CN114335720A - Electrolyte additive, electrolyte and sodium ion battery comprising electrolyte - Google Patents
Electrolyte additive, electrolyte and sodium ion battery comprising electrolyte Download PDFInfo
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- CN114335720A CN114335720A CN202111461688.XA CN202111461688A CN114335720A CN 114335720 A CN114335720 A CN 114335720A CN 202111461688 A CN202111461688 A CN 202111461688A CN 114335720 A CN114335720 A CN 114335720A
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- Prior art keywords
- electrolyte
- additive
- compound
- carbonate
- organic solvent
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 39
- 239000002000 Electrolyte additive Substances 0.000 title claims abstract description 25
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 22
- 150000001875 compounds Chemical class 0.000 claims abstract description 60
- 239000000654 additive Substances 0.000 claims abstract description 49
- 230000000996 additive effect Effects 0.000 claims abstract description 49
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 12
- 125000005843 halogen group Chemical group 0.000 claims abstract description 10
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000004417 unsaturated alkyl group Chemical group 0.000 claims abstract description 6
- 125000002252 acyl group Chemical group 0.000 claims abstract description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 3
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 239000003960 organic solvent Substances 0.000 claims description 22
- -1 propenyl sultone Chemical class 0.000 claims description 13
- 239000011734 sodium Substances 0.000 claims description 9
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 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 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 125000001589 carboacyl group Chemical group 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 229910019398 NaPF6 Inorganic materials 0.000 description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 239000007774 positive electrode material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000006245 Carbon black Super-P Substances 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910020650 Na3V2 Inorganic materials 0.000 description 1
- 229910001373 Na3V2(PO4)2F3 Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 206010016766 flatulence Diseases 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229960003351 prussian blue Drugs 0.000 description 1
- 239000013225 prussian blue Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an electrolyte additive, electrolyte and a sodium ion battery comprising the electrolyte, wherein the electrolyte additive comprises an additive a and an additive b, and the additive a comprises one or more of a first compound shown as a formula I and a second compound shown as a formula II; wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are respectively and independently selected from one of hydrogen, halogen atoms, alkyl or alkoxy groups with 1-10 carbon atoms, and alkanoyl or unsaturated alkyl groups with 2-10 carbon atoms, and H in the alkyl, unsaturated alkyl, alkoxy and alkanoyl groups can be partially or completely substituted by one or more of halogen atoms, cyano groups, carboxyl groups and sulfonic groups. The electrolyte additive is beneficial to improving the cycle performance and improving the high and low temperature capacity retention rate, the capacity recovery rate and the thickness expansion rate.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to an electrolyte additive, an electrolyte and a sodium ion battery comprising the electrolyte.
Background
Sodium is one of the elements with abundant reserves on the earth, has a working principle similar to that of a lithium ion battery, has the advantages of low cost, good safety, long-term large-scale storage and the like, and is more and more concerned by research and development personnel. However, the sodium ion battery has the defects of poor cycle performance, high-temperature storage and inflation, low first efficiency and the like, and the wide application of the sodium ion battery is restricted.
The electrolyte is one of the key materials of the sodium ion power battery, and has significant influence on the cycle, high-temperature and low-temperature performance and the like of the battery. In the three major components of the electrolyte, the formula of the lithium salt and the solvent is not changed greatly, and the additive is a key factor for improving the performance of the sodium-ion battery, so that the development of the additive and the electrolyte meeting the performance of the sodium-ion battery has important significance.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the electrolyte additive is provided, so that the circulation performance of the electrolyte is effectively improved, and the high-low temperature capacity retention rate, the capacity recovery rate and the thickness expansion rate are improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrolyte additive comprises an additive a and an additive b, wherein the additive a comprises one or more of a first compound shown as a formula I and a second compound shown as a formula II;
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are respectively and independently selected from any one of hydrogen, a halogen atom, an alkyl group with 1-10 carbon atoms, an unsaturated alkyl group with 2-10 carbon atoms, an alkoxy group with 1-10 carbon atoms or an alkanoyl group with 2-10 carbon atoms, and H in the alkyl group, the unsaturated alkyl group, the alkoxy group and the alkanoyl group can be partially or completely substituted by one or more of a halogen atom, a cyano group, a carboxyl group and a sulfonic group; wherein the additive b is one or more of ethylene carbonate, fluoroethylene carbonate, ethylene carbonate, ethylene sulfate and propenyl sultone.
Preferably, in the first compound shown in the formula I, R1, R2 and R3 are halogen atoms, in the second compound shown in the formula II, R4, R5 and R6 are halogen atoms, and R7, R8 and R9 are alkyl groups with 1-10 carbon atoms.
Preferably, in the first compound, R1, R2 and R3 are fluorine, and in the second compound, R4, R5 and R6 are fluorine, and R7, R8 and R9 are methyl.
