CN109786830B - Electrolyte containing silicon solvent and thiophene additive and lithium ion battery using electrolyte - Google Patents
Electrolyte containing silicon solvent and thiophene additive and lithium ion battery using electrolyte Download PDFInfo
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- CN109786830B CN109786830B CN201811584376.6A CN201811584376A CN109786830B CN 109786830 B CN109786830 B CN 109786830B CN 201811584376 A CN201811584376 A CN 201811584376A CN 109786830 B CN109786830 B CN 109786830B
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- carbonate
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- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000002904 solvent Substances 0.000 title claims abstract description 50
- 239000003792 electrolyte Substances 0.000 title claims abstract description 45
- 239000000654 additive Substances 0.000 title claims abstract description 37
- 230000000996 additive effect Effects 0.000 title claims abstract description 35
- 229930192474 thiophene Natural products 0.000 title claims abstract description 35
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 32
- 239000010703 silicon Substances 0.000 title claims abstract description 32
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000003960 organic solvent Substances 0.000 claims abstract description 38
- -1 thiophene compound Chemical class 0.000 claims abstract description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 150000001733 carboxylic acid esters Chemical class 0.000 claims abstract description 5
- 150000005678 chain carbonates Chemical class 0.000 claims abstract description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims abstract description 5
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- 239000008151 electrolyte solution Substances 0.000 claims description 18
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 16
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 14
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 14
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 14
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 8
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000005415 substituted alkoxy group Chemical group 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 claims description 3
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- 125000006727 (C1-C6) alkenyl group Chemical group 0.000 claims description 2
- 229910013188 LiBOB Inorganic materials 0.000 claims description 2
- 229910013406 LiN(SO2CF3)2 Inorganic materials 0.000 claims description 2
- 229910013426 LiN(SO2F)2 Inorganic materials 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 229910001540 lithium hexafluoroarsenate(V) Inorganic materials 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
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000006259 organic additive Substances 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 7
- 229910052744 lithium Inorganic materials 0.000 description 7
- 239000010408 film Substances 0.000 description 6
- 150000003577 thiophenes Chemical class 0.000 description 6
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- POFFJVRXOKDESI-UHFFFAOYSA-N 1,3,5,7-tetraoxa-4-silaspiro[3.3]heptane-2,6-dione Chemical compound O1C(=O)O[Si]21OC(=O)O2 POFFJVRXOKDESI-UHFFFAOYSA-N 0.000 description 1
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910001305 LiMPO4 Inorganic materials 0.000 description 1
- 229910013198 LiNiMn Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 229910012258 LiPO Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- VEWLDLAARDMXSB-UHFFFAOYSA-N ethenyl sulfate;hydron Chemical compound OS(=O)(=O)OC=C VEWLDLAARDMXSB-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005036 potential barrier Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte containing a silicon solvent and a thiophene additive and a lithium ion battery using the electrolyte. The electrolyte containing the silicon solvent and the thiophene additive comprises lithium salt, an organic solvent and the additive; the organic solvent comprises a silicon-substituted organic solvent, the additive comprises a thiophene compound, and the organic solvent further comprises one or more organic solvents selected from chain carbonates, cyclic carbonates and carboxylic esters. The high-voltage electrolyte of the lithium ion battery prepared by the invention has the advantages that the silicon-substituted solvent is matched with the thiophene compound, other organic solvents and additives are added, the proportion is reasonable, the conductivity of lithium ions in the electrolyte can be effectively improved, the impedance increase caused by film formation is inhibited, and the cycle performance and the low-temperature performance of the battery are effectively improved.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to an electrolyte containing a silicon solvent and a thiophene additive and a lithium ion battery using the electrolyte.
Background
Electronic equipment is developing towards miniaturization and lightness, and the electric motor car also needs higher continuation of the journey mileage, improves the energy density of battery, is the work key point of current battery enterprise and scientific research institution. The most common method for increasing the energy density of the battery is to increase the operating voltage of the battery, and various high-voltage positive electrode materials, such as spinel-structured LiNiMn, have been developed(2-x)O4And olivine-structured LiMPO4And the like. However, under high voltage, metal ions in a high oxidation state are easy to migrate to the negative electrode under the action of an electric field, electrons obtained at the negative electrode become metal to be precipitated, and therefore, the irreversible loss of the positive electrode material, the loss of the battery capacity and the reduction of the cycle life of the battery are caused. In addition, under the condition of high voltage, the active site on the surface of the anode has high oxidizability, so that the traditional carbonate electrolyte material is oxidized, decomposed and produced gas, and finally potential safety hazards are formed.
