CN116365026A - Nonaqueous electrolyte and lithium ion battery containing same - Google Patents
Nonaqueous electrolyte and lithium ion battery containing same Download PDFInfo
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- CN116365026A CN116365026A CN202111628953.9A CN202111628953A CN116365026A CN 116365026 A CN116365026 A CN 116365026A CN 202111628953 A CN202111628953 A CN 202111628953A CN 116365026 A CN116365026 A CN 116365026A
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- lithium
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- lithium ion
- ion battery
- carbonate
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 86
- 239000000654 additive Substances 0.000 claims abstract description 22
- 230000000996 additive effect Effects 0.000 claims abstract description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 14
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 14
- XBHOUXSGHYZCNH-UHFFFAOYSA-N 2-phenyl-1,3-benzothiazole Chemical compound C1=CC=CC=C1C1=NC2=CC=CC=C2S1 XBHOUXSGHYZCNH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 27
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 26
- -1 cyclic ester Chemical class 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 11
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- ZJPPTKRSFKBZMD-UHFFFAOYSA-N [Li].FS(=N)F Chemical compound [Li].FS(=N)F ZJPPTKRSFKBZMD-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 claims description 3
- VCYZVXRKYPKDQB-UHFFFAOYSA-N ethyl 2-fluoroacetate Chemical compound CCOC(=O)CF VCYZVXRKYPKDQB-UHFFFAOYSA-N 0.000 claims description 3
- ODMITNOQNBVSQG-UHFFFAOYSA-N ethyl 2-fluoropropanoate Chemical compound CCOC(=O)C(C)F ODMITNOQNBVSQG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007770 graphite material Substances 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 3
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 3
- MHAIQPNJLRLFLO-UHFFFAOYSA-N methyl 2-fluoropropanoate Chemical compound COC(=O)C(C)F MHAIQPNJLRLFLO-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 4
- 238000002161 passivation Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000000630 rising effect Effects 0.000 abstract description 2
- 239000012046 mixed solvent Substances 0.000 description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 44
- 229910013872 LiPF Inorganic materials 0.000 description 23
- 101150058243 Lipf gene Proteins 0.000 description 23
- 229910013870 LiPF 6 Inorganic materials 0.000 description 22
- 229910052757 nitrogen Inorganic materials 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000004305 biphenyl Substances 0.000 description 5
- 235000010290 biphenyl Nutrition 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 229940125904 compound 1 Drugs 0.000 description 4
- 229940125782 compound 2 Drugs 0.000 description 4
- 229940126214 compound 3 Drugs 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- KLECYOQFQXJYBC-UHFFFAOYSA-N 1-fluoro-2-phenylbenzene Chemical group FC1=CC=CC=C1C1=CC=CC=C1 KLECYOQFQXJYBC-UHFFFAOYSA-N 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 208000019901 Anxiety disease Diseases 0.000 description 1
- WXNUAYPPBQAQLR-UHFFFAOYSA-N B([O-])(F)F.[Li+] Chemical compound B([O-])(F)F.[Li+] WXNUAYPPBQAQLR-UHFFFAOYSA-N 0.000 description 1
- 230000036506 anxiety Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011815 overcharge protection agent Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Images
Classifications
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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
-
- 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 present invention relates to a nonaqueous electrolyte solution and a lithium ion battery containing the same. In order to solve the technical problem of potential safety hazards caused by overcharging of batteries in the prior art, the invention provides a non-aqueous electrolyte which comprises lithium salt, an organic solvent and an additive, wherein the additive comprises 2-phenyl-benzothiazole and derivatives thereof, a passivation film can be formed on the surface of an anode when the lithium ion battery is overcharged, the voltage of the battery is prevented from further rising in the overcharging process, the temperature of the electrolyte is slowly raised by the additive during the overcharging process, the room temperature cycle performance of the lithium ion battery can not be influenced by the addition of the additive, and even the room temperature cycle performance of the lithium ion battery can be improved, so that the potential safety hazards caused by the overcharging of the battery are effectively avoided.
Description
Technical Field
The invention belongs to the technical field of lithium batteries, and particularly relates to a nonaqueous electrolyte and a lithium ion battery containing the same.
