CN117293392A - Electrolyte with metal compensation function and application thereof - Google Patents
Electrolyte with metal compensation function and application thereof Download PDFInfo
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- CN117293392A CN117293392A CN202311450572.5A CN202311450572A CN117293392A CN 117293392 A CN117293392 A CN 117293392A CN 202311450572 A CN202311450572 A CN 202311450572A CN 117293392 A CN117293392 A CN 117293392A
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- electrolyte
- ion battery
- sodium
- metal
- carbonate
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 181
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 56
- 239000002184 metal Substances 0.000 title claims abstract description 56
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 61
- 230000000694 effects Effects 0.000 claims abstract description 34
- 239000000654 additive Substances 0.000 claims abstract description 19
- 230000000996 additive effect Effects 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007774 positive electrode material Substances 0.000 claims description 52
- 239000011734 sodium Substances 0.000 claims description 43
- 229910052708 sodium Inorganic materials 0.000 claims description 41
- 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 40
- 229910001415 sodium ion Inorganic materials 0.000 claims description 36
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 34
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 30
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- QXBUYALKJGBACG-UHFFFAOYSA-N 10-methylphenothiazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3SC2=C1 QXBUYALKJGBACG-UHFFFAOYSA-N 0.000 claims description 17
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 17
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 17
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 15
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 15
- LKPFBGKZCCBZDK-UHFFFAOYSA-N n-hydroxypiperidine Chemical compound ON1CCCCC1 LKPFBGKZCCBZDK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003365 glass fiber Substances 0.000 claims description 8
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- 229910001414 potassium ion Inorganic materials 0.000 claims description 7
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 150000003254 radicals Chemical class 0.000 claims description 6
- CJAOGUFAAWZWNI-UHFFFAOYSA-N 1-n,1-n,4-n,4-n-tetramethylbenzene-1,4-diamine Chemical compound CN(C)C1=CC=C(N(C)C)C=C1 CJAOGUFAAWZWNI-UHFFFAOYSA-N 0.000 claims description 4
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- FHCPAXDKURNIOZ-UHFFFAOYSA-N tetrathiafulvalene Chemical compound S1C=CSC1=C1SC=CS1 FHCPAXDKURNIOZ-UHFFFAOYSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- YMZRSQACICUVJT-UHFFFAOYSA-N [Mn].[Ni].[Na] Chemical compound [Mn].[Ni].[Na] YMZRSQACICUVJT-UHFFFAOYSA-N 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims description 2
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 claims description 2
- WSKOARFZINZCTI-UHFFFAOYSA-H [V+5].P(=O)([O-])([O-])[O-].[K+].P(=O)([O-])([O-])[O-] Chemical compound [V+5].P(=O)([O-])([O-])[O-].[K+].P(=O)([O-])([O-])[O-] WSKOARFZINZCTI-UHFFFAOYSA-H 0.000 claims description 2
- 150000005678 chain carbonates Chemical class 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-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
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- RZSRVBMQQGDAIS-UHFFFAOYSA-K potassium;iron(2+);phosphate Chemical compound [K+].[Fe+2].[O-]P([O-])([O-])=O RZSRVBMQQGDAIS-UHFFFAOYSA-K 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- RMZMFASTOVOJPY-UHFFFAOYSA-N [Fe].[Mn].[Ni].[Na] Chemical compound [Fe].[Mn].[Ni].[Na] RMZMFASTOVOJPY-UHFFFAOYSA-N 0.000 claims 1
- BYTVRGSKFNKHHE-UHFFFAOYSA-K sodium;[hydroxy(oxido)phosphoryl] phosphate;iron(2+) Chemical compound [Na+].[Fe+2].OP([O-])(=O)OP([O-])([O-])=O BYTVRGSKFNKHHE-UHFFFAOYSA-K 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 15
- 230000008569 process Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 51
- 238000011056 performance test Methods 0.000 description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 26
- 238000003756 stirring Methods 0.000 description 20
- -1 sodium iron pyrophosphate phosphate Chemical compound 0.000 description 18
- 230000014759 maintenance of location Effects 0.000 description 15