Disclosure of Invention
The silicon-substituted solvent has great development prospect as a novel lithium ion battery electrolyte solvent. The invention aims to overcome the defects of the background technology, and provides an electrolyte containing a silicon solvent and a thiophene additive and a lithium ion battery using the electrolyte.
In order to achieve the purpose of the invention, the electrolyte containing the silicon solvent and the thiophene additive comprises lithium salt, an organic solvent and the additive; wherein the organic solvent comprises a silicon-substituted organic solvent, and the additive comprises a thiophene compound.
Further, the organic solvent substituted by silicon of the invention is shown as formula (I) or formula (II):
in the formula (I), M1And M2Respectively represent an alkyl group containing 1 to 6 carbon atoms or a silane or siloxane containing 1 to 4 carbon atoms; wherein M is1Or M2At least one of which is a silane or siloxane having 1 to 4 carbon atoms;
in the formula (II), X1And X2Respectively represent an alkyl group containing 1 to 6 carbon atoms or a silane or siloxane containing 1 to 4 carbon atoms; wherein, X1Or X2At least one of which is a silane or siloxane having 1 to 4 carbon atoms.
Preferably, according to some embodiments of the invention, the compound of formula (I) includes, but is not limited to, the following compounds:
preferably, according to some embodiments of the invention, the compound of formula (II) includes, but is not limited to, the following compounds:
more preferably, the amount of the silylorganic solvent of formula (I) or formula (II) is from 2 to 50%, such as from 5 to 15%, and as a further example from 4 to 6% by weight of the solvent.
The silicon-substituted organic solvent has high oxidation resistance and chemical stability, can improve the high-temperature performance of a lithium battery, and is suitable for a high-voltage lithium battery system; and because the internal rotation potential barrier of the silicon-substituted back bond is reduced and the flexibility is increased, the viscosity of the original solvent is reduced, the shuttling capacity of lithium ions in the solvent is improved, and the low-temperature performance and the rate capability of the lithium battery can be improved to a greater extent.
Further, the thiophene compound is shown as a formula (III):
wherein R is1、R2、R3、R4Each independently represents a hydrogen atom, a halogen atom, an alkyl or substituted alkyl group having 1 to 6 carbon atoms, an alkoxy or substituted alkoxy group having 1 to 6 carbon atoms, the substituents in the substituted alkyl and substituted alkoxy groups being selected from the group consisting of halogen, phenyl, C1-C6Alkenyl or alkynyl.
Preferably, according to some embodiments of the invention, the compound of formula (III) includes, but is not limited to, the following compounds:
more preferably, the compound of formula (III) constitutes 0.5-15%, for example 1-2%, and as a further example 0.8-1.2% by mass of the electrolyte.
Furthermore, the organic solvent further comprises one or more organic solvents selected from chain carbonate organic solvents, cyclic carbonate organic solvents and carboxylic ester organic solvents.
Preferably, the chain carbonate-based organic solvent may be selected from one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), dipropyl carbonate (DPC); the cyclic carbonate organic solvent may be one or more selected from Ethylene Carbonate (EC), Vinylene Carbonate (VC), and Propylene Carbonate (PC); the carboxylic ester-based organic solvent may be one or more selected from Ethyl Acetate (EA), Ethyl Propionate (EP), Methyl Acetate (MA), propyl acetate (PE), Methyl Propionate (MP), Methyl Butyrate (MB), and Ethyl Butyrate (EB).
Preferably, the organic solvent comprises Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC), more preferably the Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) are mixed in a weight ratio of (20-30): (3-8): (45-55): (15-25), e.g. 25:5:50: 20.
Furthermore, the additive also comprises one or more additives of 1,3 propane sultone (1,3-PS), Vinylene Carbonate (VC), fluoroethylene carbonate (FEC), ethylene carbonate (VEC) and vinyl sulfate (DTD).
Preferably, the additive comprises 1,3 propane sultone (1,3-PS), Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC), and more preferably, the mass ratio of the 1,3 propane sultone (1,3-PS), Vinylene Carbonate (VC) and fluoroethylene carbonate (FEC) is (2-4): (0.5-1.5): (1-3), for example, 3:1: 2.
Preferably, the mass percentage of the additive in the electrolyte is 0.1-15%.
Further, the lithium salt may be selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2Preferably LiPF, preferably6And the concentration of the lithium salt in the electrolyte is 0.5-2M, preferably 1-1.5M, for example 1.1M, in terms of lithium ions.
