CN116344939A - Nonaqueous electrolyte and sodium ion battery - Google Patents
Nonaqueous electrolyte and sodium ion battery Download PDFInfo
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- CN116344939A CN116344939A CN202310478413.XA CN202310478413A CN116344939A CN 116344939 A CN116344939 A CN 116344939A CN 202310478413 A CN202310478413 A CN 202310478413A CN 116344939 A CN116344939 A CN 116344939A
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- Prior art keywords
- sodium
- ion battery
- compound
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- nonaqueous
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 59
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims abstract description 17
- 229940125904 compound 1 Drugs 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 17
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 16
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 16
- -1 sodium phosphate compound Chemical class 0.000 claims abstract description 13
- 239000007774 positive electrode material Substances 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims description 21
- 229910052708 sodium Inorganic materials 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 13
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 13
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 12
- 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 12
- 239000007773 negative electrode material Substances 0.000 claims description 12
- 239000008151 electrolyte solution Substances 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 2
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 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
- KBVUALKOHTZCGR-UHFFFAOYSA-M sodium;difluorophosphinate Chemical compound [Na+].[O-]P(F)(F)=O KBVUALKOHTZCGR-UHFFFAOYSA-M 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 1
- 150000003949 imides Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 239000002253 acid Substances 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007086 side reaction Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 239000001488 sodium phosphate Substances 0.000 abstract description 4
- 229910000162 sodium phosphate Inorganic materials 0.000 abstract description 4
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001412 amines Chemical class 0.000 abstract description 3
- 229910017053 inorganic salt Inorganic materials 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 238000003780 insertion Methods 0.000 abstract description 2
- 230000037431 insertion Effects 0.000 abstract description 2
- 239000013589 supplement Substances 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 238000007600 charging Methods 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000002156 mixing Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 3
- 229910021385 hard carbon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000005678 chain carbonates Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- 229910001182 Mo alloy Inorganic materials 0.000 description 1
- 229910020808 NaBF Inorganic materials 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 241001460678 Napo <wasp> Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910001245 Sb alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- PBHYLKMSZFULFJ-UHFFFAOYSA-N [Co].[Ni].[Na] Chemical compound [Co].[Ni].[Na] PBHYLKMSZFULFJ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000006256 anode slurry Substances 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011076 safety test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000000391 smoking effect Effects 0.000 description 1
- VCCATSJUUVERFU-UHFFFAOYSA-N sodium bis(fluorosulfonyl)azanide Chemical compound FS(=O)(=O)N([Na])S(F)(=O)=O VCCATSJUUVERFU-UHFFFAOYSA-N 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a non-aqueous electrolyte and a sodium ion battery. The nonaqueous electrolyte comprises a nonaqueous organic solvent, sodium salt and an additive, wherein the additive comprises a compound 1. The compound 1 is a sodium phosphate compound, has a structure containing three carbon-nitrogen single bonds, has stronger alkalinity and is easy to generate hydrolysis reaction with water to generate an organic amine compound, and the organic amine can continuously react with free acid in a non-aqueous electrolyte to generate neutral inorganic salt, so that more effective water removal and acid removal effects are achieved, further the effects of reducing side reaction of the non-aqueous electrolyte and protecting a positive electrode material of a sodium ion battery are achieved, and the stability of the whole battery system is improved. The sodium phosphate compound supplements sodium ions consumed by forming a solid electrolyte membrane in the steps of the first formation process and ineffective sodium ions which cannot be separated out due to the insertion of a negative electrode in the subsequent circulation process, so that the energy density and the first coulomb efficiency of the sodium ion battery are obviously improved.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a nonaqueous electrolyte and a sodium ion battery.
Background
In the periodic table, the sodium element and the lithium element are in the same main group, and the physical and chemical properties are very similar. And the working principle of the formed battery is similar, and the sodium ion battery mainly relies on sodium ions to be detached and embedded back and forth between the anode and the cathode. During charging, na + Removing the positive electrode from the negative electrode; upon discharge, na + Returning from the negative electrode to the positive electrode, and making the external circuit electrons enter the positive electrode from the negative electrode to make Na + Reducing to Na.
