CN103762380B - A kind of electrolyte - Google Patents

A kind of electrolyte Download PDF

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Publication number
CN103762380B
CN103762380B CN201410043477.8A CN201410043477A CN103762380B CN 103762380 B CN103762380 B CN 103762380B CN 201410043477 A CN201410043477 A CN 201410043477A CN 103762380 B CN103762380 B CN 103762380B
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electrolyte
lithium
formula
carbonate
fluorine
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CN103762380A (en
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夏兰
夏永高
刘兆平
胡华胜
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or 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
    • 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 invention provides a kind of electrolyte, described electrolyte comprises non-aqueous organic solvent, lithium salts and polyphosphazene compound.Side chain due to the polyphosphazene compound added in the application's electrolyte is containing the heteroatomic long chain alkyl group such as O, N or S, coating layer that is fine and close, high-lithium ion conduction can be formed on the positive electrode surface of lithium ion battery, effective suppression electrolyte contacts with the direct of positive electrode, reduce the oxidation Decomposition of electrolyte, thus improve the cyclicity of high-voltage lithium ion batteries; Meanwhile, additive polyphosphazene compound has flame-retarding characteristic, can reduce the combustibility of electrolyte, improves the security performance of battery.

Description

A kind of electrolyte
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of electrolyte.
Background technology
In recent years, exploitation high specific energy lithium ion battery is not only the active demand of day by day miniaturized novel portable electronic product, be also the New Energy Industry such as electric automobile, energy-storage battery in the urgent need to.Improve battery specific energy and mainly contain two kinds of approach: the specific capacity improving battery; Improve the operating voltage of lithium ion battery, exploitation high-voltage anode material.Current high-voltage anode material has the acid of high voltage cobalt lithium, nickel ion doped, lithium manganese phosphate and lithium-rich manganese-based layed solid-solution, the charge cutoff voltage of above-mentioned positive electrode is all at more than 4.5V, but carbonic ester electrolyte is when voltage reaches 4.3V, irreversible oxidation Decomposition will be there is on high oxidative positive electrode surface, there is flatulence in battery, causes the deterioration of circulating battery and storge quality.
In order to suppress electrolyte in the decomposition on positive electrode surface, reduce electrolyte directly to contact with positive electrode, researcher sets about from high-voltage anode material, surface modification is carried out to it, namely at positive electrode Surface coating one deck oxide or fluoride, play the effect of obstruct, thus improve circulation and the high rate performance of battery.People's reported first such as Cho Al 2o 3coated LiCoO 2at the cycle performance in high voltage discharge and recharge 4.4 ~ 2.5V interval.With not coated blank LiCoO 2battery is compared, the Al of finishing 2o 3liCoO 2circulation and the high rate performance of battery significantly improve, and 50 weeks its capability retentions that circulate are still 97%.Except Al 2o 3outward, other coating layer material is as ZrO 2, MgO, AlPO 4with AlF 3deng, the compound high-voltage anode material prepared also all has circulation and high rate performance preferably.But the preparation process complex process of clad composite material, cost are high, and relate to the heat treatment in material later stage, easily cause the change of coating layer and material interface composition, the mechanism of action making it concrete is complicated.Meanwhile, decorative layer oxide or the fluoride of compound high-voltage anode surface of active material mostly are ion insulator, are unfavorable for that the deintercalation of lithium enters, affect the high rate performance of battery.
Except being improved except its chemical property by material modification, people by adding functional additive, to meet the demand of high-voltage lithium ion batteries to high-voltage electrolyte in conventional carbonic ester electrolyte system.Such as: disclose in Japanese Unexamined Patent Publication 6-13108 publication and add phosphazene compound in nonaqueous electrolytic solution, the combustibility of electrolyte can greatly be reduced.But, because the dielectric constant of cyclic phosphazene compound is very little, conventional lithium salts LiPF 6solubility is wherein very low, the decline of the conductivity of the electrolyte causing these additives to form; Publication number is propose the mixture of fluoro phosphonitrile, fluoro-ether and ethylenic unsaturation sultones in the Chinese patent of CN103456993A as high-voltage electrolyte, because fluoro phosphonitrile has higher oxidation Decomposition current potential, and it is fire-retardant, therefore the lithium ion battery of said mixture stable cycle performance under high voltages, internal resistance change is little.But the synthesis cost of fluoro additive is high and toxicity is comparatively large, and the compound use of additive makes electrolyte system more complicated, is not easy to practical application.
