CN111883845A - Electrolyte for lithium battery, lithium battery and application of bisborate solvent - Google Patents
Electrolyte for lithium battery, lithium battery and application of bisborate solvent Download PDFInfo
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- CN111883845A CN111883845A CN202010881154.1A CN202010881154A CN111883845A CN 111883845 A CN111883845 A CN 111883845A CN 202010881154 A CN202010881154 A CN 202010881154A CN 111883845 A CN111883845 A CN 111883845A
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- electrolyte
- lithium
- lithium battery
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- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 56
- 239000002904 solvent Substances 0.000 title claims abstract description 38
- 239000000654 additive Substances 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 229910003002 lithium salt Inorganic materials 0.000 claims description 9
- 159000000002 lithium salts Chemical class 0.000 claims description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- NUKZAGXMHTUAFE-UHFFFAOYSA-N methyl hexanoate Chemical compound CCCCCC(=O)OC NUKZAGXMHTUAFE-UHFFFAOYSA-N 0.000 claims description 6
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-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 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000004450 alkenylene group Chemical group 0.000 claims description 4
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims description 4
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 claims description 4
- 125000006832 (C1-C10) alkylene group Chemical group 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- SJHAYVFVKRXMKG-UHFFFAOYSA-N 4-methyl-1,3,2-dioxathiolane 2-oxide Chemical compound CC1COS(=O)O1 SJHAYVFVKRXMKG-UHFFFAOYSA-N 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-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
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-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
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 3
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 claims description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- NLDYACGHTUPAQU-UHFFFAOYSA-N tetracyanoethylene Chemical group N#CC(C#N)=C(C#N)C#N NLDYACGHTUPAQU-UHFFFAOYSA-N 0.000 claims description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims 1
- 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 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000013538 functional additive Substances 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- 125000002619 bicyclic group Chemical group 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 150000005676 cyclic carbonates Chemical class 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910013075 LiBF Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000077 silane Inorganic materials 0.000 description 2
- GEWWCWZGHNIUBW-UHFFFAOYSA-N 1-(4-nitrophenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C([N+]([O-])=O)C=C1 GEWWCWZGHNIUBW-UHFFFAOYSA-N 0.000 description 1
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000005910 alkyl carbonate group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- RBBXSUBZFUWCAV-UHFFFAOYSA-N ethenyl hydrogen sulfite Chemical compound OS(=O)OC=C RBBXSUBZFUWCAV-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 239000011255 nonaqueous electrolyte Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000006467 substitution reaction 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0037—Mixture of solvents
-
- 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 relates to an electrolyte for a lithium battery, the lithium battery and application of a bisborate solvent. The electrolyte has a wider liquid range, simultaneously considers the high-low temperature performance and the safety performance of the battery, and the prepared lithium battery has excellent cycle life, improves the high-temperature gas production of the battery and the increase of direct-current internal resistance in the cycle process, and improves the safety and the reliability of the battery.
Description
Technical Field
The invention relates to the technical field of lithium batteries, in particular to an electrolyte for a lithium battery and application of the lithium battery and a bisborate solvent.
Background
The modern society has increasingly urgent need for high-energy power sources due to the development of mobile communication, digital products, electric tools and electric vehicles. Lithium ion batteries are widely researched as a chemical energy storage system with high energy density, excellent cycle performance and environmental friendliness, and the electrolyte plays a significant role in exerting the application range, safety performance and capacity of the batteries as a bridge for connecting the positive electrode and the negative electrode of the lithium batteries.
The ideal electrolyte should have several characteristics: high ionic conductivity, stability in a wide temperature range, low electronic conductivity, good chemical stability, low cost, nonflammability, good safety, no toxicity, no pollution and the like. The currently commonly used carbonate electrolyte can be oxidized and decomposed when the charge cut-off voltage exceeds 4.2V, so that the battery expands and the internal resistance rises, and the comprehensive performance of the whole battery is reduced. In addition, most of conventional electrolyte solvents are alkyl carbonate compounds, and the flash point of the electrolyte solvents is low, so that the safety and reliability of the electrolyte solvents cannot completely meet the use conditions.
CN111261924A provides an electrolyte for a lithium battery, including lithium salt, organic solvent and functional additive, the functional additive includes a first additive accounting for 0.1% -10% of the total mass of the lithium battery electrolyte, a second additive accounting for 0.1% -2% of the total mass of the lithium battery electrolyte and a third additive accounting for 0.1% -3% of the total mass of the lithium battery electrolyte, the first additive is fluorinated cyclic carbonate and/or fluorinated ether, the second additive is a silane compound, and the third additive is a nitrile compound. In the lithium ion battery with the high-nickel anode material matched with the silicon cathode, the coordination of the fluorinated cyclic carbonate, the fluoroether, the silane and the nitrile in the non-aqueous electrolyte improves the initial capacity, inhibits the increase of internal resistance, and improves the normal-temperature cycle performance and the high-temperature gas expansion. However, the electrolyte of the present invention has a relatively low battery capacity percentage at 25 ℃.
