CN116505080B - Nonaqueous electrolyte and secondary battery - Google Patents
Nonaqueous electrolyte and secondary battery Download PDFInfo
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- CN116505080B CN116505080B CN202310731623.5A CN202310731623A CN116505080B CN 116505080 B CN116505080 B CN 116505080B CN 202310731623 A CN202310731623 A CN 202310731623A CN 116505080 B CN116505080 B CN 116505080B
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- 239000011255 nonaqueous electrolyte Substances 0.000 title abstract description 8
- 239000000654 additive Substances 0.000 claims abstract description 132
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 126
- 230000000996 additive effect Effects 0.000 claims abstract description 126
- 239000003792 electrolyte Substances 0.000 claims abstract description 108
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 6
- 150000002367 halogens Chemical class 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 3
- 239000006259 organic additive Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 27
- 239000000126 substance Substances 0.000 abstract description 10
- 230000020169 heat generation Effects 0.000 abstract description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 65
- -1 heterocyclic aliphatic compound Chemical class 0.000 description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 49
- 229910001416 lithium ion Inorganic materials 0.000 description 49
- 238000002156 mixing Methods 0.000 description 45
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 43
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 30
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 22
- 238000001035 drying Methods 0.000 description 22
- 239000011259 mixed solution Substances 0.000 description 21
- 125000000524 functional group Chemical group 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910003002 lithium salt Inorganic materials 0.000 description 5
- 159000000002 lithium salts Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 125000005843 halogen group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 238000004880 explosion Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000002161 passivation Methods 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 229910013188 LiBOB Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001555 benzenes Chemical class 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000002541 furyl group Chemical group 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 125000004076 pyridyl group Chemical group 0.000 description 2
- 125000000168 pyrrolyl group Chemical group 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- HMUNWXXNJPVALC-UHFFFAOYSA-N 1-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)C(CN1CC2=C(CC1)NN=N2)=O HMUNWXXNJPVALC-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QRNQEHDAGXVLJA-UHFFFAOYSA-N 3,3-bis(cyanomethyl)pentanedinitrile Chemical compound N#CCC(CC#N)(CC#N)CC#N QRNQEHDAGXVLJA-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- YZSKZXUDGLALTQ-UHFFFAOYSA-N [Li][C] Chemical compound [Li][C] YZSKZXUDGLALTQ-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229930188620 butyrolactone Natural products 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BEENYAUVNJBLFC-UHFFFAOYSA-N lithium;phthalic acid Chemical compound [Li].OC(=O)C1=CC=CC=C1C(O)=O BEENYAUVNJBLFC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000004804 winding Methods 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
-
- 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
Landscapes
- 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 discloses a nonaqueous electrolyte and a secondary battery, wherein the nonaqueous electrolyte comprises electrolyte salt, an organic solvent, a film-forming additive and an ether additive; the ether additive is a compound with ether bond, halogen element and cyclic structure or a composition composed of a plurality of compounds with ether bond, halogen element and cyclic structure. The electrolyte containing the ether additive can shorten the overcharge time, reduce the chemical heat generation and inhibit the generation of combustible substances.
Description
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a non-aqueous electrolyte and a secondary battery.
Background
The lithium ion energy storage battery is the most promising energy storage battery system at present due to the remarkable advantage of the stability. However, the energy storage battery has serious overcharge safety problems in the use process, potential safety hazards are easy to generate when the battery is overcharged, fire or even explosion occurs, and the problems limit the large-scale application of the lithium ion energy storage battery.
In order to solve the problem of overcharging of a battery, a mode of adding additives into electrolyte is adopted in the prior art, and two additives are mainly adopted in the electrolyte for preventing the battery from being overcharged in the prior art: electropolymerization and redox types. The electropolymerization type additive comprises benzene derivatives such as biphenyl and cyclohexylbenzene, and the oxidative reduction type additive comprises 3, 3-bis (cyanomethyl) glutaronitrile, 1, 3, 6-hexanetrinitrile, 2' -biphenyl disulfonic acid lithium, phthalic acid lithium, benzene derivatives and the like. However, electropolymerized additives tend to form a network of electrically conductive links between the positive and negative electrodes, resulting in the risk of short circuits between the positive and negative electrodes; the local heat generation and reversible transfer processes of redox type additives during oxidation and reduction make it difficult for overcharging to reach the cut-off voltage rapidly.