Preferably, the mass ratio of the additive a to the additive b is (1-5) to (1-5). The mass ratio of the additive a to the additive b is 1:1, 1:2, 1:3, 1:4, 1:5, 2:1, 3:1, 4:1 and 5: 1.
Preferably, the additive a is the first compound and the second compound, the mass ratio of the first compound to the second compound is 2:1, and the additive b is fluoroethylene carbonate.
The second purpose of the invention is: aiming at the defects of the prior art, the electrolyte is provided, and has excellent cycle performance and high and low temperature performance.
In order to achieve the purpose, the invention adopts the following technical scheme:
an electrolyte comprises a sodium salt electrolyte, an organic solvent and the electrolyte additive.
Preferably, the electrolyte additive accounts for 2-10% of the total mass of the electrolyte. The electrolyte additive accounts for 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% and 10% of the total mass of the electrolyte.
Preferably, the organic solvent comprises a cyclic organic solvent and a chain organic solvent, the cyclic organic solvent is one or more of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain organic solvent is one or more of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
Preferably, the sodium salt electrolyte is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate and sodium bifluoroxalato borate.
The third purpose of the invention is that: aiming at the defects of the prior art, the sodium ion battery has good cycle performance, high and low temperature performance, first efficiency, no flatulence during high-temperature storage and good safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sodium ion battery comprises the electrolyte.
The sodium ion battery comprises a positive plate, a negative plate, a diaphragm, electrolyte and a shell. The positive electrode includes a current collector and an active material layer provided on the current collector. The active material layer includes but is not limited to the chemical formula of Na0.67MnxAyBzO2±δIn the molecular formula, A is one or more of Co, Ni and Cr, B is one or more of Mg, Al, Ca, Ti, Cu, Zn and Ba, and 0.6<x<1，0<y<0.1，0.6<x + y0, x + y + z is 1, 0 ≦ δ ≦ 0.1, and the positive electrode active material may also include, but is not limited to, Na1.845Mn[Fe(CN)6]0.961·1.988H2O、Na3V2(PO4)2O2F、Na3V1.95Mn0.05(PO4)2F3、Na3V1.95Mn0.05(PO4)2O2F、Na3V2(PO4)2F3And Na2.95Li0.05V2(PO4)2O2F, and the like. The positive electrode active material may be further modified, and the method of modifying the positive electrode active material is known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, and the like, and the material used in the modification may be one or a combination of more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, and the like, but is not limited thereto. And the positive electrode current collector is generally a structure or a part for collecting current, and the positive electrode current collector may be any material suitable for being used as a positive electrode current collector of a sodium ion battery in the field, for example, the positive electrode current collector may include, but is not limited to, a metal foil and the like, and more specifically, may include, but is not limited to, an aluminum foil and the like.
The negative electrode comprises a current collector and an active substance layer arranged on the surface of the current collector, wherein the active substance layer can be one or more of graphite, soft carbon, hard carbon, carbon fiber, mesocarbon microbeads, silicon-based materials, tin-based materials, lithium titanate or other metals capable of forming an alloy with sodium. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon-oxygen compound, silicon-carbon compound and silicon alloy; the tin-based material can be one or more selected from simple substance tin, tin oxide compound and tin alloy. The negative electrode current collector is generally a structure or a part for collecting current, and may be any material suitable for use as a negative electrode current collector of a sodium ion battery in the art, for example, the negative electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a copper foil, and the like.
The separator may be any material suitable for a sodium ion battery separator in the art, and for example, may be a combination including, but not limited to, one or more of polyethylene, polypropylene, polyvinylidene fluoride, aramid, polyethylene terephthalate, polytetrafluoroethylene, polyacrylonitrile, polyimide, polyamide, polyester, natural fiber, and the like.
Compared with the prior art, the invention has the beneficial effects that: in the electrolyte additive, a first compound in the additive a is oxidized and decomposed at the positive electrode to form a stable CEI film, and the interface film contains B-O bonds, so that the electrolyte additive has higher ionic conductivity, reduces the internal resistance of a battery, reduces polarization, improves cycle performance, can improve the wettability of electrolyte and forms a more uniform low-impedance interface film; the second compound in the additive a, Si-O bond breaking can react with water and HF to prevent large-size water from enteringThe crystal lattice is extruded in the anode material, the stability of the material is improved, the hydrolysis of sodium salt can be inhibited, the stability of the electrolyte is improved, and the second compound has a fluorosulfonyl structure because of fluorine atoms and SO2And the fluorine-containing compound has good wettability and low film-forming impedance, and the performance of the battery is improved. The electrolyte additive can obviously improve the cycle and high-temperature storage performance of the battery, greatly reduces the gas production in the high-temperature storage process, and forms a more uniform and compact SEI film with small film impedance by being used in cooperation with the additive b, thereby further improving the cycle and high-temperature performance of the battery.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the embodiments of the present invention are not limited thereto.