- 229910052786 argon Inorganic materials 0.000 description 13
- 239000000203 mixture Substances 0.000 description 9
- 230000001351 cycling effect Effects 0.000 description 8
- 238000007599 discharging Methods 0.000 description 7
- 230000033116 oxidation-reduction process Effects 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000001502 supplementing effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- DWYMPOCYEZONEA-UHFFFAOYSA-L fluoridophosphate Chemical compound [O-]P([O-])(F)=O DWYMPOCYEZONEA-UHFFFAOYSA-L 0.000 description 3
- 125000005287 vanadyl group Chemical group 0.000 description 3
- GVTGSIMRZRYNEI-UHFFFAOYSA-N 5,10-dimethylphenazine Chemical compound C1=CC=C2N(C)C3=CC=CC=C3N(C)C2=C1 GVTGSIMRZRYNEI-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- AWRQDLAZGAQUNZ-UHFFFAOYSA-K sodium;iron(2+);phosphate Chemical compound [Na+].[Fe+2].[O-]P([O-])([O-])=O AWRQDLAZGAQUNZ-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- QXZNUMVOKMLCEX-UHFFFAOYSA-N [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F Chemical compound [Na].FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F QXZNUMVOKMLCEX-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013589 supplement 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to an electrolyte with a metal compensation function and application thereof, and belongs to the related technical field of electrolytes. The invention mainly prepares electrolyte by metal salt solute, carbonic ester solvent and redox medium additive. The redox medium participates in the redox process in the battery, and the metal ion compensation effect is generated, so that the material exerts higher capacity when being charged for the first time, and the energy density of the battery is improved. In addition, the redox mediator additive can also participate in the formation process of an electrode interface in the metal ion battery, and compact and uniform SEI and CEI are formed in the charge and discharge process, so that the long-cycle and high-rate performance is obviously improved.
Description
Technical Field
The invention belongs to the technical field of preparation of metal supplements, and relates to an electrolyte with a metal compensation function and application thereof.
Background
Metal ion batteries (e.g., sodium/lithium/potassium ion batteries) have been widely used in the fields of portable electronic devices, electric automobiles, and the like. Compared with a lithium ion battery, the metal ion battery has the advantages of rich resource reserves, low cost, high safety and the like, and is mainly applied to markets of energy storage, base stations, electric bicycles, low-end passenger vehicles and the like. However, the formation of negative electrode SEI, the presence of surface defects and the occurrence of side reactions consume active metal ions, reduce the initial efficiency of metal ion batteries, directly affect the energy density and cycle performance, and thus it is necessary to solve this problem by pre-metallization.
The metal compensation method commonly used at present is an additive method. The additive method does not need to change the existing production process and is simple and convenient to operate. Currently, common positive electrode additives are made of inorganic oxides (Li 4 FeO 3 、Na 4 FeO 3 ) And organic salt (Na) 2 C 2 O 4 、Li 2 C 2 O 4 ) Mainly, however, the additive has the problem that solid or gas residues exist after the reaction, and the structure of the positive electrode is affected.
For example, patent CN115117558A provides a method for supplementing sodium to a separator by transferring a sodium supplementing agent and a binder, a conductive agent, etc. to the surface of the separator by means of a homogenate coating, which can improve the initial efficiency of a sodium ion battery, but this method requires dispersing the conductive agent and the binder, which increases the cost, and the conductive agent and the binder remained on the separator after the sodium supplementing agent is decomposed and consumed in the reaction process affect the performance of the separator, and reduce the energy density of the battery.
Therefore, it is necessary to develop a novel sodium supplementing method to solve the above-mentioned problems of additives, thereby improving the energy density and performance of the metal ion battery.
