CN109065949A - A kind of high stability lithium battery electrolytes and lithium ion battery - Google Patents

A kind of high stability lithium battery electrolytes and lithium ion battery Download PDF

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Publication number
CN109065949A
CN109065949A CN201810810618.2A CN201810810618A CN109065949A CN 109065949 A CN109065949 A CN 109065949A CN 201810810618 A CN201810810618 A CN 201810810618A CN 109065949 A CN109065949 A CN 109065949A
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lithium
electrolyte
carbonate
film
fluoro
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CN109065949B (en
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俞金萍
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy 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
    • 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
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of high stability lithium battery electrolytes and lithium ion battery, including organic solvent, lithium salts electrolyte, film for additive, further includes the lithium carbonate that mass fraction is 0.1-10%, and the lithium carbonate is the organic phosphonitrile lithium salt compound of fluoro.Organic phosphonitrile lithium salt compound that the present invention is added is conducive to form a film in positive and negative anodes, stable interfacial film is especially formed under high voltages, the oxidation reaction of electrolyte and material surface is prevented, inhibits electrolyte decomposition, to ensure that giving full play to for lithium ion battery electrical property.

Description

A kind of high stability lithium battery electrolytes and lithium ion battery
Technical field
The invention belongs to field of lithium ion battery more particularly to a kind of high stability lithium battery electrolytes and lithium-ion electric Pond.
Background technique
Lithium ion battery has high monomer voltage, energy and power density big, long as a kind of novel green high-energy battery Service life, memory-less effect, it is pollution-free the advantages that, have been widely used in people's daily life.But with lithium ion battery city Fieldization deepens continuously, and demand of the people to battery performance is higher and higher, especially the demand of the high-energy density of lithium battery, this is The important embodiment of lithium ion battery practical application value.The operating voltage for improving lithium battery is to promote having for lithium battery energy density One of effect approach, but existing main problem is that the electrochemistry of the carbonate group electrolyte of current business is steady in application process It is low to determine window, when battery reaches the left and right 4.5V (vs.Li/Li+), vigorous oxidation decomposition can occur for electrolyte, lead to electricity The rapid decaying of tankage, therefore the stability for improving electrolyte under high voltage is most important.
Therefore the present invention is by being added a kind of novel organophosphorus nitrile lithium salt compound, the additive be conducive to positive and negative anodes at Film improves the oxidative resistance of electrolyte and is formed under high voltages and stablize fine and close interfacial film, prevents electrolyte and material surface Oxidation reaction, inhibit electrolyte decomposition, to ensure that giving full play to for lithium ion battery electrical property.
Summary of the invention
In view of the problems in the background art, the object of the present invention is to provide a kind of high stability lithium battery electrolytes and Lithium ion battery while can be improved lithium battery energy density, positive and negative anodes surface filming, prevention electrolyte can also exist more fortunately The oxidation reaction of electrode surface improves the cyclical stability and electrical property of battery to preferably inhibit the decomposition of electrolyte It gives full play to.
In order to achieve the above purpose, the technical solution adopted by the present invention is that:
A kind of high stability lithium battery electrolytes, including organic solvent, lithium salts electrolyte, film for additive, further include matter The lithium carbonate that score is 0.1-10% is measured, the lithium carbonate is the organic phosphonitrile lithium salt compound of fluoro, the fluoro The structural formula of organic phosphonitrile lithium salt compound is as follows:
In formula R1, R2 be carbon atom number be 1~4 alkyl, part or all of fluoro alkyl.
Further scheme, the addition quality of the film for additive account for the 0.1-5% of electrolyte gross mass, organic solvent The 60-85% that quality accounts for electrolyte gross mass is added, lithium salts electrolyte is surplus.
Further scheme, the film for additive be vinylene carbonate, sulfuric acid vinyl ester, 1,3- propane sultone, Fluorinated ethylene carbonate, 1,2- difluorinated ethylene carbonate, three fluoropropylene carbonates, acrylonitrile, propylene sulfite, carbonic acid At least one of vinylethylene, dimethyl sulfoxide, 3,3,3- trifluoropropyl methyl sulfoxide, cyclohexyl benzene, trioctyl phosphate.
Further scheme, the organic solvent are diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, propylene carbonate Ester, ethyl acetate, ethyl propionate, one of nitrile, N-N- dimethylformamide or a variety of mixtures.
Further scheme, the lithium salts electrolyte be lithium hexafluoro phosphate, di-oxalate lithium borate, bis- (fluorine sulphonyl) imine lithiums, At least one in bis- (fluoroform sulphonyl) imine lithiums, LiBF4, difluorine oxalic acid boracic acid lithium, dimalonic acid lithium borate etc. Kind.
Further scheme, the concentration of the lithium salts electrolyte are 0.8-1.5mol/L.
Another goal of the invention of the invention is to provide a kind of lithium ion battery, contains such as above-mentioned electrolyte.