The invention also provides a lithium ion battery, which uses the electrolyte containing the silicon solvent and the thiophene additive, and preferably, the preparation method of the lithium ion battery comprises the steps of injecting the high-voltage electrolyte for the lithium ion battery into a fully dried 4.4V lithium cobaltate/graphite soft package battery, and carrying out the working procedures of standing at 45 ℃, forming by a high-temperature clamp and carrying out secondary sealing.
The electrolyte containing the silicon solvent and the thiophene additive can effectively inhibit metal dissolution, reduce decomposition and gas generation of the electrolyte, protect the positive electrode, improve the high-temperature storage performance and the rate capability of the battery, reduce the increase of resistance and improve the low-temperature performance of the lithium ion battery. Compared with the traditional lithium ion secondary battery, the electrolyte contains the thiophene compound, so that a thin film can be formed on the surface of the anode to cover the active site of the anode, the aim of protecting the anode is fulfilled, and the anode is prevented from reacting with the electrolyte to generate gas; and because the novel silicon solvent used in the invention is matched with thiophene compounds by utilizing the silicon solvent, is supplemented with other organic solvents and additives, and is reasonably proportioned to prepare the high-voltage electrolyte of the lithium ion battery, the conductivity of lithium ions in the electrolyte can be effectively improved, the impedance increase caused by film formation is inhibited, and the cycle performance and the low-temperature performance of the battery are effectively improved.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
As used herein, the terms "comprises," "comprising," "includes," "including," "contains," "containing," or any other variation thereof, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when a range of "1 to 5" is disclosed, the described range should be interpreted to include the ranges "1 to 4", "1 to 3", "1 to 2 and 4 to 5", "1 to 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
The indefinite articles "a" and "an" preceding an element or component of the invention are not intended to limit the number requirement (i.e., the number of occurrences) of the element or component. Thus, "a" or "an" should be read to include one or at least one, and the singular form of an element or component also includes the plural unless the number clearly indicates the singular.
Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
Comparative example 1
The electrolyte is prepared by the following method: in a glove box, Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) were mixed in a weight ratio of 25:5:50:20, and then lithium hexafluorophosphate was added to dissolve them, to prepare an electrolyte solution having a lithium hexafluorophosphate concentration of 1M. Then, 0.5% by mass of Vinylene Carbonate (VC), 1% by mass of fluoroethylene carbonate (FEC), and 1.5% by mass of 1,3 propane sulfonic acid lactone (1,3-PS) were added to the electrolyte.
And injecting the prepared high-voltage electrolyte for the lithium ion battery into the fully dried 4.4V lithium cobaltate/graphite soft package battery, and carrying out battery performance test after the procedures of standing at 45 ℃, high-temperature clamp formation, secondary sealing and the like to obtain the battery used in the comparative example 1.
Example 1
The electrolyte is prepared by the following method: mixing Ethylene Carbonate (EC), Propylene Carbonate (PC), Ethyl Methyl Carbonate (EMC) and diethyl carbonate (DEC) in a weight ratio of 25:5:50:20 in a glove box, and adding a 5% by mass of a silico-organic solvent (1) to the mixed solvent; adding lithium hexafluorophosphate for dissolution to prepare an electrolyte solution with the concentration of lithium hexafluorophosphate being 1M. Then, 0.5% by mass of Vinylene Carbonate (VC), 1% by mass of fluoroethylene carbonate (FEC), 1.5% by mass of 1,3 propane sulfonic acid lactone (1,3-PS), and 1% by mass of a thiophene compound (5) were added to the electrolyte.
The prepared high-voltage electrolyte for the lithium ion battery was injected into a fully dried 4.4V lithium cobaltate/graphite pouch battery, and after the procedures of standing at 45 ℃, high-temperature jig formation, secondary sealing and the like, a battery performance test was performed to obtain the battery used in example 1.
In the present invention, the preparation methods of the electrolyte and the battery preparation method in other comparative examples and examples are as shown in table 1 with reference to comparative example 1 and example 1.