Summary of the invention
The technical problem that the present invention solves is to provide a kind of lower-cost electrolyte, and the electrolyte that the application provides makes lithium ion battery cyclicity better.
This application provides a kind of electrolyte, comprising: non-aqueous organic solvent, lithium salts and polyphosphazene compound.
Preferably, the structure of described polyphosphazene compound is such as formula shown in (I):
Wherein, R 1with R 2independently be selected from the structure with formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII) separately;
Wherein, q, m and n are the integer of 1 ~ 10;
R 3, R 4, R 5, R 6, R 7, R 8and R 9independently be selected from the straight or branched alkyl of phenyl, halogen, C1 ~ C12.
Preferably, the structure of described polyphosphazene compound is such as formula shown in (VIII):
N, m, q are the integer of 1 ~ 10, and R is the alkyl of straight or branched of phenyl, halogen, C1 ~ C12.
Preferably, the weight average molecular weight of described polyphosphazene compound is 500 ~ 100000.
Preferably, described non-aqueous organic solvent is ethylene carbonate, propene carbonate, gamma-butyrolacton, fluorinated ethylene carbonate, difluoroethylene carbonate, vinylene carbonate, ethylene carbonate vinylene, 1, 3-propane sultone, 1, 4-butane sultones, trifluoroacetic acid methyl esters, trifluoroacetic acid ethyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, five fluorine methyl propionates, five fluorine ethyl propionates, nine fluorine butylmethyl ether, nine fluorine isobutyl methyl ether, seven fluorine n-pro-pyl methyl ethers, seven fluorine isopropyl methyl ethers, hexafluoro isopropyl methyl ether, dimethyl carbonate, in diethyl carbonate and methyl ethyl carbonate two or more.
Preferably, described lithium salts is one or more in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium and two fluorine sulfimide lithium.
Preferably, described lithium salts is 0.1M ~ 2.5M in the molar concentration of described non-aqueous organic solvent; With the mass percent of electrolyte, the content of described polyphosphazene compound is 0.01% ~ 50%.
This application provides a kind of electrolyte, comprise non-aqueous organic solvent, lithium salts and polyphosphazene compound.Because the side chain of polyphosphazene compound is for containing heteroatomic long chain alkyl group, coating layer that is fine and close, high-lithium ion conduction can be formed on the positive electrode surface of lithium ion battery, effective suppression electrolyte contacts with the direct of positive electrode, reduce the oxidation Decomposition of electrolyte, thus improve the cyclicity of high-voltage lithium ion batteries.Secondly, polyphosphazene compound has fire-retardant, that chemical stability good and thermal stability is high feature, adding of this compound makes electrolyte have good anti-flammability, and its wettability containing heteroatomic side chain and pole piece, barrier film is good, therefore described in employing the application, the battery security of electrolyte is improved.
Accompanying drawing explanation
Fig. 1 is the cycle performance curve chart of the battery of the electrolyte adopting the embodiment of the present invention 2 and comparative example 1 to prepare.
Embodiment
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.
The embodiment of the invention discloses a kind of electrolyte, comprising: non-aqueous organic solvent, lithium salts and polyphosphazene compound.
With the addition of polyphosphazene compound in electrolyte described in the application, the structure of described polyphosphazene compound is preferably such as formula shown in (I):
Wherein, R 1with R 2independently be selected from the structure with formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII) separately;
Wherein, q, m and n are the integer of 1 ~ 10;
R 3, R 4, R 5, R 6, R 7, R 8and R 9independently be selected from the straight or branched alkyl of phenyl, halogen, C1 ~ C12.
According to the present invention, described polyphosphazene compound is more preferably has the structure shown in formula (VIII):
N, m, q are the integer of 1 ~ 10, and R is phenyl, halogen, C 1~ C 12the alkyl of straight or branched.
In certain embodiments, polyphosphazene compound described in the application can be the polyphosphazene compound of following structure:
Wherein, q is the integer of 1 ~ 10.