CN103943883A discloses an application of a borate compound as an additive of a high-voltage lithium ion battery electrolyte, and the invention discloses a high-voltage lithium ion battery electrolyte which is obtained by adding a functional additive with the mass equivalent to 0.1-5% of that of a common electrolyte into the common electrolyte. The common electrolyte consists of a cyclic carbonate solvent, a linear carbonate solvent and a conductive lithium salt, and the functional additive is the borate compound. The addition of the additive optimizes the interface of the positive electrode/electrolyte, reduces the surface activity of the positive electrode and inhibits the oxidative decomposition of the electrolyte; on the other hand, the safety of the electrolyte is also improved due to the introduction of boron. The high-voltage lithium ion battery electrolyte can improve the safety performance and the cycle performance of a high-voltage (3-4.9 Vvs. Li/Li +) lithium battery. However, boron element is present as an additive in the electrolyte, and there is a limit to improvement of safety.
In conclusion, it is necessary to develop an electrolyte which has both high and low temperature performance and safety performance.
Disclosure of Invention
The invention provides an electrolyte for a lithium battery, the lithium battery and an application of a bisborate solvent, wherein the electrolyte has a wider liquid range and simultaneously gives consideration to the high-low temperature performance and the safety performance of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
an object of the present invention is to provide an electrolyte for a lithium battery, which contains a lithium salt and a solvent, the solvent including a compound represented by formula a:
in the formula A, R is1、R2And R3Each independently selected from C1-C10 (e.g., C1, C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkylene or C2-C10 (e.g., C2, C3, C4, C5, C6, C7, C8, C9, etc.) alkenylene.
The solvent shown in formula A is added into the electrolyte, and the solvent is a borate compound with a bicyclic structure. The boric acid ester compound with a bicyclic structure has a higher boiling point than that of the conventional carbonic ester>160 ℃ and lower melting point: (<-40 ℃) and exhibits good chemical stability to the decomposition of the positive electrode and, at room temperature, a strong electrical conductivity (10 ℃)-3~10-2S/cm). Oxidation potential of the electrolyte when mixed with a portion of the carbonate (e.g., ethylene carbonate)>5.8V(vsLi/Li+). Therefore, the liquid process of the solvent A is wider, and the high-temperature and low-temperature performance of the lithium battery is promoted; secondly, the solvent has better stability in a high-voltage system, and the safety and reliability of the lithium battery are improved; meanwhile, compared with other solvents, the solvent is low in viscosity and good in fluidity, pole pieces and diaphragms are easy to infiltrate, the alternating current internal resistance and the direct current internal resistance of the lithium battery are reduced, and the power performance and the cycle performance of the battery are improved.
Preferably, said R is1、R2And R3Each independently selected from-CH2-、-CH=CH-、-CH2CH2-、-CH(CH3)-、-CH2CH2CH2-、-C(CH3)2-or-C (═ CH)2) Any one of the above-mentioned. The short straight lines at both ends of the aforementioned group represent the connecting bonds.
Preferably, the solvent comprises any one or a combination of at least two of the compounds represented by formula a1 to formula A3:
the three compounds with specific structures are preferably used as solvents, and the compounds are all boric acid ester compounds with bicyclic structures, so that the high-low temperature performance, the stability and the cycle life of the lithium battery can be further improved.
Preferably, the solvent further includes any one or at least two combinations of Ethylene Carbonate (EC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dimethyl carbonate (DMC), Propylene Carbonate (PC), dipropyl carbonate (DPC), γ -butyrolactone (GBL), 1, 3-Dioxolane (DOL), dimethyl ether (DME), methyl hexanoate (MA), Methyl Propionate (MP), dimethyl sulfone, diethyl sulfone, and Tetrahydrofuran (THF).
Preferably, the solvent accounts for 60 wt% to 92 wt% of the total mass of the electrolyte, such as 62 wt%, 64 wt%, 66 wt%, 68 wt%, 70 wt%, 72 wt%, 74 wt%, 76 wt%, 78 wt%, 80 wt%, 82 wt%, 84 wt%, 86 wt%, 88 wt%, 90 wt%, etc.
Preferably, the compound represented by formula A accounts for 2 wt% to 65 wt%, such as 5 wt%, 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt%, 40 wt%, 45 wt%, 50 wt%, 55 wt%, 60 wt%, etc., of the total mass of the electrolyte.