Disclosure of Invention
Accordingly, one of the objects of the present invention is to provide an electrolyte with metal compensation function; the second object of the present invention is to provide an electrolyte with metal compensation function for use in metal ion batteries.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. an electrolyte with metal compensation effect, wherein the electrolyte comprises a metal salt solute, a carbonate solvent and a redox mediator additive;
the redox medium additive is any one or more of ferrocene, 10-methyl phenothiazine, 2, 6-tetramethyl piperidine oxide, nitroxide free radical piperidinol, N, N, N ', N' -tetramethyl p-phenylenediamine, 5, 10-dihydro-5, 10-dimethyl phenoxazine or tetrathiafulvalene.
Preferably, the metal salt solute is MClO 4 、MPF 6 、MBF 4 、MFSI、MTFSI、MBOB、MODFB、MODFP、MPO 2 F 2 Or CF (CF) 3 SO 3 M is any one or more of Li, na or K.
Preferably, the concentration of the metal salt solute in the electrolyte is 0.1mol/L to 5mol/L.
Preferably, the carbonate solvent is prepared from cyclic carbonates and chain carbonates according to 1: 3-3: 1 by volume ratio;
the cyclic carbonate is any one or more of vinylene carbonate, fluoroethylene carbonate, ethylene carbonate, propylene carbonate or ethylene carbonate;
the chain carbonic ester is any one or more of dimethyl carbonate, polycarbonate, methyl ethyl carbonate or diethyl carbonate.
Preferably, the mass of the redox mediator additive accounts for 0.1-10% of the mass of the electrolyte.
Preferably, the mass ratio of the metal salt solute, the carbonate solvent and the redox mediator additive is 1:1-19:0.002-2.
2. The electrolyte is applied to a metal ion battery, wherein the metal ion battery comprises any one of a sodium ion battery, a lithium ion battery or a potassium ion battery.
3. A metal ion battery comprises the electrolyte with metal compensation function.
Preferably, the metal ion battery further comprises a positive electrode, a negative electrode and a separator.
Preferably, when the metal ion battery is a sodium ion battery, the positive electrode material is any one or more of sodium vanadium phosphate, sodium vanadium fluorophosphate, sodium iron phosphate, sodium nickel manganese titanate or sodium nickel manganese titanate, the negative electrode is a sodium sheet, and the diaphragm is a glass fiber diaphragm;
when the metal ion battery is a lithium ion battery, the positive electrode material is any one or more of lithium iron phosphate, lithium iron manganese phosphate, lithium cobaltate or lithium manganate, the negative electrode is a sodium sheet, and the diaphragm is a glass fiber diaphragm;
when the metal ion battery is a potassium ion battery, the positive electrode material is any one or more of vanadium potassium phosphate, potassium manganate or potassium iron phosphate, the negative electrode is a sodium sheet, and the diaphragm is a glass fiber diaphragm.
The invention has the beneficial effects that: the invention discloses an electrolyte with metal compensation function, which is prepared by mainly preparing a metal salt solute, a carbonic ester solvent and a redox medium additive. The redox medium participates in the redox process in the battery, and the metal ion compensation effect is generated, so that the material exerts higher capacity when being charged for the first time, and the energy density of the battery is improved. In addition, the redox mediator additive can also participate in the formation process of an electrode interface in the metal ion battery, and compact and uniform SEI and CEI are formed in the charge and discharge process, so that the long-cycle and high-rate performance is obviously improved.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
fig. 1 is a first-turn performance test result of the electrolytes of example 1 and comparative example 1 in a metal ion battery using sodium iron pyrophosphate phosphate (NFPP) as a cathode material;
fig. 2 is a graph showing the results of rate performance test of the electrolyte of example 1 and comparative example 1 in a metal ion battery using sodium iron pyrophosphate phosphate (NFPP) as a positive electrode material;
fig. 3 is a first-turn performance test result of the electrolytes of example 1 and comparative example 1 in a metal ion battery using sodium vanadyl fluorophosphate (NVOPF) as a positive electrode material;
fig. 4 is a cycle performance test result of the electrolytes of example 1 and comparative example 1 in a metal ion battery using sodium vanadyl fluorophosphate (NVOPF) as a positive electrode material;
fig. 5 is a graph showing the results of rate performance tests of the electrolytes of example 1 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 6 is a cycle performance test result of the electrolytes of example 1 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 7 is a cycle performance test result of the electrolytes of example 2 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 8 is a cycle performance test result of the electrolytes of example 3 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 9 is a cycle performance test result of the electrolytes of example 4 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 10 is a cycle performance test result of the electrolytes of example 5 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 11 is a cycle performance test result of the electrolytes of example 6 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material;
fig. 12 is a cycle performance test result of the electrolytes of example 8 and comparative example 1 in a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, then 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 6mg of ferrocene (the mass is 0.5% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table and stirred until the solution is clear, so that the electrolyte with a metal compensation function can be obtained.