The weight average molecular weight of polyphosphazene compound of the present invention is preferably 500 ~ 100000.The content of polyphosphazene compound described in the application is preferably the 0.01wt% ~ 50wt% of described electrolyte, is more preferably 1wt% ~ 30wt%.The content of above-mentioned polyphosphazene compound is relevant with its molecular weight, when the molecular weight of polyphosphazene compound, when its addition is more, can ensure that polyphosphazene compound reaches 100% substantially at the Efficient Coverage Rate of electrode surface; When the molecular weight of polyphosphazene compound is larger, add a small amount of polyphosphazene compound, the Efficient Coverage Rate of electrode surface can be made higher.Described in the application, polyphosphazene compound is conventionally prepared, and for the source of described polyphosphazene compound, the application has no particular limits.The polyphosphazene compound added in the application's electrolyte, because its side chain is for containing the heteroatomic long chain alkyl group of O, N or S, coating layer that is fine and close, high-lithium ion conduction can be formed on the surface of lithium ion cell positive, electrolyte can be effectively suppressed to contact with the direct of positive electrode, reduce the oxidation Decomposition of electrolyte, thus improve the cyclical stability of battery.
Described in the application, non-aqueous organic solvent is preferably ethylene carbonate, propene carbonate, gamma-butyrolacton, fluorinated ethylene carbonate, difluoroethylene carbonate, vinylene carbonate, ethylene carbonate vinylene, 1, 3-propane sultone, 1, 4-butane sultones, trifluoroacetic acid methyl esters, trifluoroacetic acid ethyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, five fluorine methyl propionates, five fluorine ethyl propionates, nine fluorine butylmethyl ether, nine fluorine isobutyl methyl ether, seven fluorine n-pro-pyl methyl ethers, seven fluorine isopropyl methyl ethers, hexafluoro isopropyl methyl ether, dimethyl carbonate, two or more in diethyl carbonate and methyl ethyl carbonate.In described non-aqueous organic solvent two or more mixing time, the application has no particular limits the ratio that it mixes.Non-aqueous organic solvent described in the application is more preferably the mixture of ethylene carbonate and dimethyl carbonate, and the volume ratio of described ethylene carbonate and described dimethyl carbonate is preferably 3:7.
According to the present invention, also comprise lithium salts in described electrolyte, described lithium salts be preferably in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium and two fluorine sulfimide lithium one or more.Described in the application, lithium salts is more preferably lithium hexafluoro phosphate.The concentration of described lithium salts in non-aqueous organic solvent is preferably 0.1M ~ 2.5M, is more preferably 0.8M ~ 2M.
This application provides a kind of electrolyte, comprise non-aqueous organic solvent, lithium salts and polyphosphazene compound.The non-aqueous organic solvent that the application adopts, lithium salts all can have market to buy, and meanwhile, polyphosphazene preparation technology is simple, thus reduces the cost of electrolyte.High relative to prior art phosphazene compound autoxidation decomposition electric potential, the speciality of the non-oxidizability improving electrolyte is conducive to after being added into electrolyte, the side chain of the polyphosphazene compound added in electrolyte described in the application is for containing heteroatomic long chain alkyl group, coating layer that is fine and close, high-lithium ion conduction can be formed on the positive electrode surface of lithium ion battery, effective suppression electrolyte contacts with the direct of positive electrode, reduce the oxidation Decomposition of electrolyte, thus improve the cyclicity of high-voltage lithium ion batteries.Secondly, polyphosphazene compound has fire-retardant, that chemical stability good and thermal stability is high feature, adding of this compound makes electrolyte have good anti-flammability, and its wettability containing heteroatomic side chain and both positive and negative polarity pole piece, barrier film is good, therefore described in use the application, the battery security of electrolyte is improved.