The addition amount of the solvent of formula A is preferably 2-65 wt%, and in the range, the optimal high and low temperature performance, stability and cycle life can be obtained. The addition amount is too low, so that the liquid process of an electrolyte system can not meet the use condition, and the advantage of the solvent can not be exerted; when the amount of the additive is too high, the lithium salt concentration is insufficient, and the ionic conductivity and conductivity of the electrolyte are reduced, which deteriorates the performance of the lithium battery.
Preferably, the first and second electrodes are formed of a metal,the lithium salt includes lithium hexafluorophosphate (LiPF)6) Lithium hexafluoroarsenate (LiAsF)6) Lithium perchlorate (LiClO)4) Lithium bis (trifluoromethanesulfonate imide) (LiN (SO)2CF3)2) Lithium trifluoromethanesulfonate (LiCF)3SO3) Lithium tetrafluoroborate (LiBF)4) Lithium bis (fluorooxalato) borate (LiBF)2C2O4) Lithium bis (oxalato) borate (LiB (C)2O4)2) Or lithium bis (fluorosulfonylimide) (LiN (SO)2F)2Any one or a combination of at least two of them.
Preferably, the lithium salt accounts for 5 wt% to 30 wt%, such as 10 wt%, 15 wt%, 20 wt%, 25 wt%, etc., of the total mass of the electrolyte.
Preferably, the electrolyte further comprises an additive.
Preferably, the additive includes lithium fluoride (LiF), Fluorinated Ethylene Carbonate (FEC), Vinylene Carbonate (VC), Propylene Sulfite (PS), 1, 4-Butanesultone (BS), 1,3- (1-Propene) Sultone (PST), vinyl sulfite (ES), ethylene sulfate (DTD), ethylene sulfite, Biphenyl (BP), Cyclohexylbenzene (CHP), tetracyanoethylene, sulfur dioxide (SO)2) Carbon disulfide (CS)2) Boron trioxide (B)2O3) Any one or at least two of trimethyl phosphate (TMP) and triethyl phosphate (TEP).
Preferably, the additive comprises 0.5 wt% to 10 wt% of the total mass of the electrolyte, such as 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%, 6 wt%, 7.5 wt%, 8 wt%, 8.5 wt%, 9 wt%, 9.5 wt%, etc.
The second object of the present invention is to provide a lithium battery comprising a positive electrode, a negative electrode, a separator, a structural member and the electrolyte for a lithium battery according to the first object.
The lithium battery provided by the invention has excellent cycle life, improves the high-temperature gas production of the battery and the increase of direct-current internal resistance in the cycle process, and improves the safety and reliability of the battery.
The invention also aims to provide an application of a bisborate solvent in a battery electrolyte, wherein the bisborate solvent comprises a compound shown as a formula A;
in the formula A, R is1、R2And R3Each independently selected from C1 to C10 alkylene or C2 to C10 alkenylene. That is, the compound represented by a provided by the present application is not limited to be used in lithium battery electrolytes, but may also have potential to be used in non-lithium battery electrolytes. It should be noted that the solvent of the bisborate ester is only a transitional word, and the nature thereof is also the compound shown in the formula A. The specific form of the compound shown in the formula a is suitable for the content described in one of the purposes, and is not described herein again.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, a new solvent A is added into the lithium battery electrolyte, and the solvent A has a wider liquid process, so that the high-temperature and low-temperature performance of the lithium battery can be improved; secondly, the solvent has better stability in a high-voltage system, and the safety and reliability of the lithium battery are improved; meanwhile, compared with other solvents, the solvent is low in viscosity and good in fluidity, pole pieces and diaphragms are easy to infiltrate, the alternating current internal resistance and the direct current internal resistance of the lithium battery are reduced, and the power performance and the cycle performance of the battery are improved.
The lithium battery prepared by the electrolyte has high-low temperature capacity retention rate and overcharge failure voltage, excellent thermal shock resistance and high safety, wherein the high-temperature (45 ℃) capacity retention rate is 97-104%, most of the capacity retention rate is more than 100%, the low-temperature (-20 ℃) capacity retention rate is 86-93%, most of the capacity retention rate is more than 90%, the overshoot failure voltage is 5.0-5.9V, most of the overshoot failure voltage is more than 5.5V, and the lithium battery does not open a valve, does not ignite and does not explode under the condition of 30min at 130 ℃.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The following examples and comparative examples each provide a lithium battery whose electrolyte composition is specified in table 1, and information on the compositions of the positive electrode, the negative electrode, and the separator is specified in table 2.
