CN114156536B - Additive, electrolyte and application thereof in improving low-temperature performance of lithium battery - Google Patents
Additive, electrolyte and application thereof in improving low-temperature performance of lithium battery Download PDFInfo
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- CN114156536B CN114156536B CN202111256480.4A CN202111256480A CN114156536B CN 114156536 B CN114156536 B CN 114156536B CN 202111256480 A CN202111256480 A CN 202111256480A CN 114156536 B CN114156536 B CN 114156536B
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- carbonate
- lithium battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 87
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 68
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000654 additive Substances 0.000 title claims abstract description 42
- 230000000996 additive effect Effects 0.000 title claims abstract description 38
- 229910001416 lithium ion Inorganic materials 0.000 claims description 33
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 28
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 26
- -1 ureide compound Chemical class 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 17
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 10
- 159000000002 lithium salts Chemical class 0.000 claims description 10
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004202 carbamide Substances 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical group [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 4
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 4
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 4
- 150000005678 chain carbonates Chemical class 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 4
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 4
- 239000002000 Electrolyte additive Substances 0.000 claims description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 2
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 229940043232 butyl acetate Drugs 0.000 claims description 2
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 2
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 0.000 claims description 2
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229940017219 methyl propionate Drugs 0.000 claims description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 2
- ZFLIKDUSUDBGCD-UHFFFAOYSA-N parabanic acid Chemical compound O=C1NC(=O)C(=O)N1 ZFLIKDUSUDBGCD-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 abstract description 3
- 238000007600 charging Methods 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 3
- 229940091173 hydantoin Drugs 0.000 description 3
- AHIWWUJXDLMOKI-UHFFFAOYSA-N methoxysulfonylmethanesulfonic acid Chemical compound COS(=O)(=O)CS(O)(=O)=O AHIWWUJXDLMOKI-UHFFFAOYSA-N 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- BJWMSGRKJIOCNR-UHFFFAOYSA-N 4-ethenyl-1,3-dioxolan-2-one Chemical compound C=CC1COC(=O)O1 BJWMSGRKJIOCNR-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- SVTMLGIQJHGGFK-UHFFFAOYSA-N carbonic acid;propa-1,2-diene Chemical compound C=C=C.OC(O)=O SVTMLGIQJHGGFK-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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 invention relates to the field of batteries, in particular to an additive, electrolyte and application thereof in improving low-temperature performance of a lithium battery. The additive for the electrolyte provided by the invention can be superior to an electrolyte solvent, forms a thin and continuous SEI film in a lithium battery, and has lower impedance and better conductivity of main components compared with the SEI film formed by the traditional electrolyte, so that the lithium battery using the additive or the electrolyte provided by the invention has excellent low-temperature performance.
Description
Technical Field
The invention relates to the field of batteries, in particular to an additive, electrolyte and application thereof in improving low-temperature performance of a lithium battery.
Background
In the 21 st century, lithium batteries were widely used in many fields such as cell phones, computers, wearable devices, electric vehicles, two-wheeled bicycles, electric tools, street lamps, and the like.
In recent years, as lithium batteries are increasingly used in various fields, requirements on battery performance and application environment are increasingly high, such as high-power discharge, ultra-low temperature discharge below-30 ℃, 10000 times of ultra-long cycle life and the like. In particular, in the low temperature field, the demand is becoming more and more vigorous, however, under the low temperature condition, the lithium battery is more and more difficult to discharge as the temperature is reduced until the lithium battery cannot discharge; under the condition of low-temperature charging, the constant current charging ratio of the battery is very low, namely the battery cannot be fully charged, lithium is easy to be separated out from a low-temperature charging negative electrode, and the battery after lithium separation is easy to be spontaneous or exploded, so that safety accidents are caused.
The reduction potential of each component of the lithium ion battery electrolyte is higher than that of lithium, and the components are reduced on the surface of a carbon negative electrode in the first charging process in the electrolyte to produce a passivation film (SEI) consisting of inorganic and organic compounds. The generated SEI can prevent the reduction reaction of electrolyte at the negative electrode in the subsequent charge and discharge process of the lithium ion battery, so that the lithium ion battery has higher cycle life compared with other types of reversible batteries, but the SEI film can influence the speed of lithium ions to be inserted into the negative electrode, so that the SEI film has obvious influence on the rate performance and low-temperature performance of the lithium ion battery.