In order to understand the present invention further, be described in detail to electrolyte provided by the invention below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
25g chlordene tripolyphosphazene, 0.2g sulfamic acid, 0.15g calcium sulphate dihydrate, 50mL1-naphthalene chloride are put into in condenser pipe, drying tube, thermometer and churned mechanically 500mL four-hole boiling flask, 230 DEG C are warming up under the protection of nitrogen, isothermal reaction a few hours, when viscosity generation significant change, stop reaction;
Poured into by above-mentioned reactant liquor and fill in the 3000mL beaker of 1000mL normal heptane, at the bottom of being stirred to glass, adularescent polymer is separated out, and separates upper solution; The polymer of bottom is polydichlorophosphazenes;
Under nitrogen protection; the dry oxolane of 200mL and 34g sodium hydride is added in three mouthfuls of round-bottomed flasks of 1000mL drying; then slowly instill oxolane (200mL) solution of triethylene glycol monoethyl ether (189g), stirred at ambient temperature reacts 2 hours.And then get 16g polydichlorophosphazenes and be dissolved in 200mL dry tetrahydrofuran solution, this solution is slowly added drop-wise in the alcohol sodium solution obtained above, drips rear back flow reaction 2 days.After having reacted, be poured in large water gaging after solution cool to room temperature, filter, filter cake washes with water, and drying obtains crude product.Crude product oxolane dissolves, benzinum reprecipitation, dry 30g product after repeating 3 times, be there is formula (VIII ＇) structure gather two (diethylene glycol monomethyl ether) phosphonitrile (EEEP), its productive rate is 70%.
Embodiment 2
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, poly-two (diethylene glycol monomethyl ether) phosphonitrile (EEEP) prepared by the embodiment 1 slowly adding 0.01% of electrolyte gross mass in the most backward mixed solution, obtains lithium-ion battery electrolytes after stirring.
Embodiment 3
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, poly-two (diethylene glycol monomethyl ether) phosphonitrile (EEEP) prepared by the embodiment 1 slowly adding 5% of electrolyte gross mass in the most backward mixed solution, obtains lithium-ion battery electrolytes after stirring.
Embodiment 4
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, poly-two (diethylene glycol monomethyl ether) phosphonitrile (EEEP) prepared by the embodiment 1 slowly adding 20% of electrolyte gross mass in the most backward mixed solution, obtains lithium-ion battery electrolytes after stirring.
Embodiment 5
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, poly-two (Phenylmethoxy) phosphonitrile of 0.1% of electrolyte gross mass is slowly added in the most backward mixed solution, structural formula, as shown in (Ⅸ), obtains lithium-ion battery electrolytes after stirring.Wherein, poly-two (Phenylmethoxy) phosphonitrile is self-control, and concrete preparation method is similar to embodiment 1, and difference is: triethylene glycol monoethyl ether replaces with phenol.
Embodiment 6
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, slowly add poly-two (Phenylmethoxy) phosphonitrile of 10% of electrolyte gross mass in the most backward mixed solution, after stirring, obtain lithium-ion battery electrolytes.
Embodiment 7
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, slowly add poly-two (Phenylmethoxy) phosphonitrile of 50% of electrolyte gross mass in the most backward mixed solution, after stirring, obtain lithium-ion battery electrolytes.
Embodiment 8
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, poly-two (trifluoro ethoxy) phosphonitrile of 0.1% of electrolyte gross mass is slowly added in the most backward mixed solution, its structural formula, such as formula shown in (Ⅹ), obtains lithium-ion battery electrolytes after stirring.Wherein, poly-two (trifluoro ethoxy) phosphonitrile is self-control, and concrete preparation method is similar to embodiment 1, and difference is: triethylene glycol monoethyl ether replaces with trifluoroethanol.
Embodiment 9
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, slowly add poly-two (trifluoro ethoxy) phosphonitrile of 10% of electrolyte gross mass in the most backward mixed solution, after stirring, obtain lithium-ion battery electrolytes.
Embodiment 10
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, its molar concentration is made to be 1mol/L, slowly add poly-two (trifluoro ethoxy) phosphonitrile of 50% of electrolyte gross mass in the most backward mixed solution, after stirring, obtain lithium-ion battery electrolytes.
Comparative example 1
Be full of glove box (the moisture <<1ppm of argon gas, oxygen <1ppm) in, get the ethylene carbonate of 10mL, the organic mixed solution of dimethyl carbonate, the volume ratio of ethylene carbonate, dimethyl carbonate is 3:7, lithium hexafluoro phosphate is added in organic mixed solution, make its molar concentration be 1mol/L, after stirring, obtain lithium-ion battery electrolytes.
Lithium-ion battery electrolytes prepared by the lithium-ion battery electrolytes prepare above-described embodiment 2 ~ 10 and comparative example 1 injects just very cobalt acid lithium respectively, negative pole is graphite MCMB, barrier film is in 18650 batteries of Celgard polypropylene diaphragm, the rated capacity of battery is 1800mAh, tests battery.Within 300 weeks, carry out charge-discharge test to battery at 3.0 ~ 4.4V with 0.5C circulation, test result is in table 1.
