CN114497733A - Electrolyte and battery thereof - Google Patents
Electrolyte and battery thereof Download PDFInfo
- Publication number
- CN114497733A CN114497733A CN202111561092.7A CN202111561092A CN114497733A CN 114497733 A CN114497733 A CN 114497733A CN 202111561092 A CN202111561092 A CN 202111561092A CN 114497733 A CN114497733 A CN 114497733A
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- CN
- China
- Prior art keywords
- electrolyte
- lithium
- salt
- tbp
- thiophene compound
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 66
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- 229930192474 thiophene Natural products 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000000654 additive Substances 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 4
- 125000005843 halogen group Chemical group 0.000 claims abstract description 4
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 4
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 4
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 claims description 5
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 5
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 4
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 4
- 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
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-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
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 150000003949 imides Chemical class 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
- QVXQYMZVJNYDNG-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)methylsulfonyl-trifluoromethane Chemical compound [Li+].FC(F)(F)S(=O)(=O)[C-](S(=O)(=O)C(F)(F)F)S(=O)(=O)C(F)(F)F QVXQYMZVJNYDNG-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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000010405 anode material Substances 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229940021013 electrolyte solution Drugs 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000009461 vacuum packaging Methods 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008410 Li-Sn-O Inorganic materials 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010710 LiFePO Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006763 Li—Sn—O Inorganic materials 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910010248 TiO2—Li4Ti5O12 Inorganic materials 0.000 description 1
- PSLUFJFHTBIXMW-WYEYVKMPSA-N [(3r,4ar,5s,6s,6as,10s,10ar,10bs)-3-ethenyl-10,10b-dihydroxy-3,4a,7,7,10a-pentamethyl-1-oxo-6-(2-pyridin-2-ylethylcarbamoyloxy)-5,6,6a,8,9,10-hexahydro-2h-benzo[f]chromen-5-yl] acetate Chemical compound O([C@@H]1[C@@H]([C@]2(O[C@](C)(CC(=O)[C@]2(O)[C@@]2(C)[C@@H](O)CCC(C)(C)[C@@H]21)C=C)C)OC(=O)C)C(=O)NCCC1=CC=CC=N1 PSLUFJFHTBIXMW-WYEYVKMPSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
- YQOXCVSNNFQMLM-UHFFFAOYSA-N [Mn].[Ni]=O.[Co] Chemical compound [Mn].[Ni]=O.[Co] YQOXCVSNNFQMLM-UHFFFAOYSA-N 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002687 intercalation Effects 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
- 230000007774 longterm Effects 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002562 thickening agent Substances 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
-
- 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
Abstract
The invention discloses an electrolyte and a battery thereof, wherein the electrolyte comprises electrolyte salt, an organic solvent and an additive; wherein the additive at least comprises a thiophene compound TBP containing silicon and boron; the thiophene compound TBP is shown as the following structural general formula I:
wherein R is1、R2、R3、R6、R7、R8、R9Are respectively selected from a group containing 1 to 9 halogen atoms or a group containing 1 to 9 carbon atoms, R4、R5Is an S or O atom.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to an electrolyte and a battery thereof.
Background
A lithium ion battery is a type of rechargeable battery that mainly relies on lithium ions moving between a positive electrode and a negative electrode to operate. During charging and discharging, Li+Intercalation and deintercalation to and from two electrodes: upon charging, Li+Deintercalating from the positive electrode and intercalating into the negative electrode through the electrolyteA cathode in a lithium-rich state; the opposite is true during discharge. The lithium ion battery has the advantages of high specific energy, no memory effect, long cycle life, small self-discharge and the like, and is widely applied to the fields of digital codes, energy storage, electric vehicles and the like.
With the continuous improvement of the limiting voltage of the anode material, the gram capacity of the battery material is gradually increased, the high-temperature performance of the battery is seriously deteriorated, and the long cycle life cannot be ensured. Especially, under high voltage (more than 4.4V), the volume of the anode material can expand and cause serious cracks in the long-term cyclic charge-discharge process, and electrolyte enters the inside of the anode material to damage the structure. Meanwhile, the protective film on the surface of the negative electrode is continuously damaged, and finally the problem of serious attenuation of the battery capacity is caused.
At present, the surface of a positive electrode material is generally modified by using an oxide coating, or materials with different forms and structures are prepared, but the process is complex, the cost is high, and the protection effect is poor.