Meanwhile, compared with a lithium ion battery, the solvation energy of sodium ions is lower than that of lithium ions, the interfacial ion diffusion capacity is better, the Stokes diameter of sodium ions is smaller than that of lithium ions, and electrolyte with the same concentration has higher ion conductivity than that of lithium salt electrolyte. Allowing the use of low concentration electrolytes (same concentration electrolytes, sodium salts with conductivity about 20% higher than lithium electrolytes) to reduce costs. The sodium ion battery has more excellent high-low temperature performance and better safety performance. The internal resistance of the sodium ion battery is slightly higher than that of the lithium ion battery, and the instant heating value and the temperature rise are less under the short circuit condition. From a resource reserve perspective, lithium resources are increasingly scarce, while sodium resources are more 1353 times more abundant in the crust than lithium resources.
Therefore, as new energy automobiles enter the outbreak period, the price of lithium ores is increased, and the development space of lithium ion batteries is limited finally because the material cost of the lithium batteries is greatly increased to bring larger pressure to an industrial chain. The method has the advantages of abundant sodium resources, low price, environmental friendliness and the like, and has wide application prospects in the fields of large-scale energy storage, electric vehicles, electric ships, special engineering vehicles and the like.
However, as the ionic radius of sodium ions is larger than that of lithium ions, and the common negative electrode material hard carbon has large specific surface area and smaller interlayer spacing, so that sodium ions are difficult to separate after intercalation, the sodium ions are irreversibly consumed, and the initial coulombic efficiency of the sodium ion battery is low. Further, in general, sodium alkyl carbonate and sodium alkyl carbonate in SE1 film formed in a sodium ion battery have a higher solubility in carbonate than inorganic NaF and Na 2 CO 3 The equivalent height is 70-80 times, and the inorganic components NaF and Na in the Na-SE1 film 2 CO 3 Specific inorganic component L1-F, L1 in L1-SE1 Membrane 2 CO 3 The solubility of the sodium-ion battery is 30-40 times higher, so that the Na-SE1 film is unstable, side reactions with electrolyte are increased, and the high-temperature storage and cycle performance of the sodium-ion battery are reduced.
Therefore, how to improve the first coulombic efficiency and reduce the side reaction of the sodium ion battery is a problem to be solved in the industry.
Disclosure of Invention
In view of the above problems, an object of the present invention is to provide a nonaqueous electrolyte and a sodium ion battery, in which the additive compound 1 contained in the nonaqueous electrolyte can be used as an additive for supplementing sodium ions to compensate for the first capacity loss of the battery, which can effectively solve the problem of low first coulombic efficiency, and can improve the capacity and stability of the battery, and can also improve the safety performance of the sodium ion battery.
To achieve the above object, the first aspect of the present invention provides a nonaqueous electrolytic solution comprising a nonaqueous organic solvent, a sodium salt and an additive, the additive comprising compound 1.
The additive in the electrolyte adopted by the invention comprises the compound 1, wherein the compound 1 is a sodium phosphate compound which has a structure with three carbon-nitrogen single bonds, has stronger alkalinity and is easy to generate hydrolysis reaction with water to generate an organic amine compound, and the organic amine can continuously react with free acid in the nonaqueous electrolyte to generate neutral inorganic salt, so that more effective water removal and acid removal effects are achieved, the effects of reducing side reaction of the nonaqueous electrolyte and protecting the positive electrode material of a sodium ion battery are further achieved, the stability of the whole battery system is improved, and the cycle performance is improved. The sodium phosphate compound supplements sodium ions consumed by forming a solid electrolyte membrane in the steps of the first formation process and ineffective sodium ions which cannot be separated out due to the insertion of a negative electrode in the subsequent circulation process, so that the energy density and the first coulomb efficiency of the sodium ion battery are obviously improved. In addition, as the compound 1 also introduces the phosphoric acid group, the compound has good flame retardant property, and the safety performance of the sodium ion battery can be improved.