The main factors of the poor low-temperature performance of the lithium battery are as follows: firstly, as the temperature is reduced, the viscosity of the electrolyte is gradually increased, and the migration rate of lithium ions in electrolysis is gradually lowered; secondly, in the reciprocating process of lithium ions from the cathode to the electrolyte, the lithium ions need to pass through an SEI film, and the migration rate of the lithium ions is greatly influenced by the components and the thickness of the SEI film; thirdly, active lithium is likely to be separated out from the surface of the negative electrode plate in the low-temperature charging process, particularly in the low-temperature high-rate charging process, and the active lithium and electrolyte are irreversible, so that the thickness of the SEI film is further increased, the lithium ion migration is more difficult, the low-temperature performance of the lithium battery is poorer, and even safety accidents are caused.
In order to ensure the performance of the lithium ion battery, some negative electrode film forming additives are generally added into the electrolyte to improve the components and performance of SEI, and Vinylene Carbonate (VC), methylene ethylene carbonate or vinyl ethylene carbonate and the like are generally selected as film forming additives. However, the film forming additive has obvious defects that the SEI film formed by the film forming additive has larger resistance, so that the DC internal resistance of the battery is increased, the low-temperature performance of the battery is deteriorated, the content of the additive is increased, the deterioration is more obvious, and particularly, the lithium is easy to be separated out by low-temperature charging under the low-temperature condition, so that the safety of the battery is influenced. The cycle life of the battery is difficult to ensure by reducing the use amount of the additive or not using the additive.
In addition, CN 109659613a discloses a low-temperature electrolyte for lithium batteries in the prior art, which comprises lithium salt, an organic solvent, an organic free radical and an additive, and the electrolyte applicable to low temperature is obtained by matching the components and the proportion. However, the disadvantage is that the TEMPO alone is inferior to the soft pack battery in low temperature cycle life compared to other additives alone; meanwhile, compared with the electrolyte using LiDFOB, VC, FEC, after TEMPO is added on the basis, the cycle life is also improved by 4.45 percent, and the effect is not obvious. CN 108321433a discloses an electrolyte additive and electrolyte for improving low-temperature performance of lithium ion batteries, and mentions that the additive is pyridine containing electron-withdrawing group substituent, and the molecular structure of the additive does not contain strong electron-withdrawing group substituent. The additive is added into the electrolyte of the lithium ion battery, so that the ion transmission rate of the electrolyte under the low-temperature condition can be increased, the freezing point of the electrolyte can be reduced, the discharge capacity and the cycle performance of the lithium ion battery under the low temperature are improved, and the wettability to the positive pole piece and the negative pole piece is enhanced. However, the pyridine substance has the defect that an effective SEI film cannot be formed on the negative electrode, and in actual use, additives such as VC, FEC, TSVC, PS and the like are additionally added to form a film on the negative electrode.
Disclosure of Invention
The invention aims to provide an additive, electrolyte and application thereof in improving low-temperature performance of a lithium battery.
In order to achieve the above object, the present invention provides an additive for an electrolyte (or "low temperature additive" or "low temperature additive for an electrolyte") comprising a ureide compound selected from one or more of allylmalonyl urea, 2-oxomalonyl urea, and oxalyl urea.
The invention discovers that the ureide compound can form a thin continuous SEI film in a lithium battery in preference to an electrolyte solvent, and the main composition of the film is LiN with lower ion passing impedance and better conductivity 3 、LiNO 2 、LiNO 3 、LiF、li 2 S，Li 2 SO 3 While the main component of SEI film formed by conventional electrolyte is alkyl ester lithium (ROCO) 2 Li) n, alkyllithium CH 3 (CH 2 ) The content of nLi and the like is relatively small. Based on the SEI film with lower impedance formed by the SEI film, the SEI film has better low-temperature charge-discharge performance when applied to a battery.