The organic phosphonitrile lithium salt compound of fluoro be joined in the present invention as lithium carbonate, due to the organic phosphonitrile lithium of fluoro Because it includes fluoro benzene radicals in salt compound, can be complexed to form organic film in positive and negative pole surface, while improving electrolyte Oxidative resistance and formed stablize fine and close interfacial film under high voltages, prevent the oxidation reaction of electrolyte and material surface, from And it ensure that giving full play to for lithium ion battery electrical property.
In addition, straight chained alkyl or part or all of fluoro in the organic phosphonitrile lithium salt compound of the fluoro being added in the present invention Carbon atom number is 1~4 in alkyl, because if alkyl chain growth, will increase the viscosity and solubility problem of electrolyte.
Compared with prior art, the special lithium carbonate that electrolyte of the invention contains is the organic phosphonitrile lithium salts of fluoro Object is closed, the electrochemical window and stability of electrolyte, and with higher anti-oxidant and decomposition energy can be effectively improved, mentioned The proof voltage of high electrolyte.Meanwhile the matching of electrode material and electrolyte can be effectively improved in conjunction with film for additive, Stable SEI film can be effectively formed.
While electrolyte in the present invention can be improved lithium battery energy density, can also more fortunately positive and negative anodes surface at Film prevents electrolyte in the oxidation reaction of electrode surface, to preferably inhibit the decomposition of electrolyte, the circulation for improving battery is steady It is qualitative and electrical property to give full play to.
So high-voltage electrolyte provided by the invention has high pressure resistant, not flatulence and good matching, can be improved The cycle life of lithium battery.
Specific embodiment
In order to describe the technical content, the structural feature, the achieved object and the effect of this invention in detail, below in conjunction with embodiment It is explained in detail.
The positive electrode active materials of lithium battery used in the embodiment of the present invention select ternary material (LiNi0.6Mn0.2Co0.2O2), negative electrode material selects artificial graphite, the material of diaphragm is 2400 diaphragm of Celgard company.It selects Contain the lithium ion battery of the electrolyte assembling of different electrolytes additive as embodiment, selects without electrolysis additive The lithium ion battery of conventional electrolysis liquid assembling is as a comparison case.
Comparative example 1:
The preparation steps of conventional electrolysis liquid are as follows:
(1) in the glove box of argon atmosphere, by ethylene carbonate (EC): methyl ethyl carbonate (EMC): diethyl carbonate (DEC)=3:5:2 (vol%) is mixed to get ternary mixed solvent, accounts for the 60-85% of total weight；
(2) LiPF for being 1mol/L by appropriate lithium salts electrolyte concentration6, it is added in above-mentioned ternary mixed solvent, obtains Blank electrolysis liquid；
(3) film for additive for accounting for electrolyte gross mass 0.1-5% is added in blank electrolysis liquid, obtains basic electrolysis Liquid.
Embodiment 1:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 1 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 2:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 2 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 3:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 3 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 4:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 4 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 5:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 5 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 6:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 6 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 7:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 7 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 8:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 8 of fluoro, structural formula is as follows, after mixing static reserve.
Embodiment 9:
With comparative example 1, it is slowly added to account for electrolyte gross mass 0.5% in the basic electrolyte configured in comparative example 1 The organic phosphonitrile lithium salt compound 9 of fluoro, structural formula is as follows, after mixing static reserve.
The preparation of lithium ion battery:
Positive electrode active materials select LiNi0.6Mn0.2Co0.2O2, negative electrode material select artificial graphite, use Celgard company 2400 diaphragms, and it is injected separately into electrolyte prepared by comparative example 1 and embodiment 1-9, it is assembled into lithium ion battery.
Electric performance test:
10 lithium ion battery samples of above-mentioned assembling with operating voltage are 3.0-4.4V, 0.5C/ by cycle performance test 0.5C carries out charge and discharge cycles test, blanking voltage 2.7-4.4V to battery.Then in 60 DEG C after high temperature storage seven days, comparison Internal resistance, volume change.Concrete outcome is shown in Table 1.
1 unit for electrical property parameters of table
The correlated performance for the lithium battery that embodiment 1-9 and comparative example 1 electrolyte prepared are assembled by identical method It compares, finds effectively mention in electrolyte of the invention due to joined the organic phosphonitrile lithium salt compound of fluoro The coulombic efficiency for the first time of high lithium battery, moreover it is possible to improve under high temperature electrolyte stability under the cycle life of battery and high temperature.
The above embodiment is a preferred embodiment of the present invention, but the embodiment at this gate is not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications done without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (7)