Disclosure of Invention
The invention aims to provide an electrolyte and a battery thereof, which can improve the high-temperature performance, the low-temperature performance and the stability of the electrolyte, and have the advantages of simple process, low cost and good protection effect.
The invention discloses an electrolyte, which comprises electrolyte salt, an organic solvent and an additive; wherein the additive at least comprises a thiophene compound TBP containing silicon and boron; the thiophene compound TBP is shown as the following structural general formula I:
wherein R is1、R2、R3、R6、R7、R8、R9Are respectively selected from a group containing 1 to 9 halogen atoms or a group containing 1 to 9 carbon atoms, R4、R5Is an S or O atom.
Optionally, the additive is a thiophene compound TBP containing silicon and boron, the weight percentage of the thiophene compound TBP is 0.5-5%, and the balance is electrolyte salt and organic solvent.
Optionally, the concentration of the electrolyte salt is 0.5mol/L to 1.5 mol/L.
Optionally, the concentration of the electrolyte salt is 0.8mol/L to 1.3 mol/L.
Alternatively, the electrolyte salt is selected from at least one lithium salt of an organic lithium salt or an inorganic lithium salt.
Alternatively, the electrolyte salt is at least one lithium salt selected from compounds containing a fluorine element and a lithium element.
Alternatively, the electrolyte salt is selected from at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, and lithium tris (trifluoromethylsulfonyl) methide.
Optionally, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, tetrahydrofuran.
Alternatively, the additive comprises a thiophene compound, TBP, vinylene carbonate, vinyl sulfate, and 1, 3-propane sultone.
The invention also discloses a battery comprising the electrolyte.
In the electrolyte, under the condition of a small addition amount of the thiophene compound TBP, the contained thiophene can generate polymerization reaction on the surface of the anode, so that the electrolyte is prevented from entering and reacting with materials, and the anode materials are protected. Meanwhile, boron atoms contained in the thiophene compound TBP can be reduced to form borate, the borate is one of effective components of a Solid Electrolyte Interface (SEI) film, and the formed SEI film with excellent electrochemical stability and ionic conductivity can improve high-temperature performance and low-temperature performance. In addition, Si contained in the thiophene compound TBP can react with trace amount of water/hydrofluoric acid in the electrolyte to inhibit LiPF6The further reaction with water reduces the content of hydrofluoric acid and improves the stability of the electrolyte, and the process is simple, low in cost and good in protection effect.
Detailed Description
It is to be understood that the terminology, the specific structural and functional details disclosed herein are for the purpose of describing particular embodiments only, and are representative, but that the present invention may be embodied in many alternate forms and should not be construed as limited to only the embodiments set forth herein.
The invention is described in detail below with reference to alternative embodiments.
As an embodiment of the present invention, disclosed is an electrolyte including an electrolyte salt, an organic solvent, and an additive;
wherein the additive at least comprises a thiophene compound TBP containing silicon and boron; the thiophene compound TBP is shown as the following structural general formula I:
wherein R is1、R2、R3、R6、R7、R8、R9Are respectively selected from a group containing 1 to 9 halogen atoms or a group containing 1 to 9 carbon atoms, R4、R5Is an S or O atom. The thiophene compound TBP may be, for example, the following compounds 1 to 48:
preferably, the additive is a thiophene compound TBP containing silicon and boron, the weight percentage of the thiophene compound TBP is 0.5-5%, and the balance is electrolyte salt and organic solvent. Specifically, the TBP of the thiophene compound may be 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%. The specific occupation of the electrolyte salt and the organic solvent may be adjusted according to the actual circumstances and is not particularly limited in the present invention.
Preferably, the concentration of the electrolyte salt is 0.5mol/L to 1.5 mol/L. The electrolyte salt concentration is too low, the conductivity of the electrolyte is low, and the multiplying power and the cycle performance of the whole battery system can be influenced; the electrolyte salt concentration is too high, the viscosity of the electrolyte is too high, and the multiplying power of the whole battery system is also influenced. Specifically, the concentration of the electrolyte salt may be 0.5mol/L, 0.7mol/L, 0.9mol/L, 1.1mol/L, 1.3mol/L, 1.5 mol/L. More preferably, the concentration of the electrolyte salt is 0.8mol/L to 1.3 mol/L.
Preferably, the electrolyte lithium salt is selected from at least one of organic lithium salts or inorganic lithium salts.