Preferably, the additive for the electrolyte further comprises an auxiliary component, wherein the auxiliary component is one or more of ethylene carbonate, methylene methyldisulfonate, lithium difluorophosphate and lithium difluorooxalato borate.
More preferably, the auxiliary component is a mixture of ethylene carbonate and one or more selected from methyl methylene disulfonate, lithium difluorophosphate and lithium difluorooxalato borate, and the content of the ethylene carbonate is 40-60% based on the total mass of the auxiliary component.
The above auxiliary component forms li with low impedance in SEI film 2 S、Li 3 B、Li 3 P, the composition of the SEI film can be further improved.
More preferably, when the mass ratio of the auxiliary component to the ureide compound is 1 (0.5-1), the constituent components of the SEI film are more excellent, which is advantageous for further reducing the resistance of the SEI film.
Furthermore, the invention also provides lithium battery electrolyte (or "lithium battery low-temperature electrolyte" or "lithium iron phosphate lithium ion battery low-temperature electrolyte") which contains the additive for the electrolyte.
Preferably, the additive for the electrolyte is added in an amount of 0.2 to 2%, more preferably 1.5 to 2%, based on the total mass of the electrolyte for a lithium battery.
Preferably, the lithium battery electrolyte further contains an organic solvent, wherein the organic solvent comprises a component A and a component B in a mass ratio of 2:8-5:5; more preferably, the mass ratio of the component A to the component B is 3:7-4:6;
wherein the component A is prepared from the following components in percentage by mass (1-2): a mixture of the cyclic carbonate and the chain carbonate of (1-3); more preferably, the mass ratio of the cyclic carbonate to the chain carbonate is 1 (1-1.2);
the component B is chain carboxylic ester;
further preferably, the cyclic carbonate is one or both of ethylene carbonate and propylene carbonate.
Further preferably, the chain carbonate is one or more of dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, dipropyl carbonate and methylpropyl carbonate.
Further preferably, the chain carboxylic acid ester is one or more of methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate and propyl butyrate.
After the organic solvent is added into the lithium battery electrolyte in the mode, the electrolyte has relatively low viscosity at low temperature, and meanwhile, lithium ions have good passing performance, so that the low-temperature performance of the lithium battery is further improved.
Preferably, the lithium battery electrolyte further contains a lithium salt, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium perchlorate and lithium tetrafluoroborate.
Further preferably, the lithium salt is added in an amount of 12 to 20%, more preferably 15 to 20%, based on the total mass of the lithium battery electrolyte.
The above-described schemes can be combined by a person skilled in the art in accordance with common general knowledge to obtain a preferable scheme of the lithium battery electrolyte of the present invention.
As a preferred scheme, the lithium battery electrolyte comprises the following components in parts by weight:
78-87.8 parts of organic solvent, 12-20 parts of lithium salt and 0.2-2 parts of electrolyte additive.
Further, the invention also provides an application of the additive for the electrolyte or the lithium battery electrolyte in any one of the following aspects:
(1) The low-temperature performance of the lithium ion battery is improved;
(2) And the SEI film impedance of the lithium ion battery is reduced.
Preferably, the lithium ion battery is a lithium iron phosphate lithium ion battery.
Furthermore, the invention also provides a lithium ion battery, which contains the lithium battery electrolyte.
Preferably, the lithium ion battery is a lithium iron phosphate lithium ion battery.
Based on the technical scheme, the invention has the following beneficial effects:
the additive for the electrolyte provided by the invention can form a thin and continuous SEI film in a lithium battery in preference to an electrolyte solvent, and compared with the SEI film formed by the traditional electrolyte, the SEI film has lower impedance of main components and better conductivity. Meanwhile, after the auxiliary component is added, the composition components of the SEI film are better, so that the impedance of the SEI film is further reduced. Based on the SEI film with lower impedance formed by the SEI film, the SEI film has better low-temperature charge-discharge performance when applied to a battery. In addition, after the organic solvent is added according to the method of the invention, the electrolyte solution has relatively low viscosity at low temperature, and meanwhile, lithium ions have better passing performance. Therefore, lithium batteries (particularly lithium iron phosphate lithium ion batteries) using the electrolyte of the present invention have excellent low temperature performance.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The specific techniques or conditions are not identified in the examples and are described in the literature in this field or are carried out in accordance with the product specifications. The reagents or equipment used were conventional products available for purchase by regular vendors without the manufacturer's attention.