As an embodiment of the present invention, the sum of the mass of the nonaqueous organic solvent, the sodium salt and the additive is m, and the mass of the compound 1 is n, wherein n/m is 0.01 to 1.00%. By way of example, n/m may be, but is not limited to, 0.01%, 0.02%, 0.03%, 0.04%, 0.05%, 0.08%, 0.10%, 0.20%, 0.30%, 0.40%, 0.50%, 0.60%, 0.70%, 0.80%, 0.90%, 1.00%.
As a technical scheme of the invention, the sodium salt accounts for 6-15% of the sum of the mass of the nonaqueous organic solvent, the mass of the sodium salt and the mass of the additive. Preferably, the sodium salt accounts for 8-15%. By way of example, the sodium salt may be 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15% in ratio, but is not limited to. The sodium salt is selected from sodium hexafluorophosphate (NaPF) 6 ) Sodium tetrafluoroborate (NaBF) 4 ) Sodium difluorophosphate (NaPO) 2 F 2 ) Sodium perchlorate (NaClO) 4 ) Sodium triflate (NaCF) 3 SO 3 ) Sodium bistrifluoromethylsulfonylimide (NaN (CF) 3 SO 2 ) 2 ) Sodium bisoxalato borate (C) 4 BL1O 8 ) Sodium difluorooxalato borate (C) 2 BF 2 NaO 4 ) Second partAt least one of sodium fluorodi-oxalate phosphate (NaDFBP) and sodium bis-fluorosulfonyl imide (NaFS 1).
As an embodiment of the present invention, the nonaqueous organic solvent is at least one of a chain carbonate, a cyclic carbonate and a carboxylic acid ester. Preferably, the nonaqueous organic solvent is a mixture of a chain carbonate and a cyclic carbonate. As an example, the nonaqueous organic solvent is selected from at least one of Ethylene Carbonate (EC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), propylene Carbonate (PC), butyl acetate (n-Ba), γ -butyrolactone (γ -Bt), propyl propionate (n-Pp), ethyl Propionate (EP), and ethyl butyrate (Eb). The nonaqueous organic solvent accounts for 80% or more, preferably 85% or more of the total mass of the nonaqueous organic solvent, the sodium salt and the additive. As an example, the nonaqueous organic solvent may be, but is not limited to, 80% or more, 81% or more, 82% or more, 83% or more, 84% or more, 85% or more, 86% or more, 87% or more, 88% or more, 89% or more, 90% or more of the total mass of the nonaqueous organic solvent, sodium salt, and additive.
The second aspect of the present invention provides a sodium ion battery comprising a positive electrode material, a negative electrode material, and a nonaqueous electrolyte. The sodium ion battery has better cycle life and high-temperature storage performance, and is favorable for further industrialized development of the sodium ion battery.
As one technical scheme of the invention, the positive electrode material is a layered oxide, and the chemical formula of the layered oxide is Na x M (1-y-z) Fe y Mn z O 2 Wherein M is selected from at least one of Co, ni, cu, mg, zn, al, sn, ga, cr, sr, V and T1, 0<x≤1，0≤y<1，0≤z<1，y+z≤1。
As an aspect of the present invention, the negative electrode material is at least one selected from a carbon-based negative electrode material, a titanium-based oxide negative electrode material, and an alloy-based negative electrode material.
As an aspect of the present invention, the negative electrode material may be at least one selected from the group consisting of hard carbon, soft carbon, sodium titanate, sb alloy, sn alloy, potassium alloy, aluminum alloy, copper alloy, and molybdenum alloy.
Detailed Description
For a better description of the objects, technical solutions and advantageous effects of the present invention, the present invention will be further described with reference to specific examples. It should be noted that the following implementation of the method is a further explanation of the present invention and should not be taken as limiting the present invention.
Wherein, the specific conditions are not noted in the examples, and the method can be carried out according to the conventional conditions or the conditions suggested by manufacturers. The reagents or apparatus used were conventional products available commercially without the manufacturer's attention.
Example 1
(1) Preparation of nonaqueous electrolyte: preparing an electrolyte in a vacuum glove box with the moisture content less than 1ppm under the argon atmosphere, mixing Ethylene Carbonate (EC), diethyl carbonate (DEC) and Propylene Carbonate (PC) according to the weight ratio of EC to DEC to PC=1 to 1 in the glove box with the dry argon atmosphere, then adding the compound 1, dissolving and fully stirring, then adding sodium hexafluorophosphate, and uniformly mixing to obtain the electrolyte.