More preferably, the electrolyte salt is at least one lithium salt selected from compounds containing a fluorine element and a lithium element.
More preferably, the electrolyte salt is selected from at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluoromethanesulfonyl, lithium difluoro (trifluoromethanesulfonyl) imide, and lithium tris (trifluoromethanesulfonyl) methide.
Preferably, the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, tetrahydrofuran.
Preferably, the additive comprises a thiophene compound, TBP, vinylene carbonate, vinyl sulfate, and 1, 3-propane sultone. The additive is compounded by adopting a thiophene compound TBP, vinylene carbonate, vinyl sulfate and 1, 3-propane sultone, and the effects of high-temperature performance, low-temperature performance and stability of the battery are better improved.
In the electrolyte, under the condition of a small addition amount of the thiophene compound TBP, the contained thiophene can generate polymerization reaction on the surface of the anode, so that the electrolyte is prevented from entering and reacting with materials, and the anode materials are protected. Meanwhile, boron atoms contained in the thiophene compound TBP can be reduced to form borate, the borate is one of effective components of a Solid Electrolyte Interface (SEI) film, the formed SEI film with excellent electrochemical stability and ionic conductivity can improve high-temperature performance and low-temperature performance. In addition, Si contained in the thiophene compound TBP can react with trace amount of water/hydrofluoric acid in the electrolyte to inhibit LiPF6And further of waterThe reaction reduces the content of hydrofluoric acid, improves the stability of the electrolyte, and has simple process, low cost and good protection effect.
The embodiment also discloses a battery comprising the electrolyte. The battery also comprises an isolating film among the positive pole, the negative pole and the positive and negative pole pieces.
The positive electrode comprises a positive electrode current collector and a positive electrode active slurry layer positioned on the positive electrode current collector, wherein the positive electrode active slurry layer comprises a positive electrode active material. The negative plate comprises a negative current collector and a negative active slurry layer positioned on the negative current collector, wherein the negative active slurry layer comprises a negative active material. The specific types of the positive electrode active material, the positive electrode binder and the negative electrode active material are not particularly limited and can be selected according to requirements.
Preferably, the positive active material is selected from lithium cobaltate (LiCoO)2) Lithium nickel manganese cobalt ternary material, lithium iron phosphate (LiFePO)4) Lithium manganate (LiMn)2O4) One or more of (a).
Preferably, the negative active material is graphite and/or silicon, such as natural graphite, artificial graphite, mesophase micro carbon spheres (MCMB), hard carbon, soft carbon, silicon-carbon composite, Li-Sn alloy, Li-Sn-O alloy, Sn, SnO2Spinel-structured lithiated TiO2-Li4Ti5O12And Li-Al alloy can be used as the negative active material.
The embodiment also discloses a preparation method of the battery, which comprises the following steps:
manufacturing a positive plate: the positive active material of the nickel-cobalt-manganese-oxygen ternary material NCM, the conductive agent CNT and the adhesive polyvinylidene fluoride are fully stirred and mixed in an N-methyl pyrrolidone solvent according to the weight ratio of 97:1.5:1.5 to form uniform positive slurry. And coating the slurry on an Al foil of a positive current collector, drying and cold pressing to obtain the positive plate.
And (3) manufacturing a negative plate:
the negative electrode active material graphite, the conductive agent acetylene black, the binder styrene butadiene rubber and the thickening agent sodium carboxymethyl cellulose are fully stirred and mixed in a proper amount of deionized water solvent according to the mass ratio of 95:2:2:1 to form uniform negative electrode slurry. And coating the slurry on a Cu foil of a negative current collector, drying and cold pressing to obtain a negative pole piece.
Preparing an electrolyte:
the preparation steps of the electrolyte are as follows: EC (ethylene carbonate)/DEC (diethyl carbonate)/PC (propylene carbonate) was mixed in accordance with 1: mixed at a mass ratio of 1:1 as an organic solvent. Adding additive thiophene compound TBP into organic solvent, uniformly mixing, adding LiPF6(lithium hexafluorophosphate) to obtain LiPF6The mixed solution with the concentration of 1.1mol/L is obtained to obtain the electrolyte of the invention.
Manufacturing the lithium ion battery:
the positive pole piece, the isolating membrane and the negative pole piece are sequentially stacked, so that the isolating membrane is positioned between the positive pole and the negative pole to play an isolating role. And then winding to obtain a naked electric core. And placing the bare cell in an outer packaging bag, injecting electrolyte into the dried battery, and performing vacuum packaging, standing, formation, shaping and other processes to complete the preparation of the lithium ion battery.