Background
Lithium ion batteries have the highest energy density among secondary batteries currently commercially used, and thus are widely used in the fields of mobile electronics, green transportation, large-scale energy storage, and the like. The lithium ion battery industry has remained rapidly growing since the first commercial application in 1990. The lithium ion battery rapidly occupies the market of mobile electronic energy storage products from the appearance of commercial products by virtue of the characteristic of high energy density. In recent decades, with the emphasis on energy safety and sustainable energy development in countries around the world, lithium ion batteries have been pushed into the fast lanes of scientific research and industrial development as an important electrochemical energy storage device.
Currently, the electrolyte used in commercial lithium ion batteries consists of an organic solvent and LiPF dissolved therein 6 And lithium salt. Among them, the organic solvents are usually binary or ternary mixed solvents based on Ethylene Carbonate (EC) having a large dielectric constant, in which chain carbonates (dimethyl carbonate (DMC), diethyl carbonate (DEC), methyl ethyl carbonate (EMC), carboxylic esters or ethers are co-solvents, and these common solvents have characteristics of good solubility with lithium salts, high conductivity of the composed electrolyte, and stable SEI films at positive and negative electrodes, and thus are considered as the best choice of electrolyte systems, particularly electrolyte solvents for electric automobile batteries, however, the inflammable characteristics of these solvents necessitate restrictions on abuse of batteries in daily use of batteries.
Currently, as the application of lithium ion batteries is becoming wider and wider, safety accidents caused by battery abuse due to various reasons occur from time to time, so that the public generates great safety anxiety on the application of lithium ion batteries.
The overcharge prevention of the lithium ion battery mainly prevents the electrolyte from decomposing and heating to cause chain reaction and further burning due to overcharge. The additive is added into the electrolyte, and the additive can not react with the electrolyte or other components of the electrolyte in the working potential range of the battery material, and once the positive electrode potential is higher than the maximum charging potential of the positive electrode material, the sacrificial additive can form a layer of compact passivation film on the surface of the material to prevent migration of ions or exchange of electrons, so that the battery is close to an off state, and the battery is disabled in an overcharged state and cannot burn due to continuous increase of voltage. Biphenyl has been used in the past as an overcharge-preventing additive in lithium ion battery electrolytes, which has certain overcharge-preventing properties but causes an increase in battery temperature and has a certain effect on the cycle performance of the battery. Therefore, there is a need in the market to develop new anti-overcharge additives to replace biphenyl.
Disclosure of Invention
The invention aims to provide a nonaqueous electrolyte solution which has overcharge prevention characteristics and can improve the room-temperature cycle performance of a lithium ion battery.
The invention further aims to provide the lithium ion battery which has good normal-temperature cycle performance, is not obvious in temperature rise during overcharging and can effectively prevent overcharging to a certain extent.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a nonaqueous electrolyte comprising a lithium salt, an organic solvent and an additive comprising 2-phenyl-benzothiazole having a structure represented by the general formula (1) and derivatives thereof,
wherein R is 1 、R 2 And R is 3 Independently is H, a halogen atom or an alkyl group.
Preferably, R 1 、R 2 And R is 3 H, cl, F, C independently 1 ～C 4 Linear alkyl or tert-butyl.
Preferably, R 1 、R 2 And R is 3 H, cl or F, independently.
Preferably, the additive comprises one or more of the following compounds:
preferably, the 2-phenyl-benzothiazole and the derivatives thereof of the structure shown in the general formula (1) account for 0.1-10wt% of the total mass of the nonaqueous electrolyte.
Further preferably, the 2-phenyl-benzothiazole and its derivatives represented by the general formula (1) account for 0.1 to 5wt% of the total mass of the nonaqueous electrolytic solution. When the addition amount of the additive is in a proper range, overcharge can be effectively prevented, and the influence on the room temperature cycle performance of the battery is small.
Preferably, the organic solvent comprises cyclic ester and/or chain ester, wherein the cyclic ester is one or more of gamma-butyrolactone, ethylene carbonate, propylene carbonate and fluoroethylene carbonate; the chain ester is one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, ethyl fluoropropionate and ethyl fluoroacetate.
Further preferably, the organic solvent is a mixture of a cyclic ester and a chain ester, wherein the mass ratio of the cyclic ester to the chain ester is 1: (1-2.5) mixing.
Still more preferably, the mass ratio of the cyclic ester to the chain ester is 1: (1.5-2) mixing.