Example 1
Preparing an electrolyte: mixing NaPF6Mixing organic solvent (EC (ethylene carbonate): DEC (diethyl carbonate): EMC (ethyl methyl carbonate): 3:2:5), additive a and additive b to obtain electrolyte, NaPF6The mass fractions of the organic solvent, the additive a and the additive b are 14%, 83%, 1% and 2%, respectively. The additive a is a mixture of a first compound and a second compound, wherein the mass ratio of the first compound to the second compound is 2:1, and the structures of the first compound and the second compound are as follows:
preparing a positive plate: the positive electrode material is Prussian blue positive electrode material Na1.72MnFe (CN)6, the positive electrode material, binder PVDF and conductive agent Super-P are dispersed in NMP organic solvent according to the mass ratio of 90:4:6, and are stirred to be stable and uniform under the action of a vacuum stirrer, and are uniformly coated on an aluminum foil with the thickness of 12 mu m. And (3) airing the aluminum foil at room temperature, transferring the aluminum foil to a blast oven at 120 ℃ for drying for 1h, and then performing cold pressing and die cutting to prepare the positive plate.
Preparing a negative plate: the spherical hard carbon, the PVDF binder and the Super-P conductive agent are mixed together according to the mass ratio of 97:2:1, and are dispersed in an NMP organic solvent, so that the spherical hard carbon, the PVDF binder and the Super-P conductive agent are uniformly coated on an aluminum foil with the thickness of 15 mu m. And (3) airing the aluminum foil at room temperature, transferring the aluminum foil to a blast oven at 120 ℃ for drying for 1h, and then performing cold pressing and die cutting to prepare the negative plate.
Preparing a sodium ion battery: and (2) obtaining a naked battery core by laminating the positive plate, the negative plate and the polypropylene ceramic diaphragm, filling the battery core into an aluminum-plastic film packaging shell, injecting the electrolyte, sequentially sealing, standing, performing hot-cold pressing, forming, grading and other processes, and thus obtaining the sodium ion battery.
Example 2
The difference from example 1 is that: the NaPF6The mass fractions of the organic solvent, the additive a and the additive b are 14%, 82%, 2% and 2%, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
Example 3
The difference from example 1 is that: the NaPF6The mass fractions of the organic solvent, the additive a and the additive b are 14%, 79%, 5% and 2%, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
Example 4
The difference from example 1 is that: the NaPF6The mass fractions of the organic solvent, the additive a and the additive b are 14%, 77%, 7% and 2%, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
Example 5
The difference from example 1 is that: the additive a comprises a first compound and a second compound, and the structure is as follows:
the rest is the same as embodiment 1, and the description is omitted here.
Example 6
The difference from example 1 is that: the additive a comprises a first compound and a second compound, and the structure is as follows:
the rest is the same as embodiment 1, and the description is omitted here.
Example 7
The difference from example 1 is that: the additive a comprises a first compound and a second compound, and the structure is as follows:
the rest is the same as embodiment 1, and the description is omitted here.
Example 8
The difference from example 1 is that: additive a includes only the first compound, and the structure is as follows:
the rest is the same as embodiment 1, and the description is omitted here.
Example 9
The difference from example 1 is that: additive a includes only the second compound, and the structure is as follows:
the rest is the same as embodiment 1, and the description is omitted here.
Example 10
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 1: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 11
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 3: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 12
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 4: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 13
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 5: 1.
The rest is the same as embodiment 1, and the description is omitted here.
Example 14
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 1: 2.
The rest is the same as embodiment 1, and the description is omitted here.
Example 15
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 1: 3.
The rest is the same as embodiment 1, and the description is omitted here.
Example 16
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 1: 4.
The rest is the same as embodiment 1, and the description is omitted here.
Example 17
The difference from example 1 is that: the mass ratio of the first compound to the second compound is 1: 5.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 1
The difference from example 1 is that: NaPF6The mass fractions of the organic solvent and the additive b are 14%, 84% and 2%, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
Comparative example 2
The difference from example 1 is that: NaPF6The mass fractions of the organic solvent and the additive a are 14%, 84% and 2%, respectively.
The rest is the same as embodiment 1, and the description is omitted here.
And (3) performance testing: the electrolyte additives prepared in the above examples 1 to 17 and comparative examples 1 and 2 were applied to an electrolyte and a sodium ion battery was prepared and tested, and the test results are reported in table 1.
