte into through entering the mouth, will enter the mouth with stopper 43 then 42 seals.
Electrode terminal 30 connects the positive contact 17 of anode 15 or connects the negative contact 16 of negative electrode 13, thereby serves as anode terminal or cathode terminal.
Chargeable lithium cell according to the present invention is not limited to above-mentioned shape, but can have any other shape applicable to battery, comprises cylindrical shape, box-like etc.
To use the following examples to describe the present invention now.Should be appreciated that following embodiment only is illustrative, and the invention is not restricted to this.
Utilize the AM1 method, the lumo energy of the additive 1 to 4 in the non-aqueous organic solvent of witness mark example 1 to 6 and the adding non-aqueous organic solvent.The results are shown in the following table 1.
Table 1
Sequence number Chemical substance LUMO(eV)
Reference example 1 EC (ethylene carbonate) 1.17553
Reference example 2 PC (propylene carbonate) 1.23594
Reference example 3 DMC (dimethyl carbonate) 1.24846
Reference example 4 DEC (diethyl carbonate) 1.25499
Reference example 5 EMC (ethylene methyl esters) 1.28819
Reference example 6 GBL (gamma-butyrolacton) 1.04899
Additive 1 FEC (carbonic acid fluoroethyl) 0.905
Additive 2 LiBF4 (LiBF4) 0.2
Additive 3 TMSP (trimethyl silyl phosphate) 0.415
Additive 4 VC (vinylene carbonate) 0.09007
As shown in table 1, additive 1 to 4 has the reduction potential that is lower than reference example 1 to 6.Thereby they decomposed before the non-aqueous organic solvent of reference example 1 to 6 decomposes.
Embodiment 1
Being suspended in the carboxymethyl cellulose aqueous solution of the anode active material of making by Delanium.Styrene butadiene rubbers is added wherein as adhesive, thus the slurry of formation anode active material.Described slurry is applied on the thick Copper Foil of 10 μ m dry and rolling formation anode.
Comprise LiCoO 2Cathode active material with combine as the polyvinylidene fluoride of adhesive with as the carbon of conductive agent.These compounds are dispersed in the N-N-methyl-2-2-pyrrolidone N-as solvent with 92: 4: 4 weight ratio, form the slurry of cathode active material.Described slurry is applied on the thick aluminium foil of 15 μ m dry and rolling formation negative electrode.
Is that the polyethylene separator of 16 μ m is reeled and compressed with negative electrode and anode with thickness.Element cell with gained inserts in the rhombus jar then., electrolyte added in jar, form chargeable lithium cell thereafter.Electrolyte prepares by following method: the LiPF that adds 1.0M 6To comprising that volume ratio is EC: EMC: DMC=3: in the mixed solvent of 6: 1 ethylene carbonate, ethylene methyl esters and dimethyl carbonate.In addition, based on the weight of mixture, in electrolyte mixture, add LiBF4 and the carbonic acid fluoroethyl of 0.2wt% and 2.0wt% respectively again.
Embodiment 2
Repeat embodiment 1, different is based on the weight of mixture, to add the LiBF4 of 1.0wt% and the carbonic acid fluoroethyl of 2.0wt%.
Embodiment 3
Repeat embodiment 1, different is based on the weight of mixture, to add the trimethyl silyl phosphate of 0.5wt% and the carbonic acid fluoroethyl of 2.0wt%.
Embodiment 4
Repeat embodiment 1, different is based on the weight of mixture, to add the trimethyl silyl phosphate of 1.0wt% and the carbonic acid fluoroethyl of 2.0wt%.
Embodiment 5
Repeat embodiment 1, different is based on the weight of mixture, to add LiBF4, the trimethyl silyl phosphate of 0.5wt% and the carbonic acid fluoroethyl of 2.0wt% of 0.2wt%.
Embodiment 6
Repeat embodiment 1, different is based on the weight of mixture, to add the LiBF4 of 0.2wt% and the vinylene carbonate of 2.0wt%.
Embodiment 7
Repeat embodiment 1, different is based on the weight of mixture, to add the LiBF4 of 1.0wt% and the vinylene carbonate of 2.0wt%.
Embodiment 8
Repeat embodiment 1, different is based on the weight of mixture, to add the trimethyl silyl phosphate of 0.5wt% and the vinylene carbonate of 2.0wt%.