Disclosure of Invention
The inventor finds out through a large number of experiments that the reason for the overcharge thermal runaway of the battery cell is mainly that the overcharge time is too long in the use process, the chemical heat generation is too much and the unsaturated combustible gas is generated. The overcharge time and chemical heat generation are related to the stability of the SEI film, and the stable conversion of combustible species can effectively reduce the risk of fire and explosion. The stability of SEI film is very big to the effect of overcharging inefficacy, and the premature decomposition of SEI film can accelerate the reaction of electrolyte and negative pole embedded lithium carbon for the holistic thermal runaway of electric core. The stable SEI film can enable the anode and the cathode to be stable in the overcharging process, prevent the SEI film from being decomposed and repaired when the stable voltage reaches the overcharging cut-off voltage, and inhibit the speed of chemical heat generation and thermal runaway.
The electrolyte is the most flammable component in the lithium battery and is closely related to the use safety of the battery. Therefore, there is a need to develop an effective and safe electrolyte capable of shortening the overcharge time, reducing chemical heat generation, and suppressing the generation of combustible substances.
In order to overcome the defects in the prior art, the invention provides a non-aqueous electrolyte for a battery, which comprises electrolyte salt, an organic solvent, a film-forming additive and an ether additive;
the ether additive is one or more compounds with ether bonds, halogen elements and cyclic structures;
the structure of the ether additive is one or more of the formulas (I-A), (I-B) and (I-C),
/>。
wherein R1 and R2 each independently represent a H, C C6 alkyl group or a C1C 6 alkyl group substituted with a halogen atom;
r3 represents an alkyl group of 0 to 12 carbon atoms, or is substituted by a halogen atom, -OH, -CHO, -COOH, -NO 2 、-SO 3 H、-NH 2 An alkyl group of 0 to 12 carbon atoms substituted with one or more functional groups of RCO-, furyl, thienyl, pyridyl, pyrrolyl, phenyl;
r4 and R5 each independently represent a halogen atom or a C1-C6 alkyl group substituted with a halogen atom;
x represents-F, -Cl, -I;
R ring representing a functional group having cyclic character.
The additive molecule contains ether bond, which is beneficial to neutralizing unsaturated alkane generated in the overcharging stage and inhibiting further generation of chemical heat; the cyclic structure in the additive molecule can enable the additive to effectively contact the surface of a negative electrode (such as graphite) to promote the film forming reaction; C-X bond, especially C-F bond, is favorable for film formation and stabilization of ether bond. In addition, because of the presence of the C-X ether linkage at the alpha position, wherein the ether linkage can be stabilized by the C-X linkage at the alpha position, the generation of oxygen is avoided.
According to one embodiment of the invention, the additive further comprises a film-forming additive. The film forming additive is a conventional film forming substance in the field, and the film forming additive and the ether additive jointly act to form a stable SEI film.
According to a specific embodiment of the invention, the ether additive has one or more of the structures of formula (I-A) and formula (I-B).
According to one embodiment of the invention, X is-F.
According to one embodiment of the invention, R1 and R2 are both H.
According to one embodiment of the invention, R4 is F.
According to a specific embodiment of the invention, the ether additive is selected from
。
According to one embodiment of the invention, R ring The functional group obtained after one H atom in the structure shown in the following structural formula is replaced:
。
wherein Y1, Y2, Y3, Y4, Y5, Y6, Y7 are each independently represented by H, alkyl, -X (X=F, cl, br), -OH, -CHO, -COOH, -NO 2 、-SO 3 H、-NH 2 One or more of RCO-, furans, thiophenes, pyridines, pyrroles.
According to one embodiment of the invention, R ring The functional group obtained after one H atom in the structure shown in the following structural formula is replaced:
。
wherein B1-B8 represent each bond in the 3-8 membered structure compound, namely a single bond or more than or equal to 1 double bond.
According to one embodiment of the invention, R ring The functional group obtained after one H atom in the structure shown in the following structural formula is replaced:
。
wherein the atoms A1-A8 are carbon atoms or atoms of boron, nitrogen, oxygen, sulfur, phosphorus, silicon and the like to form a multi-membered heterocyclic aliphatic compound.
According to one embodiment of the invention, R ring The functional group obtained after one H atom in the structure shown in the following structural formula is replaced:
。
wherein, in the above structure, H on each cyclisation can be defined by one or more of-X (X=F, cl, br), -OH, -CHO, -COOH, -NO 2 、-SO 3 H、-NH 2 RCO-, furyl, thienyl, pyridyl, pyrrolyl; at the same time, the C atom on the ring can be replaced by any boron, nitrogen, oxygen, sulfur, phosphorus and silicon to form heterocyclic compounds or thick compounds.