Preferably, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium difluorodioxalate phosphate, lithium difluorophosphate, lithium trifluoromethylsulfonate, lithium difluorodioxalate phosphate, lithium difluoroborate, lithium monooxalato difluoroborate and lithium difluorosulfimide.
Preferably, the concentration of the lithium salt is 0.6-1.5 mol/L.
Further preferably, the concentration of the lithium salt is 0.8 to 1.3mol/L.
A lithium ion battery comprises a positive electrode, a negative electrode and electrolyte, wherein the electrolyte is the non-aqueous electrolyte.
Preferably, the positive electrode is a lithium cobaltate material.
Preferably, the negative electrode is a graphite material.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the 2-phenyl-benzothiazole and the derivative thereof with the structure shown in the general formula (1) can form a passivation film on the surface of the positive electrode when the lithium ion battery is overcharged, so that the voltage of the battery is prevented from further rising in the overcharged process, the temperature of electrolyte rises slowly when the battery is overcharged, the addition of the additive does not influence the room temperature cycle performance of the lithium ion battery, and even the room temperature cycle performance of the lithium ion battery can be improved, and potential safety hazards caused by the overcharged battery are effectively avoided.
Drawings
FIG. 1 is a cyclic voltammogram of a nonaqueous electrolyte of example 1 under a three electrode system, scan speed: 5mV/s.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
The invention mainly carries out a great deal of research and experimental verification on the additive of the lithium battery electrolyte from the aspect of preventing the battery from being overcharged, and finally provides a non-aqueous electrolyte and a lithium ion battery related to the non-aqueous electrolyte.
According to the invention, the non-aqueous solution comprises lithium salt, solvent and additive, the additive comprises 2-phenyl-benzothiazole and derivatives thereof with a structure shown in a general formula (1),
wherein R is 1 、R 2 And R is 3 Independently is H, a halogen atom or an alkyl group.
Preferably, R 1 、R 2 And R is 3 H, cl, F, C independently 1 ～C 4 Linear alkyl or tert-butyl.
Preferably, R 1 、R 2 And R is 3 H, cl or F, independently.
According to the invention, compounds 1-6 are preferably selected, the molecular structure is as follows:
according to the invention, the 2-phenyl-benzothiazole and derivatives thereof are used in an amount of 0.1 to 10 wt.%, for example 0.1 wt.%, 0.5 wt.%, 1 wt.%, 1.5 wt.%, 2 wt.%, 2.5 wt.%, 3 wt.%, 3.5 wt.%, 4 wt.%, 4.5 wt.%, 5 wt.%, 5.5 wt.%, 6 wt.%, 6.5 wt.%, 7 wt.%, 8.5 wt.%, 9 wt.%, 9.5 wt.%, 10 wt.%. The proper amount of 2-phenyl-benzothiazole and the derivatives thereof can effectively prevent overcharge, and have little influence on the room temperature cycle performance of the lithium ion battery.
According to the invention, the organic solvent is cyclic ester and/or chain ester, and the cyclic ester is one or more of gamma-butyrolactone, ethylene carbonate, propylene carbonate and fluoroethylene carbonate; the chain ester is one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, ethyl fluoropropionate and ethyl fluoroacetate.
Preferably, the organic solvent is a mixture of a cyclic ester and a chain ester, wherein the mass ratio of the cyclic ester to the chain ester is 1: (1-2.5), for example 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.5.
According to the invention, the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, anhydrous lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium difluorodioxalate phosphate, lithium difluorophosphate, lithium trifluoromethylsulfonate, lithium difluorodioxalate phosphate, lithium dioxalate borate, lithium monooxalato difluoroborate and lithium difluorosulfimide.
According to the invention, the concentration of the lithium salt is 0.6 to 1.5mol/L, for example 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.5mol/L.
The performance of the lithium ion battery can be improved by selecting an organic solvent with a special formula to be matched with the 2-phenyl-benzothiazole, the derivative thereof and the lithium salt.
According to the invention, the lithium ion battery comprises a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the non-aqueous electrolyte, the positive electrode is a lithium cobaltate positive electrode material, and the negative electrode is a graphite material.
The nonaqueous electrolyte provided by the invention has the advantages of overcharge prevention property in a lithium ion battery, insignificant increase of battery temperature when overcharged to 130% SOC and improvement of the room temperature cycle performance of the battery.
The technical scheme and technical effect of the present invention are further illustrated by examples and comparative examples below.