(2) Preparation of positive electrode: ternary material NaNi of sodium nickel cobalt aluminate 1/3 Fe 1./3 Mn 1/3 O 2 Uniformly mixing the adhesive PVDF and the conductive agent SuperP according to the mass ratio of 96:2:3 to prepare sodium ion battery anode slurry with certain viscosity, coating the mixed slurry on two sides of an aluminum foil, and drying and rolling to obtain the anode plate.
(3) Preparation of the negative electrode: preparing slurry from hard carbon, a conductive agent SuperP, a thickener CMC and an adhesive SBR (styrene butadiene rubber emulsion) according to the mass ratio of 96:1:1:2, uniformly mixing, coating the mixed slurry on two sides of a copper foil, drying and rolling to obtain the negative plate.
(4) Preparation of sodium ion battery: and (3) preparing the positive plate, the diaphragm and the negative plate into square cells in a lamination mode, packaging by adopting polymers, filling the prepared nonaqueous electrolyte of the sodium ion battery, and preparing the sodium ion battery with the capacity of 1400mAh through the procedures of formation, capacity division and the like.
The electrolyte formulations of examples 1 to 6 and comparative example 1 are shown in table 1, and the steps of preparing electrolytes and preparing batteries of examples 2 to 6 and comparative example 1 are the same as those of example 1.
Table 1 electrolyte components of examples and comparative examples
| Group of | Nonaqueous organic solvent/Mass (g) | Sodium salt/mass (g) | Additive (g) |
| Example 1 | EC:DEC:PC＝1:1:1(87.49g) | NaPF 6 (12.5g) | Compound 1 (0.01 g) |
| Example 2 | EC:DEC:PC＝1:1:1(87.45g) | NaPF 6 (12.5g) | Compound 1 (0.05 g) |
| Example 3 | EC:DEC:PC＝1:1:1(87.4g) | NaPF 6 (12.5g) | Compound 1 (0.1 g) |
| Example 4 | EC:DEC:PC＝1:1:1(87.0g) | NaPF 6 (12.5g) | Compound 1 (0.5 g) |
| Example 5 | EC:DEC:PC＝1:1:1(86.5g) | NaPF 6 (12.5g) | Compound 1 (1.0 g) |
| Example 6 | PC/EMC/DEC＝1:2:1(87.0g) | NaPF 6 (7.7g)+NaFSI(4.3g) | Compound 1 (1.0 g) |
| Comparative example 1 | EC:DEC:PC＝1:1:1(87.5g) | NaPF 6 (12.5g) | / |
The sodium ion batteries manufactured in examples 1 to 6 and comparative example 1 were subjected to a first efficiency performance test, a high temperature cycle test, and a safety test, respectively, under the following specific test conditions, and the test results are shown in table 2.
(1) First-time efficiency test of sodium ion battery
And (3) charging the sodium ion battery to 3.2V at a constant current of 0.1C under the condition of normal temperature (25 ℃) for 60min, charging to 3.2V at a constant current of 0.2C for 120min, sealing after the formation of C1+C2, charging to 4.0V at a constant current of 0.5C, discharging to 2.0V at a constant current of 0.5C, discharging to C4, and standing for 10min after the completion of the formation.
First efficiency = C4/(c1+c2+c3) ×100%
(2) High temperature cycle test of sodium ion battery
And placing the sodium ion battery in a 45 ℃ incubator, and standing for 30min to keep the sodium ion battery at a constant temperature. The first-turn discharge capacity of the battery was recorded by charging to a voltage of 4.0V with a constant current of 1C, then charging to a current of 0.05C with a constant voltage of 4.0V, and then discharging to a voltage of 2.0V with a constant current of 1C. This is a charge-discharge cycle. The cycle was continued for 400 weeks, and the discharge capacity of the first cycle and the discharge capacity of the last cycle were recorded, and the capacity retention was calculated as follows.