Embodiment 9
Repeat embodiment 1, different is based on the weight of mixture, to add the trimethyl silyl phosphate of 1.0wt% and the vinylene carbonate of 2.0wt%.
Embodiment 10
Repeat embodiment 1, different is based on the weight of mixture, to add LiBF4, the trimethyl silyl phosphate of 0.5wt% and the vinylene carbonate of 2.0wt% of 0.2wt%.
Embodiment 11
Repeat embodiment 1, different is based on the weight of mixture, to add LiBF4, the vinylene carbonate of 0.5wt% and the carbonic acid fluoroethyl of 1.5wt% of 0.2wt%.
Embodiment 12
Repeat embodiment 1, different is based on the weight of mixture, to add LiBF4, the vinylene carbonate of 0.5wt% and the carbonic acid fluoroethyl of 1.5wt% of 1.0wt%.
Embodiment 13
Repeat embodiment 1, different is based on the weight of mixture, to add trimethyl silyl phosphate, the vinylene carbonate of 0.5wt% and the carbonic acid fluoroethyl of 1.5wt% of 0.5wt%.
Embodiment 14
Repeat embodiment 1, different is based on the weight of mixture, to add trimethyl silyl phosphate, the vinylene carbonate of 0.5wt% and the carbonic acid fluoroethyl of 1.5wt% of 0.2wt%.
Embodiment 15
Repeat embodiment 1, different is based on the weight of mixture, to add LiBF4, the trimethyl silyl phosphate of 0.5wt%, the vinylene carbonate of 0.5wt% and the carbonic acid fluoroethyl of 1.5wt% of 0.2wt%.
Comparative Examples 1
Repeat embodiment 1, different is not add additive to described electrolyte.
Comparative Examples 2
Repeat embodiment 1, different is based on the weight of mixture, to add the carbonic acid fluoroethyl of 2.0wt%.
Comparative Examples 3
Repeat embodiment 1, different is based on the weight of mixture, to add the carbonic acid fluoroethyl of 5.0wt%.
Comparative Examples 4
Repeat embodiment 1, different is based on the weight of mixture, to add the vinylene carbonate of 2.0wt%.
Comparative Examples 5
Repeat embodiment 1, different is based on the weight of mixture, to add the vinylene carbonate of 5.0wt%.
Experimental example 2
At electric current is that 158mA, voltage are under the condition of constant current-constant voltage (CC-CV) of 4.2V, will derive from battery (battery capacity 1C=790mAh) charging of embodiment 1 to 15 and Comparative Examples 1 to 5, and place 1 hour.Then, battery discharge and was placed 1 hour to 2.75V under 395mA.After the charge/discharge cycle on repeat 3 times, under the electric current of 395mA, 3 hours charging voltages of battery charge to 4.2V.Then, calculate initial charge/discharging efficiency (%), that is, and [(initial discharge capacity-initial charge capacity)/(initial charge capacity)] * 100 (%).For each of embodiment 1 to 15 and Comparative Examples 1 to 5, determine discharge capacity/charging capacity ratio in first charge/discharge cycle by the mean value (it is as shown in the table) that utilizes 10 batteries in following table 2 and 3.
In addition, the high-temperature storage test is carried out as follows.Under 85 ℃, each battery storage 4 hours.Then, the thickness after storing is compared with storing preceding thickness, increase ratio (%): [(thickness before the thickness-high-temperature storage after the high-temperature storage)/(thickness before the high-temperature storage)] * 100 (%) by utilizing the following formula calculated thickness.
And cycling life test is carried out as follows.Under constant current-constant voltage (CC-CV) condition and each temperature (10 ℃/25 ℃/45 ℃) of 1C/4.2V, each battery ends discharge through 0.1C by charging and 1C/3.0V.Keep (%) by the capacity that utilizes following formula to calculate in each circulation: [(in the discharge capacity of particular cycle)/(in the discharge capacity of first circulation)] * 100 (%).