Example 1
The present embodiment provides an additive for an electrolyte, which contains the components in a mass ratio of 1:1:1, methyl disulfonate, ethylene carbonate and allyl malonyl urea.
The embodiment further provides a lithium battery electrolyte containing the additive, which comprises the following formula: 15.6g of lithium hexafluorophosphate, 0.5g of methyl methylene disulfonate, 0.5g of ethylene carbonate, 0.5g of allyl malonyl urea and 82.9g of organic solvent (12.435 g of ethylene carbonate, 14.922g of methyl ethyl carbonate and 55.543g of propyl propionate, wherein the mass percentage of the three is 15:18:67).
In the preparation process, lithium hexafluorophosphate, methyl disulfonate, ethylene carbonate and allyl malonyl urea are dissolved in an organic solvent and are uniformly mixed to prepare electrolyte.
Example 2
The present embodiment provides an additive for an electrolyte, which contains the components in a mass ratio of 5:5:8 lithium difluorooxalato borate, ethylene carbonate and 2-oxomalonyl urea.
The embodiment further provides a lithium battery electrolyte containing the additive, which comprises the following formula: 20g of lithium hexafluorophosphate, 0.5g of lithium difluorooxalate borate, 0.5g of ethylene carbonate, 0.8g of 2-oxomalonyl urea and 78.2g of organic solvent (15.640 g of ethylene carbonate, 15.640g of ethyl methyl carbonate and 46.920g of ethyl propionate, wherein the mass percentages of the three are 20:20:60).
In the preparation process, lithium hexafluorophosphate, lithium difluorooxalato borate, ethylene carbonate and 2-oxo-malonyl urea are dissolved in an organic solvent and are uniformly mixed to prepare the electrolyte.
Example 3
The present embodiment provides an additive for an electrolyte, which contains the components in a mass ratio of 1:1:2 lithium difluorooxalato borate, ethylene carbonate and hydantoin.
The embodiment further provides a lithium battery electrolyte containing the additive, which comprises the following formula: 18.0g of lithium hexafluorophosphate, 0.5g of lithium difluorooxalato borate, 0.5g of ethylene carbonate, 1.0g of hydantoin and 80g of organic solvent (12.800 g of ethylene carbonate, 15.200g of dimethyl carbonate and 52.000g of propyl propionate, wherein the mass percentage of the three is 16:19:65).
In the preparation process, lithium hexafluorophosphate, lithium difluorooxalato borate, ethylene carbonate and hydantoin are dissolved in an organic solvent and are uniformly mixed to prepare the electrolyte.
Comparative example 1
The comparative example provides an electrolyte, which is prepared as follows: 15.6g of lithium hexafluorophosphate, 0.5g of methyl methylene disulfonate, 0.5g of ethylene carbonate and 83.4g of organic solvent (12.510 g of ethylene carbonate, 15.012g of methyl ethyl carbonate and 55.878g of propyl propionate, the mass percentages of the three are 15:18:67) are uniformly mixed to prepare an electrolyte.
Comparative example 2
The comparative example provides an electrolyte, which is prepared as follows: 20g of lithium hexafluorophosphate, 0.5g of lithium difluorooxalato borate and 0.5g of ethylene carbonate are dissolved in 79.0g of organic solvent (15.800 g of ethylene carbonate, 15.800g of methyl ethyl carbonate and 47.400g of ethyl propionate, the mass percentages of the three are 20:20:60), and the electrolyte is prepared after uniform mixing.