According to one embodiment of the invention，R ring The functional group obtained after one H atom in the structure shown in the following structural formula is replaced:
。
according to an embodiment of the present invention, the battery nonaqueous electrolyte is a lithium ion battery nonaqueous electrolyte.
According to one embodiment of the present invention, the electrolyte salt is LiPF 6 、LiBF 4 、LiAsF 6 、LiClO 4 、LiCF 3 SO 3 、Li(CF 3 SO 3 ) 2 N, liBOB, liDOFB.
According to one embodiment of the invention, the concentration of lithium salt in the electrolyte is 0.5 to 1.8 mol/L, preferably 1.2 mol/L, calculated as lithium ion.
According to an embodiment of the present invention, the non-aqueous organic solvent is a mixture of cyclic carbonates and/or chain carbonates, and the cyclic carbonates are one or more selected from the group consisting of ethylene carbonate, propylene carbonate, butyrolactone and butylene carbonate; the chain carbonic ester is one or a combination of a plurality of the derivatives of the carbonic ester synthesized by carbonic acid, wherein the chain carbonic ester is selected from dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, dipropyl carbonate, straight-chain or branched-chain fatty monoalcohol with 3-16 carbon atoms.
According to an embodiment of the present invention, the film forming additive is one or more of ethylene carbonate, fluoroethylene carbonate (FEC).
According to a specific embodiment of the invention, the film-forming additive accounts for 0.1% -5% of the total mass of the electrolyte.
According to a specific embodiment of the invention, the ether additive accounts for 6-wt wt% to 16wt% of the total mass of the electrolyte.
Another object of the present invention is to provide a secondary battery comprising the above electrolyte.
According to an embodiment of the present invention, the secondary battery is a lithium ion battery.
The beneficial effects are that:
according to the invention, an ether additive (especially an additive with the structural characteristics of a general formula A, a general formula B and a general formula C) containing ether bonds, halogen elements and a cyclic structure is added into electrolyte, and the delocalized pi bond formed by the cyclic structure can enable additive molecules to interact with a negative electrode (such as graphite), so that the whole additive molecules are driven to contact the surface of the negative electrode, and further a C-X (X represents-F, -Cl, -I) group is promoted to participate in the formation of an SEI film, and in addition, a rich and stable LiX compact passivation film can be formed, the film surface resistance of a battery cell on the positive electrode side and the negative electrode side in overcharging is stabilized, so that the voltage is stably increased to an overcharging cut-off voltage, the overcharging time of the battery cell is shortened, and overload input of electric energy and the generation of Joule heat are fundamentally reduced. Meanwhile, the stable and compact passivation film can effectively avoid damage and repair of the SEI film, reduce chemical heat generation in overcharge and integrally improve overcharge thermal runaway of the battery. In addition, the ether bond can neutralize unsaturated alkane generated in the overcharging process to form a cyclic compound, and C-X at the alpha position can further stabilize the formed cyclic compound to inhibit the risks of combustion and explosion. Therefore, the invention adopts ether additives added with ether bonds, halogen elements and cyclic structures to cooperatively play roles among functional groups, effectively solves the overcharge problem of the secondary battery, shortens the overcharge time of the secondary battery, reduces the input of electric energy and the continuous deterioration of side reaction heat production, and improves the overcharge stability of the battery core.
Detailed Description
The present invention will be further illustrated by the following examples. It should also be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the invention, since various insubstantial modifications and adaptations of the invention to those skilled in the art based on the foregoing disclosure are intended to be within the scope of the invention and the specific process parameters and the like set forth below are merely one example of a suitable range within which one skilled in the art would choose from the description herein without being limited to the specific values set forth below.
Example 1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of lithium hexafluorophosphate being 1.2 mol/L calculated by lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5-wt% of the total mass of the electrolyte, and an overcharging additive formed by mixing an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 12-wt% of the total mass of the electrolyte and a film forming additive of fluoroethylene carbonate (FEC) accounting for 1-wt% of the total mass of the electrolyte, and uniformly mixing to obtain the required electrolyte.
Example 1-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding a mixed overcharging additive of an ether additive of 1, 2-tetrafluoroethyl phenyl ether and a film forming additive of fluoroethylene carbonate (FEC) accounting for 8 wt% of the total mass of the electrolyte into the mixture, and uniformly mixing to obtain the required electrolyte.