From table 1 high voltage cycle performance test data, the cycle performance under the battery high voltage of the electrolyte of additive polyphosphazene compound is adopted to be better than not containing the battery of the comparative example 1 of additive, simultaneously, adopt the embodiment battery of the nonaqueous electrolytic solution of the additive of different polyphosphazene compound after concentration optimization, its circulate 300 weeks after capability retention be greater than 75%, and not containing the capability retention of comparative example 1 battery of additive lower than 50%.
Table 1 embodiment and comparative example loop test result
Group 300 weeks room temperature cycles capability retentions
Embodiment 2 65%
Embodiment 3 84%
Embodiment 4 56%
Embodiment 5 67%
Embodiment 6 81%
Embodiment 7 62%
Embodiment 8 71%
Embodiment 9 83%
Embodiment 10 55%
Comparative example 1 45%
Accompanying drawing 1 is LiCoO prepared by the electrolyte of comparative example 1 and embodiment 2 2the cycle performance figure of/MCMB battery 3.0 ~ 4.4V discharge and recharge under 0.25C multiplying power under normal temperature environment, in figure ● curve is the cycle performance curve of battery prepared by the electrolyte of embodiment 2 employing, curve is the cycle performance curve of battery prepared by the electrolyte of comparative example 1 employing, as seen from the figure, the LiCoO for preparing of electrolyte of the present invention 2/ MCMB battery normal temperature high voltage cycle performance is obviously better than comparative example 1.
Flame retardant effect compares: the self-extinguishing time of lithium-ion battery electrolytes prepared by testing example 2 ~ 10 and lithium-ion battery electrolytes prepared by comparative example 1.
The method of testing of self-extinguishing time (SET) is as follows: take mineral wool as the glass cotton balls that raw material makes that diameter is 0.3 ~ 0.5cm, be weighed as 16mg, then glass cotton balls is placed in electrolyte to be measured and fully soaks, take out and weigh again, before and after soaking, the difference of the quality of glass cotton balls is the quality of cotton balls institute Electolyte-absorptive, this cotton balls gas igniter is lighted, record igniter is removed to the time of flame automatic distinguishing, each sample retest is averaged for 8 times, this time is self-extinguishing time, with the self-extinguishing time of unit mass electrolyte for standard, the fire resistance of different electrolytes can be compared.The anti-flammability of electrolyte can describe with fire-retardant rate F, F=1-SET/SET 0, SET 0for the self-extinguishing time of not additivated electrolyte, during definition 0<F<1/3, electrolyte is flammable, electrolyte flame-retardant during 1/3<F<2/3, during 2/3<F<1, electrolyte does not fire.Result is as shown in table 2, and the fire resistance of electrolyte prepared by visible the present invention is good.
The fire resistance tables of data of electrolyte prepared by table 2 embodiment and comparative example
Group Self-extinguishing time SET/s Fire-retardant rate F
Embodiment 2 17.0 0.010
Embodiment 3 10.7 0.377
Embodiment 4 8.3 0.517
Embodiment 5 16.5 0.039
Embodiment 6 8.2 0.522
Embodiment 7 5.6 0.674
Embodiment 8 16.8 0.022
Embodiment 9 10.5 0.388
Embodiment 10 9.8 0.429
Comparative example 1 17.17 0
The explanation of above embodiment just understands method of the present invention and core concept thereof for helping.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection range of the claims in the present invention.
To the above-mentioned explanation of the disclosed embodiments, professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.

Claims (6)

1. an electrolyte, comprising: non-aqueous organic solvent, lithium salts and polyphosphazene compound;
The structure of described polyphosphazene compound is such as formula shown in (I), formula (Ⅸ) or formula (Ⅹ):
In described formula (I), R 1with R 2independently be selected from the structure with formula (II), formula (III), formula (IV), formula (V), formula (VI) or formula (VII) separately;
Wherein, q, m and n are the integer of 1 ~ 10, and q is not 1;
R 3, R 4, R 5, R 6, R 7, R 8and R 9independently be selected from the straight or branched alkyl of phenyl, halogen, C1 ~ C12.
2. electrolyte according to claim 1, is characterized in that, the structure of described polyphosphazene compound is such as formula shown in (VIII):
N, m, q are the integer of 1 ~ 10 and q is not 1, R is the alkyl of straight or branched of phenyl, halogen, C1 ~ C12.