In the following examples and comparative examples, all the raw materials used were commercially available unless otherwise specified.
Example 1
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 1 was added to the electrolyte to prepare a target electrolyte.
Example 2
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC andthe EMC is uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 2 was added to the electrolyte to prepare a target electrolyte.
Example 3
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 3 was added to the electrolyte to prepare a target electrolyte.
Example 4
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 4 was added to the electrolyte to prepare a target electrolyte.
Example 5
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 5 was added to the electrolyte to prepare a target electrolyte.
Example 6
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of compound 6 was added to the electrolyte to prepare a target electrolyte.
Example 7
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 1 was added to the electrolyte to prepare a target electrolyte.
Example 8
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 2 was added to the electrolyte to prepare a target electrolyte.
Example 9
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 3 was added to the electrolyte to prepare a target electrolyte.
Example 10
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 4 was added to the electrolyte to prepare a target electrolyte.
Example 11
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 5 was added to the electrolyte to prepare a target electrolyte.
Example 12
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of compound 6 was added to the electrolyte to prepare a target electrolyte.
Example 13
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 1 was added to the electrolyte to prepare a target electrolyte.
Example 14
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 2 was added to the electrolyte to prepare a target electrolyte.
Example 15
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 3 was added to the electrolyte to prepare a target electrolyte.
Example 16
In nitrogen atmosphereIn glove box (H) 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 4 was added to the electrolyte to prepare a target electrolyte.
Example 17
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 5 was added to the electrolyte to prepare a target electrolyte.
Example 18
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of compound 6 was added to the electrolyte to prepare a target electrolyte.
Comparative example 1
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is a target electrolyte of (a).
Comparative example 2
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 1wt% of 2-fluorobiphenyl was added to the electrolyte to prepare a target electrolyte.
Comparative example 3
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 3wt% of 2-fluorobiphenyl was added to the electrolyte to prepare a target electrolyte.
Comparative example 4
In a glove box filled with nitrogen (H 2 O<10ppm，O 2 <10 ppm), DMC, EC and EMC are uniformly mixed according to the mass ratio of 1:1:1 to prepare a mixed solvent. Then, 1 equivalent of LiPF was weighed 6 Is dissolved in the mixed solvent to contain 1mol/L LiPF 6 Is used as an electrolyte. Finally, 5wt% of 2-fluorobiphenyl was added to the electrolyte to prepare a target electrolyte.
Performance comparison:
(1) Additive oxidative polymerization potential test:
a three electrode test system was used in which a 3mm diameter platinum disk electrode was used as the working electrode, two metallic lithium sheets were used as the reference electrode and the counter electrode, respectively, to characterize the passivation initiation potential of the electrode and the oxidative decomposition potential of the electrolyte in each electrolyte. FIG. 1 shows a cyclic voltammogram of example 1 under test conditions, with the initial oxidative polymerization potential of the additive and the oxidative decomposition potential of the electrolyte noted. The test results of examples 1-6 are shown in Table 1. The experimental results show that the compounds 1 to 6 used in examples 1 to 6 are all at 4.5V (vs. Li/Li) + ) The above-mentioned oxidative polymerization reaction occurs. After three electrode testing, the working electrode surface was covered with a layer of dark polymer. The polymer can play a role in inhibiting the further increase of the battery voltage when the lithium ion battery is overcharged.
TABLE 1 initial oxidative polymerization potential and oxidative decomposition potential of the electrolytes of examples 1-6
(2) The 1C rate cycle test of the lithium cobaltate/graphite battery with the room temperature of 4.2V is carried out, and the charge and discharge cut-off voltages are respectively 2.75V and 4.2V. The battery capacity retention rates after 1C rate cycling for 200 weeks, 400 weeks and 600 weeks are shown in table 2. From the experimental results of comparative examples 1 to 4, it can be seen that the addition of the conventional overcharge-preventing additive, biphenyl, seriously affects the cycle performance of the battery. Comparative examples 2 to 4 have significantly lower battery capacity retention rates at 200 weeks, 400 weeks and 600 weeks than comparative example 1, i.e., a battery without any overcharge protection agent added. In the examples, however, the battery capacity retention rates at 200 weeks, 400 weeks and 600 weeks of the other examples were not deteriorated compared to comparative example 1, even better than comparative example 1, except examples 11, 12, 17 and 18.