Examples 1-2: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding a mixed overcharging additive of an ether additive of 1, 2-tetrafluoroethyl phenyl ether and a film forming additive of fluoroethylene carbonate (FEC) accounting for 16wt% of the total mass of the electrolyte into the mixture, and uniformly mixing to obtain the required electrolyte.
Examples 1-3: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding a mixed overcharge additive of an ether additive of 1, 2-tetrafluoroethyl phenyl ether and a film forming additive of fluoroethylene carbonate (FEC) accounting for 6wt% of the total mass of the electrolyte into the mixture, and uniformly mixing to obtain the required electrolyte.
Examples 1 to 4: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 6wt% of the total mass of the electrolyte and a mixed overcharge additive of a film forming additive of fluoroethylene carbonate (FEC) accounting for 1 wt% of the total mass of the electrolyte, and uniformly mixing to obtain the required electrolyte.
Comparative examples 1-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding a mixed overcharge additive of an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 18 wt% of the total mass of the electrolyte and a film forming additive of fluoroethylene carbonate (FEC) accounting for 0.2 wt%, and uniformly mixing to obtain the required electrolyte.
Comparative examples 1-2: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 0.2 wt% of the total mass of the electrolyte and a mixed overcharge additive of 3 wt% of a film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Comparative examples 1-3: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding a mixed overcharging additive of an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 19 wt% of the total mass of the electrolyte and a film forming additive of fluoroethylene carbonate (FEC) accounting for 3 wt%, and uniformly mixing to obtain the required electrolyte.
Example 2: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl ether accounting for 10 wt% of the total mass of the electrolyte and a mixed overcharge additive of a film forming additive of fluoroethylene carbonate (FEC) accounting for 1 wt% of the total mass of the electrolyte, and uniformly mixing to obtain the required electrolyte.
Example 2-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 8 wt% of the total mass of the electrolyte and a mixed overcharge additive of 1 wt% of a film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Example 2-2: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 16wt% of the total mass of the electrolyte and a mixed overcharge additive of 1 wt% of a film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Examples 2-3: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 6wt% of the total mass of the electrolyte and a mixed overcharging additive of 0.2 wt% of the film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Examples 2 to 4: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 17 wt% of the total mass of the electrolyte and a mixed overcharging additive of 0.2 wt% of the film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Comparative example 2-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 19. 19 wt% of the total mass of the electrolyte and a mixed overcharging additive of 0.2 wt% of film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Comparative example 2-2: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 0.2 wt% of the total mass of the electrolyte and a mixed overcharging additive of 3 wt% of the film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Comparative examples 2 to 3: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 5wt% of the total mass of the electrolyte and a mixed overcharge additive of 3 wt% of a film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Example 3: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L calculated by lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5-wt% of the total mass of the electrolyte, adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 3-wt% of the total mass of the electrolyte, and adding a mixed overcharge additive of 3-wt% of an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether and 0% of FEC into the mixture, and uniformly mixing to obtain the required electrolyte.
Example 3-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L calculated by lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt percent of the total mass of the electrolyte, adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 8 wt percent of the total mass of the electrolyte, and adding a mixed overcharge additive of an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 8 wt percent of the ether additive and fluoroethylene carbonate (FEC) accounting for 0.2 percent of the film forming additive, and uniformly mixing to obtain the required electrolyte.
Comparative 3-1: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) according to the volume ratio of 1:1:1, adding lithium hexafluorophosphate into the mixture to prepare a mixed solution with the concentration of the lithium hexafluorophosphate being 1.2 mol/L based on lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt percent of the total mass of the electrolyte, adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 2.5 wt percent of the total mass of the electrolyte, and adding a mixed overcharging additive of an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 2.5 wt percent of the ether additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Example 4: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium salt LiBOB into the mixture to prepare a mixed solution with a lithium salt concentration of 1.2 mol/L calculated by lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of 1, 2-tetrafluoroethyl phenyl ether accounting for 8. 8 wt% of the total mass of the electrolyte and a mixed overcharging additive of 1. 1 wt% of a film forming additive of fluoroethylene carbonate (FEC), and uniformly mixing to obtain the required electrolyte.