3. electrolyte according to claim 1, is characterized in that, the weight average molecular weight of described polyphosphazene compound is 500 ~ 100000.
4. electrolyte according to claim 1, it is characterized in that, described non-aqueous organic solvent is ethylene carbonate, propene carbonate, gamma-butyrolacton, fluorinated ethylene carbonate, difluoroethylene carbonate, vinylene carbonate, ethylene carbonate vinylene, 1, 3-propane sultone, 1, 4-butane sultones, trifluoroacetic acid methyl esters, trifluoroacetic acid ethyl ester, trifluoro-acetate, Trifluoroacetic Acid Ethyl Ester, five fluorine methyl propionates, five fluorine ethyl propionates, nine fluorine butylmethyl ether, nine fluorine isobutyl methyl ether, seven fluorine n-pro-pyl methyl ethers, seven fluorine isopropyl methyl ethers, hexafluoro isopropyl methyl ether, dimethyl carbonate, in diethyl carbonate and methyl ethyl carbonate two or more.
5. electrolyte according to claim 1, it is characterized in that, described lithium salts is one or more in lithium hexafluoro phosphate, LiBF4, lithium perchlorate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two (trimethyl fluoride sulfonyl) imine lithium and two fluorine sulfimide lithium.
6. electrolyte according to claim 1, is characterized in that, described lithium salts is 0.1M ~ 2.5M in the molar concentration of described non-aqueous organic solvent; With the mass percent of electrolyte, the content of described polyphosphazene compound is 0.01% ~ 50%.
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CN105098236B (en) * 2014-05-14 2017-07-07 宁德时代新能源科技股份有限公司 Lithium ion battery and electrolyte thereof
JP2017120765A (en) * 2015-12-25 2017-07-06 パナソニック株式会社 Nonaqueous electrolyte secondary battery
CN106159327B (en) * 2016-08-29 2019-08-30 恺时浦(上海)检测技术有限公司 Lithium ion secondary battery
CN106229548A (en) * 2016-08-30 2016-12-14 凯思普科技有限责任公司 Lithium battery electrolytes
CN107293790B (en) * 2017-07-25 2019-08-20 合肥国轩高科动力能源有限公司 A kind of fire-retardant lithium ion battery and its electrolyte
EP3706227A4 (en) * 2017-10-31 2021-09-08 Kanto Denka Kogyo Co., Ltd. Nonaqueous electrolyte solution and nonaqueous electrolyte battery
CN108912335A (en) * 2018-05-04 2018-11-30 惠州市大道新材料科技有限公司 Application in phosphonitrile polyanion alkali metal salt and preparation method thereof and nonaqueous electrolytic solution
CN110828894B (en) * 2019-11-01 2021-10-08 天津市捷威动力工业有限公司 High-safety electrolyte and lithium ion battery
CN111129467B (en) * 2019-12-30 2021-10-15 国联汽车动力电池研究院有限责任公司 Positive electrode slurry and preparation method thereof
CN112189278B (en) * 2020-01-11 2022-07-29 山东理工大学 Preparation method of flame-retardant lithium ion battery electrolyte easily soluble in organic solvent
CN111193070B (en) * 2020-01-11 2022-05-17 山东理工大学 Preparation method of lithium ion battery flame-retardant electrolyte containing polyphosphazene main chain
US20220255129A1 (en) * 2021-02-02 2022-08-11 Global Graphene Group, Inc. Phosphazene compound-based electrolyte compositions, quasi-solid and solid-state electrolytes, and lithium batteries
CN113363579B (en) * 2021-06-08 2023-02-28 清华大学深圳国际研究生院 Flame-retardant electrolyte, preparation method and lithium metal battery

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102668221A (en) * 2009-10-28 2012-09-12 Nec能源元器件株式会社 Nonaqueous electrolyte solution and device comprising same
CN103081183A (en) * 2010-09-06 2013-05-01 新神户电机株式会社 Nonaqueous electrolyte battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102668221A (en) * 2009-10-28 2012-09-12 Nec能源元器件株式会社 Nonaqueous electrolyte solution and device comprising same
CN103081183A (en) * 2010-09-06 2013-05-01 新神户电机株式会社 Nonaqueous electrolyte battery

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