Capacity retention = last cycle discharge capacity/first cycle discharge capacity x 100%
(3) Sodium ion battery safety performance test
And (3) placing the sodium ion battery in a 60 ℃ oven, heating to 60 ℃ at a heating speed of 5 ℃/min, keeping the temperature at 60 ℃ for 30min, carrying out 1C constant-current constant-voltage charging on the sodium ion battery, wherein the upper limit voltage is 10V, and observing whether the battery has serious swelling, smoking, fire, explosion and other phenomena.
Table 2 sodium ion battery performance test results
From the results of table 2, it is understood that the first coulombic efficiency of the sodium ion batteries in examples 1 to 6 is higher based on comparative example 1, because the additives in the electrolytes of examples 1 to 6 include compound 1. Compound 1 complements the sodium ions consumed to form the solid electrolyte membrane in the steps of the first formation process, thus improving the first coulombic efficiency of the sodium ion battery.
Similarly, based on the results of table 2, the sodium ion batteries in examples 1 to 6 have higher capacity retention rate after 400 weeks of circulation at 45 ℃ 1C, and the high-temperature circulation performance is better than that of comparative example 1, because the compound 1 contained in the sodium ion batteries in examples 1 to 6 has a structure containing three carbon-nitrogen single bonds, has stronger alkalinity and is easy to react with water to generate organic amine compounds, and the organic amine can continuously react with free acid in the nonaqueous electrolyte to generate neutral inorganic salt, thereby achieving more effective water removal and acid removal effects, further playing a role of reducing side reaction of the nonaqueous electrolyte, protecting the cathode material of the sodium ion battery, being beneficial to improving the stability of the whole battery system and being beneficial to improving the circulation performance.
Based on the results of table 2, the safety performance of the sodium ion batteries in examples 1 to 6 was more superior to that of comparative example 1. This is because the sodium ion battery in examples 1 to 6 contains the compound 1, which has a phosphoric acid group introduced therein, so that it has a good flame retardant property, and the safety performance of the sodium ion battery can be improved.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the present invention can be modified or substituted without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. A nonaqueous electrolyte comprising a nonaqueous organic solvent, a sodium salt and an additive, characterized in that the additive comprises a compound 1,
2. the nonaqueous electrolytic solution according to claim 1, wherein a sum of mass of the nonaqueous organic solvent, the sodium salt and the additive is m, and the mass of the compound 1 is n, n/m is 0.01 to 1.00%.
3. The nonaqueous electrolytic solution according to claim 1, wherein the sodium salt is 6 to 15% of the sum of the mass of the nonaqueous organic solvent, the mass of the sodium salt and the mass of the additive.
4. The nonaqueous electrolytic solution according to claim 3, wherein the sodium salt is at least one selected from the group consisting of sodium hexafluorophosphate, sodium tetrafluoroborate, sodium difluorophosphate, sodium perchlorate, sodium trifluoromethylsulfonate, sodium bistrifluoromethylsulfonylimide, sodium bisoxalato borate, sodium difluorooxalato borate, sodium difluorodioxaato phosphate and sodium bisfluorosulfonyl imide.
5. The nonaqueous electrolytic solution according to claim 1, wherein the nonaqueous organic solvent is at least one selected from the group consisting of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methylethyl carbonate, propylene carbonate, butyl acetate, γ -butyrolactone, propyl propionate, ethyl propionate and ethyl butyrate.
6. A sodium ion battery comprising a positive electrode material, a negative electrode material and the nonaqueous electrolytic solution according to any one of claims 1 to 5.
7. The sodium ion battery of claim 6, wherein the positive electrode material is a layered oxide having a chemical formula of Na x M (1-y-z) Fe y Mn z O 2 Wherein M is selected from at least one of Co, ni, cu, mg, zn, al, sn, ga, cr, sr, V and T1, 0<x≤1，0≤y<1，0≤z<1，y+z≤1。
8. The sodium ion battery of claim 6, wherein the negative electrode material is selected from at least one of a carbon-based negative electrode material, a titanium-based oxide negative electrode material, and an alloy-based negative electrode material.
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| CN116895839B (en) * | 2023-08-29 | 2024-04-05 | 合肥市赛纬电子材料有限公司 | Nonaqueous electrolyte and sodium ion battery containing same |
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