Example 2
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, then 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 12mg of ferrocene (the mass is 1% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table and stirred until the solution is clear, so that the electrolyte with metal compensation effect can be obtained.
Example 3
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, then 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 18mg of ferrocene (the mass is 1.5% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table and stirred until the solution is clear, so that the electrolyte with a metal compensation function can be obtained.
Example 4
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, then 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 6mg of 10-methylphenothiazine (the mass is 0.5% of the total mass of the electrolyte) are added, and the mixture is heated and stirred on a stirring table until the solution is clear, so that the electrolyte with metal compensation effect can be obtained.
Example 5
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 12mg of 10-methylphenothiazine (the mass is 1% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table and stirred until the solution is clear, so that the electrolyte with a metal compensation function can be obtained.
Example 6
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 18mg of 10-methylphenothiazine (the mass is 1.5% of the total mass of the electrolyte) are added, and the electrolyte with metal compensation effect is obtained by heating and stirring on a stirring table until the solution is clear.
Example 7
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 6mg of nitroxide-free piperidinol (the mass is 0.5% of the total mass of the electrolyte) are added, and the mixture is heated and stirred on a stirring table until the solution is clear, so that the electrolyte with metal compensation effect can be obtained.
Example 8
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 12mg of nitroxide-free piperidinol (the mass is 1% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table while stirring until the solution is clear, so that the electrolyte with a metal compensation function can be obtained.
Example 9
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate is added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 18mg of nitroxide-free piperidinol (the mass is 1.5% of the total mass of the electrolyte) are added, and the electrolyte with metal compensation effect is obtained by heating and stirring on a stirring table until the solution is clear.
Example 10
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, then 0.1mol of sodium hexafluorophosphate is added, then 6mg of ferrocene (the mass is 0.5% of the total mass of the electrolyte) is added, and the electrolyte with metal compensation function is obtained by heating and stirring on a stirring table until the solution is clear.
Example 11
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.05mol of sodium hexafluorophosphate and 0.05mol of sodium bis (trifluoromethylsulfonyl) imide (NaTFSI) are added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and 6mg of ferrocene (the mass is 0.5% of the total mass of the electrolyte) are added, and the mixture is heated on a stirring table while stirring until the solution is clear, thus obtaining the electrolyte with metal compensation function.
Example 12
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate are uniformly mixed to prepare 100ml of carbonate solvent, 0.05mol of sodium hexafluorophosphate and 0.05mol of sodium bis-fluorosulfonyl imide (NAFSI) are added, 60mg of fluoroethylene carbonate (the mass is 5% of the total mass of the electrolyte) and ferrocene (the mass is 0.5% of the total mass of the electrolyte) are added, and the electrolyte with metal compensation function is obtained by heating and stirring on a stirring table until the solution is clear.
Comparative example 1
An electrolyte with metal compensation function is prepared by the following steps:
in a glove box filled with argon, 50ml of ethylene carbonate and 50ml of diethyl carbonate were uniformly mixed to prepare 100ml of carbonate solvent, 0.1mol of sodium hexafluorophosphate was added, 60mg of fluoroethylene carbonate (mass 5% of the total mass of the electrolyte) was then added, and the mixture was heated on a stirring table while stirring until the solution was clear, to obtain an electrolyte of comparative example.