Example 5: preparing lithium ion battery electrolyte in a drying room at 20 ℃): firstly, uniformly mixing Ethylene Carbonate (EC), dimethyl carbonate (DMC) and methyl ethyl carbonate (EMC) in a volume ratio of 1:1:1, adding lithium salt LiBOB into the mixture to prepare a mixed solution with a lithium salt concentration of 1.2 mol/L calculated by lithium ions, then adding a film forming additive of ethylene carbonate accounting for 0.5wt% of the total mass of the electrolyte, and adding an ether additive of benzyl-1, 2-tetrafluoroethyl phenyl ether accounting for 8. 8 wt% of the total mass of the electrolyte and a mixed overcharge additive of a film forming additive of fluoroethylene carbonate (FEC) accounting for 1. 1 wt%, and uniformly mixing to obtain the required electrolyte.
Experimental example
The lithium ion battery is prepared by adopting the electrolyte prepared by the method, and the specific preparation process is as follows:
s1, preparing a positive plate: mixing lithium iron phosphate, conductive carbon and adhesive according to the mass ratio of 95:3:2, dispersing in N-methyl-2-pyrrolidone, uniformly coating the obtained positive slurry on two sides of an aluminum foil, and drying; the thickness of the positive electrode plate is 130-210 and um;
s2, preparing a negative plate: according to 94.8:2:1:2.2 The quality of the composite material is that the composite material comprises graphite and conductive carbon, wherein the graphite and the conductive carbon are adhesive Styrene Butadiene Rubber (SBR) and carboxymethyl cellulose CMC, which are dispersed in water, and the obtained negative electrode slurry is uniformly coated on two sides of a copper foil and dried; the thickness of the positive electrode plate is between 90 and 180 and um;
s3, diaphragm: a single-layer PP diaphragm with the diameter of 12-20um is adopted;
s4, lithium ion battery assembly: placing the positive plate and the negative plate on two sides of the diaphragm, winding a three-layer structure formed by the positive plate, the negative plate and the diaphragm to form a bare cell, and then carrying out vacuum baking on the bare cell at 80-120 ℃ to obtain the cell to be injected with liquid; then electrolyte is injected into the battery cell, and the battery cell is subjected to standing formation to be tested.
The batteries made from the above electrolytes were subjected to overcharge performance tests, and the results are summarized in table 1: after the battery is pre-charged, the full-charge state of 100% SOC of the battery is ensured, and then the battery is charged to 1.5 times of SOC by constant current of 1C rate. And collecting the cut-off time, temperature and final voltage of the battery cell after the overcharge is finished and the battery cell is kept stand for 1h in the test process. The final voltage is considered in the normal state as the effectiveness of the additive in improving thermal runaway by overcharging, the result of which is directly judged. The shorter the overcharge time, the lower the highest temperature, indicating that the better the improvement effect.
TABLE 1
When the total content of the ether additives shown herein is less than 6%, the effect thereof on the surface of the negative electrode is reduced, and a sufficiently dense and stable SEI passivation film cannot be formed. In the overcharge stage, irreversible heat accumulation in the battery cell leads to internal temperature rise, and an SEI film with insufficient compactness and stability is decomposed after reaching 80 ℃, so that self-heating accelerates internal heat generation and leads to thermal runaway. When the content of the additive is more than 16%, the formed SEI film is super-thick, the impedance of the battery is seriously increased, so that the battery core rapidly generates a large amount of Joule heat in overcharge, the temperature breaks through the tolerance temperature of the diaphragm, the final diaphragm is melted, and thermal runaway occurs in the anode and the cathode. And it can be seen from the data of table 1 that the manner of mixing multiple ether additives is superior to a single ether additive.
Unless otherwise defined, all terms used herein are intended to have the meanings commonly understood by those skilled in the art.
The described embodiments of the present invention are intended to be illustrative only and not to limit the scope of the invention, and various other alternatives, modifications, and improvements may be made by those skilled in the art within the scope of the invention, and therefore the invention is not limited to the above embodiments but only by the claims.
Claims (3)
1. A secondary battery, characterized in that an electrolyte of the battery comprises electrolyte salt, organic solvent and additive; the additive comprises an ether additive; the ether additive is one or more compounds with ether bonds, halogen elements and cyclic structures;
the structure of the ether additive is that
；
The ether additive accounts for 6-wt wt% of the total mass of the electrolyte.
2. The secondary battery according to claim 1, wherein the additive further comprises a film-forming additive.
3. The secondary battery according to claim 2, wherein the film-forming additive accounts for 0.1% to 5% of the total mass of the electrolyte.
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