TABLE 1
In table 1, the percentages represent the percentages of the respective components in the total mass of the electrolyte;
in table 1, the structure of D1 is as follows:
TABLE 2
In the anode formula, the numbers represent the mass ratio of different anode materials, and the anode formula is the same.
The materials and sources for the english abbreviations referred to in table 2 are shown in table 3:
TABLE 3
Performance testing
For the lithium batteries of the above examples and comparative examples, the following performance tests were performed:
(1) high and low temperature capacity retention rate test: the test is carried out according to GB/T31486-2015, and the low-temperature capacity retention rate is not lower than 70% of the initial capacity; the high-temperature capacity retention ratio is not less than 90% of the initial capacity.
(2) And (3) testing the overshoot failure voltage: the test was carried out with reference to GB 38031-2020.
(3) And (3) thermal shock test: the test was carried out with reference to GB 38031-2020.
The above test results are shown in table 4:
TABLE 4
As can be seen from Table 1, the lithium battery prepared by the electrolyte has high and low temperature retention rate and overshoot failure voltage, and has excellent thermal shock performance and high safety, wherein the high temperature (45 ℃) capacity retention rate is 97-104%, most of the capacity retention rate is more than 100%, the low temperature (-20 ℃) capacity retention rate is 86-93%, most of the capacity retention rate is more than 90%, the overshoot failure voltage is 5.0-5.9V, most of the capacity retention rate is more than 5.5V, and the lithium battery does not open a valve, does not ignite and does not explode under the condition of 30min at 130 ℃.
It is understood from comparative examples 1 and 6 to 9 that when the ratio of the solvent of the formula A is in the range of 2 wt% to 65 wt% (examples 1 and 6 to 7), the high/low temperature capacity retention ratio and the overshoot failure voltage can be further improved, and that the effect is deteriorated when the ratio is too low or too high.
The present invention is illustrated in detail by the examples described above, but the present invention is not limited to the details described above, i.e., it is not intended that the present invention be implemented by relying on the details described above. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
2. The electrolyte for lithium battery according to claim 1, wherein R is1、R2And R3Each independently selected from-CH2-、-CH=CH-、-CH2CH2-、-CH(CH3)-、-CH2CH2CH2-、-C(CH3)2-or-C (═ CH)2) Any one of the above-mentioned.
4. the electrolyte for a lithium battery according to any one of claims 1 to 3, wherein the solvent further comprises any one or a combination of at least two of ethylene carbonate, diethyl carbonate, ethyl methyl carbonate, dimethyl carbonate, propylene carbonate, dipropyl carbonate, γ -butyrolactone, 1, 3-dioxolane, dimethyl ether, methyl hexanoate, methyl propionate, dimethyl sulfone, diethyl sulfone, or tetrahydrofuran.
5. The electrolyte for a lithium battery according to any one of claims 1 to 4, wherein the solvent accounts for 60 to 92 wt% of the total mass of the electrolyte;
preferably, the compound shown in the formula A accounts for 2-65 wt% of the total mass of the electrolyte.
6. The electrolyte for a lithium battery according to any one of claims 1 to 5, wherein the lithium salt comprises any one or a combination of at least two of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium perchlorate, lithium bis (trifluoromethylsulfonyl) imide, lithium trifluoromethylsulfonate, lithium tetrafluoroborate, lithium difluorooxalato borate, lithium dioxaoxalato borate, or lithium difluorosulfonylimide.
7. The electrolyte for a lithium battery according to any one of claims 1 to 6, wherein the lithium salt accounts for 5 to 30 wt% of the total mass of the electrolyte.
8. The electrolyte for a lithium battery according to any one of claims 1 to 7, further comprising an additive;
preferably, the additive comprises any one or at least two of lithium fluoride, fluorinated ethylene carbonate, vinylene carbonate, propylene sulfite, 1, 4-butanesultone, 1,3- (1-propylene) sultone, ethylene sulfite, ethylene sulfate, ethylene sulfite, biphenyl, cyclohexylbenzene, tetracyanoethylene, sulfur dioxide, carbon disulfide, diboron trioxide, trimethyl phosphate or triethyl phosphate;
preferably, the additive accounts for 0.5 wt% -10 wt% of the total mass of the electrolyte.
9. A lithium battery comprising a positive electrode, a negative electrode, a separator, a structural member, and the electrolyte for a lithium battery as claimed in any one of claims 1 to 8.
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WO1997016862A1 (en) * | 1995-11-03 | 1997-05-09 | Arizona Board Of Regents | Wide electrochemical window solvents for use in electrochemical devices and electrolyte solutions incorporating such solvents |
JPH113728A (en) * | 1997-04-17 | 1999-01-06 | Fuji Photo Film Co Ltd | Nonaqueous electrolyte secondary battery |
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