Performance testing
The positive electrode material, the binder PVDF and the conductive agent acetylene black are mixed according to the following ratio of 8:1: mixing 1 mass ratio in NMP, adjusting to proper viscosity, coating on aluminum foil, baking, compacting, rolling, cutting to obtain positive pole piece, respectively combining 150 mu L of the electrolyte in the examples 1-12 and the comparative example 1, wherein the sodium piece is a negative pole, and the glass fiber diaphragm is a diaphragm, thereby forming different metal ion batteries.
The electrochemical performance test is carried out on the metal ion batteries obtained by the electrolyte assembly of the examples 1 to 12 and the comparative example 1 by adopting a blue electric test system, the temperature is 25 ℃, the voltage interval is 2.5 to 4.3V, and the electrochemical performance test is specifically as follows:
the electrolyte prepared in example 1 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium iron phosphate (NFPP) as a positive electrode material. The first-cycle performance test was performed by charging and discharging at a constant current of 0.1C, and the results are shown in fig. 1. As can be seen from fig. 1, NFPP is used as a positive electrode material of sodium ions, and the electrolyte containing 0.5wt% of ferrocene in example 1 and the electrolyte without ferrocene in comparative example 1 are used as electrolytes, respectively, and the electrolyte in example 1 can increase the specific charge capacity of NFPP from 100mAh/g to 170mAh/g, while the specific discharge capacity is not changed at 80 mAh/g, thereby showing that the electrolyte in example 1 has a significant sodium compensation effect on NFPP in a sodium ion battery. The charge and discharge were performed at a rate of 0.1C, 0.2C, 0.5C, 1C, 2C, 3C, and 0.1C, and the results of the rate performance test were shown in fig. 2. As can be seen from fig. 2, the electrolyte containing 0.5wt% of ferrocene in example 1 is added to the electrolyte containing no ferrocene in comparative example 1 as the positive electrode material of the sodium ion battery, and the rate performance is compared, the NFPP performance after the electrolyte in comparative example 1 is added is fast, the NFPP performance at 1C is attenuated to be 0, the NFPP rate-increasing effect after the electrolyte in example 1 is added is obvious, the specific capacity of 70mAh/g is maintained at 1C, and the attenuation is slow, which indicates that the electrolyte in example 1 performs sodium compensation on the NFPP positive electrode material in the sodium ion battery in the previous 5 circles, so that the subsequent rate performance is optimized.
The electrolyte prepared in example 1 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadyl fluorophosphate (NVOPF) as a positive electrode material. The first-cycle performance test was performed by charging and discharging at a constant current of 0.1C, and the results are shown in fig. 3. As can be seen from fig. 3, the electrolyte of example 1 was able to increase the specific charge capacity of NVOPF from 70mAh/g to 140mAh/g without change in specific discharge capacity of 60 mAh/g, by comparing the electrolyte of example 1 containing 0.5wt% of ferrocene with the electrolyte of comparative example 1 without ferrocene as the electrolyte, respectively, as the positive electrode material of sodium ion, thereby demonstrating that the electrolyte of example 1 has a remarkable sodium compensation effect on NVOPF in sodium ion batteries.