Table 2
The embodiment sequence number Additive 1 Additive 2 Initial charge/discharging efficiency (%) Store back thickness in 85 ℃/4 hours and increase ratio (%) -20 ℃/0.5C discharge capacity (%) 100 thCirculation low temperature (10 ℃) capacity keeps (%) 300 thCirculation room temperature capacity keeps (%) 300 thCyclic high-temperature (60 ℃) capacity keeps (%)
1 LiBF 4 0.2wt％ FEC 2wt％ 96 14 59 86 88 83
2 LiBF 4 1.0wt％ FEC 2wt％ 93 15 58 85 87 80
3 TMSP 0.5wt％ FEC 2wt％ 95 16 60 88 90 79
4 TMSP 1.0wt％ FEC 2wt％ 94 23 63 89 91 77
5 LiBF 4 0.2wt％+ TMSP 0.5wt％ FEC 2wt％ 95 17 61 87 93 80
6 LiBF 4 0.2wt％ VC 2wt％ 93 17 40 70 86 73
7 LiBF 4 1.0wt％ VC 2wt％ 93 19 38 70 86 70
8 TMSP 0.5wt％ VC 2wt％ 94 20 51 83 86 76
9 TMSP 1.0wt％ VC 2wt％ 92 23 55 86 87 75
10 LiBF 4 0.2wt％+ TMSP 0.5wt％ VC 2wt％ 93 18 53 85 90 80
11 LiBF 4 0.2wt％ VC 0.5wt％+ FEC 1.5wt％ 94 17 58 87 86 75
12 LiBF 4 1.0wt％ VC 0.5wt％+ FEC 1.5wt％ 91 20 57 87 87 76
13 TMSP 0.5wt％ VC 0.5wt％+ FEC 1.5wt％ 93 21 60 87 88 75
14 TMSP 1.0wt％ VC 0.5wt％+ FEC 1.5wt％ 92 23 63 86 90 73
15 LiBF 4 0.2wt％+ TMSP 0.5wt％ VC 0.5wt％+ FEC 1.5wt％ 93 19 62 84 89 75
Table 3
The Comparative Examples sequence number Additive 1 Additive 2 Initial charge/discharging efficiency (%) Store back thickness in 85 ℃/4 hours and increase ratio (%) -20 ℃/0.5 C discharge capacity (%) 100 thCirculation low temperature (10 ℃) capacity keeps (%) 300 thCirculation room temperature capacity keeps (%) 300 thCyclic high-temperature (60 ℃) capacity keeps (%)
1 - - 97 10 70 40 30 20
2 - FEC 2wt％ 96 25 67 83 79 75
3 - FEC 5wt％ 95 30 50 80 84 77
4 - VC 2wt％ 93 28 40 70 82 69
5 - VC 5wt％ 90 35 30 65 85 63
As shown in table 3, because film forms lacking of required irreversible capacity, in Comparative Examples 1, do not use the battery of additive to have good electrochemical charge/discharging efficiency.Yet because do not form stable SEI film, in repetitive cycling, battery quality worsens.
In addition, compare with Comparative Examples 1, the independent use vinylene carbonate or the carbonic acid fluoroethyl of Comparative Examples 2 to 5 have the cycle life of improvement as the battery of additive.Yet because do not form stable SEI film, the SEI film rupture in each battery is subsequently in the part vinylene carbonate that breaks or decomposition of carbonic acid fluoroethyl and consumption.Therefore, must add a large amount of vinylene carbonate or carbonic acid fluoroethyl, in repetitive cycling, to obtain stable battery capacity.Yet, because the amount of vinylene carbonate increases, thus the cycle life of battery can improve, but because battery may swelling when at high temperature storing.In addition, the low temperature discharge capacity reduces.
When using the carbonic acid fluoroethyl to replace vinylene carbonate, as he is the same when using vinylene carbonate, the cycle life of battery can improve, and the problem of discharge capacity reduction at low temperatures becomes not serious.Yet discharge capacity decline and high temperature swelling still have problems under the low temperature.
From Comparative Examples 2 and 3 and Comparative Examples 4 and 5 as can be seen, vinylene carbonate provides than the higher room temperature capacity of carbonic acid fluoroethyl and keeps (%).Yet when using vinylene carbonate, the low temperature discharge capacity reduces greatly, and the amount of high temperature swelling and vinylene carbonate increases proportional increase.And the cycle life characteristics under high temperature and low temperature is poor.When using the carbonic acid fluoroethyl, high temperature swelling may take place in the amount increase according to the carbonic acid fluoroethyl.Yet, when vinylene carbonate and carbonic acid fluoroethyl equivalent increase, to compare with vinylene carbonate, the carbonic acid fluoroethyl provides the decline of littler low temperature discharge capacity.Finally, along with their amount increase, carbonic acid fluoroethyl and vinylene carbonate can cause the reduction of high temperature swelling problem and low temperature capacity.