1. a kind of high stability lithium battery electrolytes, including organic solvent, lithium salts electrolyte, film for additive, it is characterised in that: It further include the lithium carbonate that mass fraction is 0.1-10%, the lithium carbonate is the organic phosphonitrile lithium salt compound of fluoro, The structural formula of the organic phosphonitrile lithium salt compound of fluoro is as follows:
In formula R1, R2 be carbon atom number be 1~4 alkyl, part or all of fluoro alkyl.
2. electrolyte according to claim 1, it is characterised in that: it is total that the addition quality of the film for additive accounts for electrolyte The 0.1-5% of quality, the addition quality of organic solvent account for the 60-85% of electrolyte gross mass, and lithium salts electrolyte is surplus.
3. electrolyte according to claim 1, it is characterised in that: the film for additive is vinylene carbonate, sulfuric acid Vinyl acetate, 1,3- propane sultone, fluorinated ethylene carbonate, 1,2- difluorinated ethylene carbonate, three fluoropropylene carbonates, Acrylonitrile, propylene sulfite, vinylethylene carbonate, dimethyl sulfoxide, 3,3,3- trifluoropropyl methyl sulfoxide, cyclohexyl benzene, phosphorus At least one of sour three monooctyl esters.
4. electrolyte according to claim 1, it is characterised in that: the organic solvent is diethyl carbonate, carbonic acid two Methyl esters, methyl ethyl carbonate, propene carbonate, ethyl acetate, ethyl propionate, one of nitrile, N-N- dimethylformamide or A variety of mixtures.
5. electrolyte according to claim 1, it is characterised in that: the lithium salts electrolyte is lithium hexafluoro phosphate, double oxalic acid Lithium borate, bis- (fluorine sulphonyl) imine lithiums, bis- (fluoroform sulphonyl) imine lithiums, LiBF4, difluorine oxalic acid boracic acid lithium, double third At least one of diacid lithium borate etc..
6. electrolyte according to claim 1, it is characterised in that: the concentration of the lithium salts electrolyte is 0.8-1.5mol/ L。
7. a kind of lithium ion battery, it is characterised in that: contain electrolyte as claimed in any one of claims 1 to 6.
CN201810810618.2A 2018-07-19 2018-07-19 high-stability lithium battery electrolyte and lithium ion battery Active CN109065949B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110176630A (en) * 2019-05-31 2019-08-27 宁德新能源科技有限公司 Electrolyte and the electrochemical appliance for using it

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009066559A1 (en) * 2007-11-19 2009-05-28 Central Glass Company, Limited Electrolyte solution for nonaqueous battery and nonaqueous battery using the same
CN103855428A (en) * 2012-12-04 2014-06-11 三星Sdi株式会社 Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same
US20170317385A1 (en) * 2014-12-17 2017-11-02 Basf Corporation Electrolyte Compositions For Rechargeable Lithium Ion Batteries

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009066559A1 (en) * 2007-11-19 2009-05-28 Central Glass Company, Limited Electrolyte solution for nonaqueous battery and nonaqueous battery using the same
CN103855428A (en) * 2012-12-04 2014-06-11 三星Sdi株式会社 Electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same
US20170317385A1 (en) * 2014-12-17 2017-11-02 Basf Corporation Electrolyte Compositions For Rechargeable Lithium Ion Batteries

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110176630A (en) * 2019-05-31 2019-08-27 宁德新能源科技有限公司 Electrolyte and the electrochemical appliance for using it

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