The electrolyte prepared in example 1 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 1C, and the results are shown in fig. 4. As can be seen from fig. 4, as the positive electrode material of the sodium ion battery, in the cycle of 1C, the electrolyte containing 0.5wt% of ferrocene in example 1 and the electrolyte without ferrocene in comparative example 1 were compared as electrolytes, respectively, and the electrolytes in example 1 in the previous two turns of comparison have significant sodium compensation effect on NVP in the sodium ion battery, and as the cycle increases, the efficiency of the sodium ion battery gradually approaches 100%, indicating that the overall performance of the battery is not adversely affected. The charge and discharge were performed at 1C, 2C, 3C, 5C, 10C, 15C, 20C, and 1C magnifications, and the results of the rate performance tests are shown in fig. 5. As can be seen from fig. 5, the same NVP was used as the positive electrode material of the sodium ion battery, and the electrolytes of example 1 and comparative example 1 were added respectively, and the rate performance test was performed respectively, the performance of the NVP was fast decayed after the electrolyte of comparative example 1 was added, the decay was 20mAh/g at 20C, the effect of improving the rate performance of the NVP after the electrolyte of example 1 was added was obvious, the specific capacity of 95mAh/g was remained at 20C, and the decay was slow, which indicates that the electrolyte of example 1 performs sodium compensation on the positive electrode material of the NVP in the sodium ion battery in the previous 5 cycles, so that the subsequent rate performance was optimized. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 6. As can be seen from fig. 6, NVP was used as a positive electrode material of a sodium ion battery, and after the electrolyte containing 0.5wt% of ferrocene in example 1 was added to the electrolyte containing no ferrocene in comparative example 1 in a long cycle of 10C, the electrolyte containing no ferrocene in comparative example 1 was compared with the electrolyte containing no ferrocene in example 1, and after 350 cycles, the electrolyte containing no ferrocene in comparative example 1 was added to a volume retention of 28%, whereas the electrolyte containing sodium compensation in example 1 was added to a volume retention of 86%, indicating that the sodium compensation electrolyte containing 0.5wt% of ferrocene was also suitable for charging and discharging of a positive electrode material of NVP in a sodium ion battery at a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 2 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 7. As can be seen from fig. 7, NVP was used as a positive electrode material for sodium ions, and in a long cycle of 10C, the electrolyte containing 1wt% of ferrocene in example 2 and the electrolyte containing no ferrocene in comparative example 1 were added, respectively, and after 350 cycles, the capacity retention rate of NVP after the electrolyte of blank comparative example 1 was added was only 28%, whereas the capacity retention rate of NVP after the electrolyte of example 2 having sodium compensation was added was 88%, indicating that the electrolyte containing 1wt% of ferrocene having sodium compensation was added was also suitable for charging and discharging of positive electrode material NVP in sodium ion battery at a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 3 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 8. As can be seen from fig. 8, NVP was used as a positive electrode material for sodium ions, and in a long cycle of 10C, the electrolyte containing 1.5wt% of ferrocene in example 3 and the electrolyte containing no ferrocene in comparative example 1 were added, respectively, and after 350 cycles, the capacity retention rate of NVP after the electrolyte of blank comparative example 1 was added was only 28%, whereas the capacity retention rate of NVP after the electrolyte of example 2 was added was 67%, indicating that the electrolyte containing 1.5wt% of ferrocene with sodium compensation was added was also suitable for charging and discharging of positive electrode material NVP in sodium ion batteries at a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 4 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 9. As can be seen from fig. 9, NVP was used as a positive electrode material for sodium ions, and in a long cycle of 10C, the electrolyte containing 0.5wt% of 10-methylphenothiazine in example 4 and the electrolyte not containing 10-methylphenothiazine in comparative example 1 were added, respectively, and after 350 cycles, the capacity retention rate of NVP after the electrolyte of blank comparative example 1 was added was only 28%, whereas the capacity retention rate of NVP after the electrolyte of example 4 having a sodium compensation effect was added was 50%, indicating that the electrolyte having a sodium compensation effect with 0.5wt% of 10-methylphenothiazine was added was also suitable for charging and discharging of the positive electrode material NVP in sodium ion batteries at a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 5 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 10. As can be seen from fig. 10, NVP was used as a positive electrode material for sodium ions, and in the long cycle of 10C, the electrolyte containing 1.0wt% of 10-methylphenothiazine in example 5 