As mentioned above, when independent use, additive such as vinylene carbonate and carbonic acid fluoroethyl can not be guaranteed low temperature discharge capacity, high-temperature stability and the cycle life characteristics of battery.
As shown in table 2, when reducing the amount of vinylene carbonate or carbonic acid fluoroethyl, derive from the battery of embodiment 1 to 15 according to the present invention, can improve charge/discharge cycle life characteristic and low temperature discharge capacity, and can solve the high temperature swelling problem, described battery comprises at least a first additive that is selected from LiBF4 and trimethyl silyl phosphate and at least a second additive that is selected from vinylene carbonate and carbonic acid fluoroethyl.
From embodiment 1 to 10 as can be seen, when each amount of vinylene carbonate that uses and carbonic acid fluoroethyl is reduced to 2.0wt%, and when adding LiBF4s and trimethyl silyl phosphate with various amounts, may obtain with at the vinylene carbonate of use 5.0wt% or the similar room temperature cycle life characteristics of situation of ethylene carbonate.
The adding of LiBF4 has also improved cycle life characteristics and has reduced the high temperature swelling degree, and the adding of trimethyl phosphate has improved cycle life characteristics and low temperature discharge capacity characteristic.In other words, LiBF4 has the function of improving cycle life characteristics and suppressing high temperature swelling, and the trimethyl silyl phosphate has the function of improving cycle life characteristics and low temperature discharge capacity characteristic.
Yet when the amount of LiBF4 increased the optimum level that surpasses it, high temperature swelling became seriously, and initial capacity and low temperature discharge capacity all reduce.Similarly, when the amount of trimethyl silyl phosphate increased the optimum level that surpasses it, high temperature swelling became seriously, and cycle life characteristics descends.In addition, when exceedingly using LiBF4 and trimethyl silyl phosphate, in the SEI film forms, consume these a large amount of additives, thereby form undesirable thick film.And, may at high temperature decompose the resistance that maybe can serve as at low temperatures discharge in the unreacted rest additive of first charging cycle, thus the degraded battery quality.
Because when comparing with the carbonic acid fluoroethyl, vinylene carbonate provides good room temperature cycle life characteristics, but reduce the low temperature discharge capacity greatly, so preferably use the vinylene carbonate of minimum with the carbonic acid fluoroethyl, with as embodiment 11 to 15, improve cycle life characteristics and low temperature discharge capacity characteristic simultaneously.
To one skilled in the art, can carry out various modifications and changes in the present invention, and not break away from design of the present invention and scope.Thereby, the invention is intended to cover its modifications and changes, suppose that they are in the scope of appending claims and their equivalent.

Claims (24)

1. electrolyte that is used for chargeable lithium cell, it comprises:
Lithium salts;
Non-aqueous organic solvent;
First additive, when calculating by AM1 (Austin model) method in the Quantum chemical calculation, the lowest unoccupied molecular orbital (LUMO) of this first additive (LUMO) energy level is 0.3～0.5eV; And
Second additive, when calculating by the AM1 method, the lumo energy of described second additive is-0.2～0.3eV or 0.5～1.0eV.
2. according to the electrolyte of claim 1, wherein said first additive is at least a compound that is selected from following: trimethyl silyl phosphate and LiBF4.
3. according to the electrolyte of claim 1, wherein, based on the total weight of electrolyte, the concentration of described first additive is 0.01～3.0% weight.
4. according to the electrolyte of claim 3, the concentration of wherein said first additive is 0.2～0.5% weight.
5. according to the electrolyte of claim 1, wherein said second additive is at least a compound that is selected from following: vinylene carbonate and carbonic acid fluoroethyl.
6. according to the electrolyte of claim 5, wherein, based on the total weight of electrolyte, the concentration of described second additive is 0.01～10.0% weight.
7. according to the electrolyte of claim 6, the concentration of wherein said second additive is 0.1～5.0% weight.