TABLE 1 electrolyte formulations for the examples and comparative examples
Lithium ion battery performance testing
1. High temperature cycle performance
Under the condition of high temperature (45 ℃), the lithium ion battery is charged to 4.4V under the constant current and the constant voltage of 1C, and then is discharged to 3.0V under the constant current of 1C. After 500 cycles of charge and discharge, capacity retention rate after 500 cycles was calculated:
2. high temperature storage Properties
The lithium ion battery was subjected to primary 1C/1C charging and discharging (discharge capacity is designated DC) at room temperature (25 ℃ C.)0) Then charging the battery to 4.4V under the condition of 1C constant current and constant voltage; the lithium ion battery is stored in a high-temperature box at 60 ℃ for 7 days, and after being taken out, 1C discharge (the discharge capacity is recorded as DC) is carried out at normal temperature1) (ii) a Then, 1C/1C charging and discharging (discharge capacity is designated as DC) were carried out under ambient conditions2) Calculating the capacity retention rate and the capacity recovery rate of the lithium ion battery by using the following formulas:
3. low temperature cycle performance
Under the condition of low temperature (10 ℃), the lithium ion battery is charged to 4.4V under the constant current and the constant voltage of 1C, and then is discharged to 3.0V under the constant current of 1C. After 100 cycles of charge and discharge, the capacity retention rate after the 100 th cycle was calculated as:
the cell performance results for each of the above specific examples are shown in table 2.
Table 2 results of cell performance test of each example and comparative example
As can be seen from the data in the above table, in comparative example 1, the high voltage 4.4VLiCoO was applied2When the AG soft package battery is used, 0.5 percent of ethylene carbonate is addedAlkenyl ester (VC), 1% fluoroethylene carbonate (FEC), 1.5% 1,3 propane sultone (1,3-PS) and 1% lithium difluorophosphate (LiPO)2F2) And then, the VC is not high-temperature resistant and is easy to decompose at a high temperature because the film is mainly formed on the cathode of the VC, but the VC can be polymerized on the surface of the anode to form a film, but has poor thermal stability, and meanwhile, the VC has a low oxidation potential and is easy to oxidize and decompose at a high potential, so that the high-temperature cycle performance of the battery is poor, the high-temperature storage performance is general, the battery can generate gas to a certain extent to cause the expansion of the battery, and the cycle performance of the battery under the low-temperature condition is also general.
After the novel silicon-substituted solvent with the content of 5% is added into the electrolyte (comparative examples 2, 3, 4 and 5), the high-temperature cycle performance of the battery is improved to a certain extent on the whole; the oxidation resistance and the high-temperature resistance of the silicon solvent are improved, so that the high-temperature storage performance of the battery is improved to a certain extent; due to the excellent fluidity and low viscosity of the silicon-substituted solvent, the impedance of the battery is reduced, so that the low-temperature cycle performance of the battery is greatly improved, and particularly the compound (1) and the compound (3) have more obvious improvement effect.
After the thiophene compounds with the content of 1 percent (comparative examples 6 and 8) are independently added without adding a silicon-substituted solvent, the discovery that the high-temperature cycle performance and the high-temperature storage performance of the battery are greatly improved because the thiophene compounds can form a film on the surface of the positive electrode and protect the active sites of the positive electrode, but the low-temperature cycle effect is poor because the impedance is increased after the film is formed; especially when the amount of the thiophenic compound was increased to 2% (comparative examples 7 and 9), the low-temperature cycle performance of the battery was suddenly lowered due to excessive film formation resistance.
The high-voltage electrolyte disclosed by the invention is prepared by combining the novel silicon-substituted solvent disclosed by the invention with thiophene compounds, preferably selecting four novel silicon-substituted solvents, namely a compound (1), a compound (2), a compound (3) and a compound (4), wherein the addition amounts of the four novel silicon-substituted solvents are respectively 5% and 15% of the total mass of the solvent, adjusting two thiophene compounds, namely a compound (5) and a compound (6), are respectively 1% and 2% of the total mass of the electrolyte, adding other organic solvents and additives disclosed by the invention, and reasonably mixing and collocating the two thiophene compounds, so that 32 high-voltage electrolytes are prepared to serve as an exemplary embodiment for experiment. By analyzing the experimental data of the examples and comparing with the comparative examples, the following conclusions can be drawn:
in general, the novel silicon-substituted solvent (the addition amount is 2-50% of the mass of the solvent, preferably 5-15%, more preferably 5%) is matched with the thiophene compound (the addition amount is 0.5-15% of the mass of the electrolyte, preferably 1-2%, more preferably 1%) for use, so that the high-temperature cycle and high-temperature storage performance of the battery can be remarkably improved on the basis of ensuring the low-temperature cycle performance of the battery;
the organic silicon carbonate solvent shown in the formula (I) is more excellent in the aspects of improving the high-temperature cycle performance and the high-temperature storage performance of the high-voltage lithium battery, can also well improve the low-temperature cycle performance of the battery, and has better comprehensive performance;
the viscosity of the organic silicon carboxylic ester solvent shown in the formula (II) is lower, the performance of the battery is greatly improved by adding 5 percent of the organic silicon carboxylic ester solvent, particularly the low-temperature performance is greatly improved, but the high-temperature cycle performance of the battery is deteriorated after adding too much, namely 15 percent of the organic silicon carboxylic ester solvent;
and fourthly, although certain performances of the battery are better when the novel silicon-substituted solvent or the thiophene compound is singly used, the novel silicon-substituted solvent and the thiophene compound are mixed and used, and other organic solvents and additives are added, so that the reasonable proportion is realized, and the performances of the high-voltage battery are improved to a certain extent.