and the electrolyte not containing 10-methylphenothiazine in comparative example 1 were respectively added, and after 350 cycles, the capacity retention rate of the blank comparative example was only 28%, while the capacity retention rate of the sodium compensation electrolyte in example 5 was 60%, indicating that the positive electrode material NVP in the sodium ion battery having sodium compensation effect by adding 1wt% of 10-methylphenothiazine was also suitable for charge and discharge of the electrolyte under a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 6 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 11. As can be seen from fig. 11, NVP was used as a positive electrode material for sodium ions, and in a long cycle of 10C, the electrolyte containing 1.5wt% of 10-methylphenothiazine in example 6 and the electrolyte not containing 10-methylphenothiazine in comparative example 1 were respectively added, and after 350 cycles, the capacity retention rate of the blank comparative example was only 28%, while the capacity retention rate of the sodium compensation electrolyte in example 6 was 50%, which indicates that the positive electrode material NVP in a sodium ion battery having sodium compensation effect by adding 10-methylphenothiazine containing 1.5wt% was equally applicable to charge and discharge of the electrolyte under a large current. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
The electrolyte prepared in example 8 and the electrolyte prepared in comparative example 1 were assembled to form a metal ion battery using sodium vanadium phosphate (NVP) as a positive electrode material. The cycle performance test was performed by cycling under charge and discharge at a constant current of 10C, and the results are shown in fig. 12. As can be seen from fig. 12, NVP was used as the positive electrode material of sodium ion, and in the long cycle of 10C, the electrolyte containing 1wt% of nitroxide radical piperidinol in example 8 and the electrolyte containing no nitroxide radical piperidinol in comparative example 1 were added respectively, and after 350 cycles, the capacity retention rate of the blank comparative example was only 28%, while the capacity retention rate of the sodium compensation electrolyte in example 8 was 60%, which indicates that the positive electrode material NVP in the sodium ion battery having sodium compensation effect by adding nitroxide radical piperidinol containing 1wt% was also suitable for charging and discharging under a large current in the electrolyte. In the large-current long cycle, the oxidation-reduction medium plays a certain role in forming compact and uniform SEI and CEI on the surface of the electrode, so that the cycle stability is improved.
Specific capacities of the electrolytes of examples 1 to 12 and comparative example 1, and sodium ion batteries formed with NVP positive electrode, metallic sodium sheet negative electrode and glass fiber separator are shown in table 1.
Table 1 specific capacities of metal-ion batteries formed in different examples
| Group of | Specific capacity/mAh/g |
| Example 1 | 176 |
| Example 2 | 220 |
| Example 3 | 155 |
| Example 4 | 167 |
| Example 5 | 144 |
| Example 6 | 174 |
| Example 7 | 171 |
| Example 8 | 164 |
| Example 9 | 175 |
| Example 10 | 190 |
| Example 11 | 185 |
| Example 12 | 183 |
| Comparative example 1 | 110 |
As can be seen from table 1, the electrolytes of examples 1 to 12, in which different redox mediators were added, were used as electrolytes, and the specific capacity of the positive electrode material in the sodium ion battery was improved as compared with the electrolyte of comparative example 1. Wherein 1wt% of the electrolyte after the addition of ferrocene showed the best first-round sodium compensation effect with the increase of the concentration in examples 1 to 3, 1.5wt% of the electrolyte after the addition of 10-methylphenothiazine showed the best first-round sodium compensation effect with the increase of the concentration in examples 4 to 6, and the sodium compensation effect of the electrolyte after the addition of nitroxide piperidinol was not very remarkable with the increase of the concentration in examples 7 to 9, but was still higher than that of the electrolyte in comparative example 1. In example 10, compared with example 1, the effect of ferrocene on sodium compensation was still apparent with the same concentration, and the difference was not so apparent, indicating that the effect of fluoroethylene carbonate on the sodium compensation electrolyte was not critical. Examples 11 and 12 are conducted to investigate the influence of sodium salt on the sodium compensation electrolyte, and comparison shows that only ferrocene component is contained in the electrolyte, so that capacity improvement is obvious, and the influence of sodium salt change on capacity is weak. Therefore, the redox medium added into the electrolyte has the main metal compensation effect on the sodium ion battery, so that the corresponding sodium ion battery has higher specific capacity, better rate capability and better cycle performance.
Likewise, the redox mediator of the examples was selected from any one or more of ferrocene, 10-methylphenothiazine, nitroxide piperidinol, 2, 6-tetramethylpiperidine oxide, N, N, N ', N' -tetramethylp-phenylenediamine, 5, 10-dihydro-5, 10-dimethylphenazine or tetrathiafulvalene, which still was capable of sodium ion compensation in sodium ion batteries.