8. according to the electrolyte of claim 1, the weight ratio of wherein said first additive and second additive is 0.1: 1～1: 1.
9. electrolyte according to Claim 8, the weight ratio of wherein said first additive and second additive is 0.2: 1～0.5: 1.
10. according to the electrolyte of claim 1, wherein said non-aqueous organic solvent is selected from: cyclic carbonate, non-annularity carbonic ester, alphatic carboxylic acid ester, acyclic ether, cyclic ethers, alkyl phosphate and fluoride thereof or comprise two or more mixture in them.
11. according to the electrolyte of claim 10, wherein said cyclic carbonate is at least a compound that is selected from following: ethylene carbonate, propylene carbonate, butylene carbonate and vinylene carbonate.
12. according to the electrolyte of claim 10, wherein said non-annularity carbonic ester is at least a compound that is selected from following: dimethyl carbonate, diethyl carbonate, ethylene methyl esters, carbonic acid first propyl ester, ethyl propyl carbonic acid ester, dipropyl carbonate and methyl ethyl carbonate.
13. according to the electrolyte of the chargeable lithium cell of claim 10, wherein said alphatic carboxylic acid ester is at least a compound that is selected from following: methyl formate, methyl acetate, methyl propionate and ethyl propionate.
14. according to the electrolyte of the chargeable lithium cell of claim 10, wherein said acyclic ether is at least a compound that is selected from following: gamma lactone, 1,2-dimethoxy-ethane, 1,2-diethoxyethane and ethyoxyl methoxy base ethane.
15. according to the electrolyte of the chargeable lithium cell of claim 10, wherein said cyclic ethers is at least a compound that is selected from following: oxolane and 2-methyltetrahydrofuran.
16. according to the electrolyte of the chargeable lithium cell of claim 10, wherein said alkyl phosphate is at least a compound that is selected from following: methyl-sulfoxide, 1,2-dioxolanes, trimethyl phosphate, triethyl phosphate and trioctyl phosphate.
17. according to the electrolyte of the chargeable lithium cell of claim 1, wherein said lithium salts is to be selected from least a in following: LiPF 6, LiBF 4, LiAsF 6, LiClO 4, LiCF 3SO 3, LiSbF 6, LiN (SO 2CF 3) 2, LiC 4F 9SO 3, LiAlF 4, LiAlCl 4, LiN (SO 2C 2F 5) 2, LiN (C xF 2x+1SO 2) (C yF 2y+1SO 2) (in the formula, x and y respectively do for oneself integer), LiCl and LiI.
18. an electrolyte that is used for chargeable lithium cell, it comprises:
Lithium salts;
Non-aqueous organic solvent;
First additive, when calculating by the AM1 method, the lumo energy of described first additive is 0.3～0.5eV;
Second additive, when calculating by the AM1 method, the lumo energy of described second additive is 0.5～1.0eV; And
The 3rd additive, when calculating by the AM1 method, the lumo energy of described the 3rd additive is-0.2～0.3eV.
19. a rechargeable lithium ion batteries, it comprises:
Electrolyte according to claim 1;
The negative electrode that comprises cathode active material;
The anode that comprises anode active material; And
Place the dividing plate between negative electrode and the anode.
20. according to the rechargeable lithium ion batteries of claim 19, wherein said cathode active material is the insert type oxide that contains lithium.
21. according to the rechargeable lithium ion batteries of claim 19, wherein said anode active material is selected from: crystalline carbon, amorphous carbon, carbon composite and lithium metal.
22. according to 21 rechargeable lithium ion batteries of claim, wherein said anode active material is a crystalline carbon, the Lc of this crystalline carbon is 150 or bigger, and d (002) is 3.35～3.38 , and real density is 2.2g/cm 3Or bigger, the BET specific area is 0.5～50m 2/ g, average particulate diameter (D50) are 1～30 μ m.
23. according to the rechargeable lithium ion batteries of claim 21, wherein in Raman spectrum, the strength ratio [I (1360cm on the I of described anode active material (1360) surface and I (1590) surface -1)/I (1590cm -1)] be 0.05 or bigger.
24. according to the rechargeable lithium ion batteries of claim 21, wherein in X-ray diffractogram, the I of described anode active material (110) surface is lower than 0.2 with the peak intensity on I (002) surface than [X (I (110)/I (002))].
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