TABLE 2
(3) The lithium cobaltate/graphite battery with room temperature of 4.2V is overcharged to 10V with 1C multiplying power after full charge, and the platform voltage during the overcharging process and the battery surface temperature (measured by a thermocouple) under the condition that the battery reaches 130% SOC are recorded. The results are shown in Table 3. The results show that the other examples and comparative examples, except comparative example 1, can maintain an overcharge platform voltage of 5V or less at the time of overcharge of the battery, showing remarkable overcharge prevention performance. Also, when the battery was overcharged to 130% SOC, examples 1-18 were each at a lower temperature than comparative examples 2-4, indicating that compounds 1-6 exhibited superior overcharge protection compared to biphenyl, with significantly less heat evolved during their oxidative polymerization than biphenyl.
TABLE 3 Table 3
Considering the cycle capacity retention rate and overcharge prevention performance of the battery, the mass fraction of the compound 4> compound 2> compound 3> compound 1> is 3% optimal and 1% times.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, but are not intended to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A nonaqueous electrolyte comprising a lithium salt, an organic solvent and an additive, characterized in that the additive comprises 2-phenyl-benzothiazole and derivatives thereof having a structure represented by the general formula (1),
wherein R is 1 、R 2 And R is 3 Independently is H, a halogen atom or an alkyl group.
2. The nonaqueous electrolytic solution according to claim 1, wherein R 1 、R 2 And R is 3 H, cl, F, C independently 1 ～C 4 Linear alkyl or tert-butyl.
3. The nonaqueous electrolytic solution according to claim 2, wherein R 1 、R 2 And R is 3 H, cl or F, independently.
4. The non-aqueous electrolyte of claim 1, wherein the additive comprises one or more of the following compounds:
5. the nonaqueous electrolytic solution according to claim 1, wherein the 2-phenyl-benzothiazole having a structure represented by the general formula (1) and its derivatives account for 0.1 to 10% by weight of the total mass of the nonaqueous electrolytic solution.
6. The nonaqueous electrolyte according to claim 1, wherein the organic solvent comprises a cyclic ester and/or a chain ester, and the cyclic ester is one or more of γ -butyrolactone, ethylene carbonate, propylene carbonate, and fluoroethylene carbonate; the chain ester is one or more of dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, methyl propyl carbonate, methyl propionate, ethyl propionate, propyl propionate, methyl acetate, ethyl acetate, propyl acetate, methyl butyrate, ethyl butyrate, propyl butyrate, methyl fluoropropionate, ethyl fluoropropionate and ethyl fluoroacetate.
7. The nonaqueous electrolyte according to claim 1, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium perchlorate anhydrous, lithium bis (trifluoromethylsulfonyl) imide, lithium difluorodioxalate phosphate, lithium difluorophosphate, lithium trifluoromethylsulfonate, lithium difluorodioxalate phosphate, lithium dioxalate borate, lithium monooxalato difluoroborate, and lithium difluorosulfimide.
8. The nonaqueous electrolytic solution according to claim 1, wherein the concentration of the lithium salt is 0.6 to 1.5mol/L.
9. A lithium ion battery comprising a positive electrode, a negative electrode and an electrolyte, wherein the electrolyte is the nonaqueous electrolyte according to any one of claims 1 to 8.
10. The lithium ion battery of claim 9, wherein the positive electrode is a lithium cobaltate material and the negative electrode is a graphite material.
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| CN108736065A (en) * | 2017-04-25 | 2018-11-02 | 惠州比亚迪电池有限公司 | A kind of electrolyte and the lithium ion battery containing the electrolyte and/or anode |
| CN112310477A (en) * | 2019-08-02 | 2021-02-02 | 杉杉新材料（衢州）有限公司 | Overcharge-preventing lithium ion battery electrolyte |
| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108736065A (en) * | 2017-04-25 | 2018-11-02 | 惠州比亚迪电池有限公司 | A kind of electrolyte and the lithium ion battery containing the electrolyte and/or anode |
| CN112310477A (en) * | 2019-08-02 | 2021-02-02 | 杉杉新材料（衢州）有限公司 | Overcharge-preventing lithium ion battery electrolyte |
| CN112635827A (en) * | 2020-12-04 | 2021-04-09 | 上海应用技术大学 | Electrolyte additive, electrolyte containing additive and lithium ion battery |
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