It will be readily understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention, and any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (17)
1. An electrolyte containing a silicon solvent and a thiophene additive, wherein the electrolyte comprises a lithium salt, an organic solvent and an additive, and is characterized in that the organic solvent comprises a substituted organic solvent, the additive comprises a thiophene compound, and the substituted organic solvent is selected from one of the following compounds:
the thiophene compound is shown as a formula (III):
wherein R is1、R2、R3、R4Each independently represents a hydrogen atom, a halogen atom, an alkyl or substituted alkyl group having 1 to 6 carbon atoms, an alkoxy or substituted alkoxy group having 1 to 6 carbon atoms, the substituents in the substituted alkyl and substituted alkoxy groups being selected from the group consisting of halogen, phenyl, C1-C6Alkenyl or alkynyl; the organic solvent with silicon substituted accounts for 5-15% of the solvent.
2. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 1, wherein the compound represented by formula (III) is selected from one of the following compounds:
3. the electrolyte solution containing the silicon solvent and the thiophene additive according to claim 1, wherein the compound represented by the formula (III) accounts for 1-2% by mass of the electrolyte solution.
4. The electrolyte solution containing the silicon solvent and the thiophene additive according to claim 1, wherein the organic solvent further comprises one or more organic solvents selected from a chain carbonate organic solvent, a cyclic carbonate organic solvent, and a carboxylic ester organic solvent.
5. The electrolyte solution containing the silicon solvent and the thiophene additive according to claim 4, wherein the chain carbonate organic solvent is selected from one or more of dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and dipropyl carbonate; the cyclic carbonate organic solvent is selected from one or more of ethylene carbonate, vinylene carbonate and propylene carbonate; the carboxylic ester organic solvent is selected from one or more of ethyl acetate, ethyl propionate, methyl acetate, propyl acetate, methyl propionate, methyl butyrate and ethyl butyrate.
6. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 5, wherein the organic solvent comprises ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate.
7. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 6, wherein the ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate are mixed in a weight ratio of (20-30): (3-8): (45-55): (15-25).
8. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 7, wherein the ethylene carbonate, propylene carbonate, ethyl methyl carbonate, and diethyl carbonate are mixed in a weight ratio of 25:5:50: 20.
9. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 1, wherein said additive further comprises one or more additives selected from 1,3 propane sultone, vinylene carbonate, fluoroethylene carbonate, ethylene carbonate, and ethylene sulfate.
10. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 9, wherein said additive comprises 1,3 propane sultone, vinylene carbonate, and fluoroethylene carbonate.
11. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 10, wherein the mass ratio of the 1,3 propane sultone, vinylene carbonate and fluoroethylene carbonate is (2-4): (0.5-1.5): (1-3).
12. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 11, wherein the mass ratio of 1,3 propane sultone, vinylene carbonate, and fluoroethylene carbonate is 3:1: 2.
13. The electrolyte of claim 1, wherein the lithium salt is selected from LiPF6、LiBF4、LiClO4、LiBOB、LiODFB、LiAsF6、LiN(SO2CF3)2、LiN(SO2F)2One or more of (a).
14. The electrolyte of claim 13, wherein the lithium salt is LiPF6And the concentration of the lithium salt in the electrolyte is 0.5 to 2M in terms of lithium ions.
15. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 1, wherein the concentration of said lithium salt in the electrolyte solution is 1-1.5M in terms of lithium ions.
16. The electrolyte solution containing a silicon solvent and a thiophene additive according to claim 1, wherein the concentration of said lithium salt in the electrolyte solution is 1.1M in terms of lithium ions.
17. A lithium ion battery using the electrolyte containing the silicon solvent and the thiophene-based additive according to any one of claims 1 to 16.
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