Test examples
In test examples 1 to 3, the electrolyte solutions of test examples 1 to 3 were obtained by changing the ratio of the thiophene compound TBP as the additive in the electrolyte solutions and the other components were the same. The following table 1 is specifically provided:
TABLE 1
The structural formula of TBP is as follows (i.e., Compound 45):
comparative example
Comparative example 1: the electrolyte was not supplemented with a thiophene compound TBP, and the remaining components were the same as in test examples 1 to 3, to obtain an electrolyte of comparative example 1.
Comparative example 2/3: the thiophene compound TBP in the electrolyte was replaced with Vinylene Carbonate (VC) and vinyl sulfate (DTD), respectively, and the remaining components were the same as in test examples 1 to 3, to obtain electrolytes of comparative examples 2 and 3. The following table 2 is specifically provided:
TABLE 2
Test results
The lithium ion batteries were prepared by injecting the batteries of test examples 1 to 3 and comparative examples 1 to 3 into the dried batteries, respectively, and then performing vacuum packaging, standing, formation, shaping, and the like, to obtain batteries in order.
1. High temperature cycling test of batteries
The test method comprises the following steps: and (3) placing the battery in an environment of 45 +/-2 ℃, and calculating the capacity retention rate of the battery after circulation according to the standard charge-discharge circulation, the circulation multiplying power of 1C and the charging voltage of 3.0-4.4V.
The calculation formula is as follows:
the nth cycle capacity retention (%) was (nth cycle discharge capacity)/(first cycle discharge capacity) × 100%
2. Low temperature testing of batteries
The test method comprises the following steps: and fully charging the divided battery cell at normal temperature, placing the fully charged battery in an environment of 0 ℃ for 4 hours, then discharging at a discharge capacity of 0.2C until the discharge capacity reaches 3.0V, and recording the capacity before and after low temperature.
The cell test conditions are as follows in table 3:
as can be seen from Table 3, VC, DTD and TBP all can improve high temperature performance, wherein the TBP improvement effect is the best. As can be seen from test examples 1 to 3, 0.5% TBP exhibited excellent performance even at a low temperature of 0 ℃. While comparative examples 1 and 2 show that VC deteriorates low temperature performance instead.
The foregoing is a more detailed description of the invention in connection with specific alternative embodiments, and the practice of the invention should not be construed as limited to those descriptions. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. An electrolyte, characterized by comprising an electrolyte salt, an organic solvent and an additive;
wherein the additive comprises at least a thiophene compound TBP containing silicon and boron; the thiophene compound TBP is represented by the following structural general formula I:
wherein R is1、R2、R3、R6、R7、R8、R9Are respectively selected from a group containing 1 to 9 halogen atoms or a group containing 1 to 9 carbon atoms, R4、R5Is an S or O atom.
2. The electrolyte according to claim 1, wherein the additive is a thiophene compound TBP containing silicon and boron, the thiophene compound TBP being 0.5 to 5% by mass, and the balance being an electrolyte salt and an organic solvent.
3. The electrolyte of claim 2, wherein the concentration of the electrolyte salt is 0.5mol/L to 1.5 mol/L.
4. The electrolyte of claim 3, wherein the concentration of the electrolyte salt is 0.8mol/L to 1.3 mol/L.
5. The electrolyte of claim 1, wherein the electrolyte salt is selected from at least one of an organic lithium salt or an inorganic lithium salt.
6. The electrolyte of claim 5, wherein the electrolyte salt is at least one lithium salt selected from compounds containing fluorine and lithium.
7. The electrolyte of claim 5, wherein the electrolyte salt is selected from at least one of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium trifluorosulfonyl, lithium difluoro (trifluoromethylsulfonyl) imide, and lithium tris (trifluoromethylsulfonyl) methide.
8. The electrolyte of claim 1, wherein the organic solvent is selected from at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, methyl formate, ethyl propionate, propyl propionate, methyl butyrate, and tetrahydrofuran.
9. The electrolyte of claim 1, wherein the additive comprises a thiophene compound, TBP, vinylene carbonate, vinyl sulfate, and 1, 3-propane sultone.
10. A battery comprising the electrolyte of any one of claims 1 to 9.
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