Comparative example 3
The comparative example provides an electrolyte, which is prepared as follows: 18.0g of lithium hexafluorophosphate, 0.5g of lithium difluorooxalato borate and 0.5g of ethylene carbonate are dissolved in 81.0g of organic solvent (12.960 g of ethylene carbonate, 15.390g of dimethyl carbonate and 52.650g of propyl propionate, the mass percentage of the three is 16:19:65), and the electrolyte is prepared after uniform mixing.
Test examples
The electrolyte for lithium batteries prepared in examples and comparative examples was injected into 26650-4.0Ah cells (positive electrode lithium iron phosphate, negative electrode graphite) to prepare batteries.
(1) Charging the prepared battery at-20deg.C rate of 0.2C rate and at-40deg.C rate of 0.5C rate, and recording constant current charging ratio data;
(2) The battery thus obtained was subjected to a charge-discharge cycle test of 1C/1C at-20℃and cycled 300 times to record the capacity retention, and the results are shown in Table 1 below.
TABLE 1
From the above results, it can be seen that the electrolyte of the present invention has excellent low temperature properties.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (16)
1. An additive for an electrolyte, characterized in that it contains a ureide compound selected from 2-oxomalonyl urea and/or oxalyl urea.
2. The additive for an electrolyte according to claim 1, further comprising an auxiliary component, wherein the auxiliary component is one or more of ethylene carbonate, methylene methyldisulfonate, lithium difluorophosphate, and lithium difluorooxalato borate.
3. The additive for an electrolyte according to claim 2, wherein the auxiliary component is a mixture of ethylene carbonate and one or more selected from the group consisting of methylene methyldisulfonate, lithium difluorophosphate and lithium difluorooxalato borate, and the content of ethylene carbonate is 40 to 60% based on the total mass of the auxiliary component.
4. The additive for an electrolyte according to any one of claims 1 to 3, wherein the mass ratio of the auxiliary component to the ureide compound is 1 (0.5 to 1).
5. A lithium battery electrolyte comprising the additive for an electrolyte according to any one of claims 1 to 4.
6. The lithium battery electrolyte according to claim 5, wherein the additive for the electrolyte is added in an amount of 0.2 to 2% based on the total mass of the lithium battery electrolyte.
7. The lithium battery electrolyte according to claim 6, wherein the additive for the electrolyte is added in an amount of 1.5 to 2% based on the total mass of the lithium battery electrolyte.
8. The lithium battery electrolyte according to claim 5, further comprising an organic solvent comprising component a and component B in a mass ratio of 2:8-5:5;
wherein the component A is prepared from the following components in percentage by mass (1-2): a mixture of the cyclic carbonate and the chain carbonate of (1-3);
the component B is chain carboxylic ester;
the cyclic carbonate is one or two of ethylene carbonate and propylene carbonate;
and/or the chain carbonic ester is one or more of dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate and methyl propyl carbonate;
and/or the chain carboxylic acid ester is one or more of methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate and propyl butyrate.
9. The lithium battery electrolyte according to claim 8, further comprising a lithium salt, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium perchlorate, and lithium tetrafluoroborate.
10. The lithium battery electrolyte according to claim 9, wherein the lithium salt is added in an amount of 12 to 20% based on the total mass of the lithium battery electrolyte.
11. The lithium battery electrolyte according to claim 10, wherein the lithium salt is added in an amount of 15 to 20% based on the total mass of the lithium battery electrolyte.
12. The lithium battery electrolyte according to claim 9, which comprises the following components in parts by weight:
78-87.8 parts of organic solvent, 12-20 parts of lithium salt and 0.2-2 parts of electrolyte additive.
13. Use of the additive for an electrolyte according to any one of claims 1 to 4 or the lithium battery electrolyte according to any one of claims 5 to 12 in any one of the following:
(1) The low-temperature performance of the lithium ion battery is improved;
(2) And the SEI film impedance of the lithium ion battery is reduced.
14. The use according to claim 13, wherein the lithium ion battery is a lithium iron phosphate lithium ion battery.
15. A lithium ion battery, characterized in that it contains the lithium battery electrolyte according to any one of claims 5-12.
16. The lithium ion battery of claim 15, wherein the lithium ion battery is a lithium iron phosphate lithium ion battery.
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