TABLE 1
The performance of the electrolyte additive prepared by the invention is better than that of comparative example 1 and comparative example 2, the capacity retention rate of the electrolyte additive in 500 cycles at 55 ℃ reaches 94.3%, the capacity retention rate of the electrolyte additive in high-temperature storage at 60 ℃/7d reaches 97.1%, the capacity recovery rate is 99.8%, and the thickness expansion rate is 0.52%. From the comparison of examples 1-4, when the NaPF is set6And when the mass fractions of the organic solvent, the additive a and the additive b are 14%, 83%, 1% and 2%, respectively, the prepared electrolyte has better performance. From comparison of examples 1 and 5 to 9, when the additive a is set to have the following chemical formulas for the first compound and the second compound, respectively, the prepared electrolyte has better performance.
From comparison of examples 1 and 10 to 17, when the mass ratio of the first compound to the second compound is set to 2:1, the prepared electrolyte has better performance. From comparison of example 1 and comparative examples 1-2, the electrolyte prepared by using only additive a or only additive b has poor performance.
In conclusion, the sodium ion battery provided by the invention can effectively improve the cycle performance of the electrolyte and improve the high-low temperature capacity retention rate, the capacity recovery rate and the thickness expansion rate.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.
Claims (10)
1. An electrolyte additive is characterized by comprising an additive a and an additive b, wherein the additive a comprises one or more of a first compound shown as a formula I and a second compound shown as a formula II;
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 are respectively and independently selected from any one of hydrogen, a halogen atom, an alkyl group with 1-10 carbon atoms, an unsaturated alkyl group with 2-10 carbon atoms, an alkoxy group with 1-10 carbon atoms or an alkanoyl group with 2-10 carbon atoms, and H in the alkyl group, the unsaturated alkyl group, the alkoxy group and the alkanoyl group can be partially or completely substituted by one or more of a halogen atom, a cyano group, a carboxyl group and a sulfonic group; wherein the additive b is one or more of ethylene carbonate, fluoroethylene carbonate, ethylene carbonate, ethylene sulfate and propenyl sultone.
2. The electrolyte additive as claimed in claim 1, wherein in the first compound represented by formula i, R1, R2 and R3 are halogen atoms, and in the second compound represented by formula ii, R4, R5 and R6 are halogen atoms, and R7, R8 and R9 are alkyl groups having 1 to 10 carbon atoms.
3. The electrolyte additive according to claim 1 or 2, wherein R1, R2, R3 are fluorine in the first compound, R4, R5, R6 are fluorine, and R7, R8, and R9 are methyl in the second compound.
4. The electrolyte additive as claimed in claim 1, wherein the mass ratio of the additive a to the additive b is (1-5): 1-5.
5. The electrolyte additive according to claim 1 or 4, wherein the additive a comprises the first compound and the second compound, the mass part ratio of the first compound to the second compound is 2:1, and the additive b is fluoroethylene carbonate.
6. An electrolyte comprising a sodium salt electrolyte, an organic solvent and the electrolyte additive of any one of claims 1 to 5.
7. The electrolyte of claim 6, wherein the electrolyte additive comprises 2% to 10% by mass of the total mass of the electrolyte.
8. The electrolyte of claim 6, wherein the organic solvent comprises a cyclic organic solvent and a chain organic solvent, the cyclic organic solvent is one or more of ethylene carbonate, propylene carbonate and butylene carbonate, and the chain organic solvent is one or more of dimethyl carbonate, diethyl carbonate and ethyl methyl carbonate.
9. The electrolyte of claim 6, wherein the sodium salt electrolyte is one or more of sodium hexafluorophosphate, sodium perchlorate, sodium tetrafluoroborate, and sodium bifluorodioxalato.
10. A sodium ion battery comprising the electrolyte of any one of claims 6 to 9.
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| CN1409430A (en) * | 2001-09-20 | 2003-04-09 | 丰田自动车株式会社 | Secondary battery of non-water electrolyte |
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| CN111477955A (en) * | 2019-01-23 | 2020-07-31 | 现代自动车株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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| CN1409430A (en) * | 2001-09-20 | 2003-04-09 | 丰田自动车株式会社 | Secondary battery of non-water electrolyte |
| JP2004006237A (en) * | 2002-04-09 | 2004-01-08 | Toyota Motor Corp | Polymer electrolyte and polymer lithium battery |
| CN102035045A (en) * | 2009-09-24 | 2011-04-27 | 上海图尔实业发展有限公司 | Novel low-temperature flame-retardant electrolyte |
| US20150263386A1 (en) * | 2012-10-30 | 2015-09-17 | Basf Se | Lithium ion secondary battery comprising a silicon anode |
| CN111477955A (en) * | 2019-01-23 | 2020-07-31 | 现代自动车株式会社 | Electrolyte for lithium secondary battery and lithium secondary battery comprising the same |
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