Similarly, the positive electrode material is changed to form different metal ion batteries (such as ion batteries and potassium ion batteries), and the electrolyte with the metal compensation function provided by the invention can still generate the metal ion compensation function on the positive electrode material in the metal ion batteries, so that the corresponding electrical performance is improved.
It can be seen that the electrolyte with metal compensation effect disclosed by the invention comprises metal salt, carbonic ester and a redox medium, wherein the redox medium is any one or more of ferrocene, 10-methylphenothiazine, 2, 6-tetramethylpiperidine oxide, nitroxide free radical piperidinol, N, N, N ', N' -tetramethyl p-phenylenediamine, 5, 10-dihydro-5, 10-dimethyl phenazine or tetrathiafulvalene. As can be seen from fig. 1 and 3, the redox mediator can participate in the redox reaction of the metal ion battery, and the specific charge capacity is greatly increased while the specific discharge capacity is not changed, and metal ion compensation is performed, thereby increasing the energy density of the battery. The invention tests the electrochemical properties of three different positive electrode materials, and has the same metal compensation effect, which proves that the electrolyte has universality and also has effects of lithium ion batteries and potassium ion batteries. Fig. 2 and 5 show that, in the rate test, a small amount of redox mediator in the electrolyte has electrochemical activity, so as to promote stabilization of the CEI and SEI on the surface of the electrode, promote rapid migration of metal ions, and further improve the high rate performance of the metal ion battery. The circulation of the metal ion battery at 1C in FIG. 4 is obviously improved; fig. 6-12, the metal ion battery also improved under the high current cycle of 10C, using three different redox mediators, all with effects, demonstrate that the series of redox mediators also have metal compensating effects, and with concentration regulation, a best performance can be obtained. In FIG. 7, the capacity retention was highest at a ferrocene content of 1 wt%.
In summary, the invention discloses an electrolyte with metal compensation effect, which is prepared from metal salt solute, carbonate solvent and redox mediator additive. The redox medium participates in the redox process in the battery, and the metal ion compensation effect is generated, so that the material exerts higher capacity when being charged for the first time, and the energy density of the battery is improved. In addition, the redox mediator additive can also participate in the formation process of an electrode interface in the metal ion battery, and compact and uniform SEI and CEI are formed in the charge and discharge process, so that the long-cycle and high-rate performance is obviously improved.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, 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 modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (10)
1. An electrolyte with metal compensation function, which is characterized by comprising a metal salt solute, a carbonate solvent and a redox mediator additive;
the redox medium additive is any one or more of ferrocene, 10-methyl phenothiazine, 2, 6-tetramethyl piperidine oxide, nitroxide free radical piperidinol, N, N, N ', N' -tetramethyl p-phenylenediamine, 5, 10-dihydro-5, 10-dimethyl phenoxazine or tetrathiafulvalene.
2. The electrolyte of claim 1 wherein the metal salt solute is MClO 4 、MPF 6 、MBF 4 、MFSI、MTFSI、MBOB、MODFB、MODFP、MPO 2 F 2 Or CF (CF) 3 SO 3 M is any one or more of Li, na or K.
3. The electrolyte of claim 1, wherein the concentration of metal salt solute in the electrolyte is between 0.1mol/L and 5mol/L.
4. The electrolyte of claim 1, wherein the carbonate solvent is prepared from a cyclic carbonate and a chain carbonate according to 1: 3-3: 1 by volume ratio;
the cyclic carbonate is any one or more of vinylene carbonate, fluoroethylene carbonate, ethylene carbonate, propylene carbonate or ethylene carbonate;
the chain carbonic ester is any one or more of dimethyl carbonate, polycarbonate, methyl ethyl carbonate or diethyl carbonate.
5. The electrolyte of claim 1, wherein the redox mediator additive comprises 0.1% to 10% by mass of the electrolyte.
6. The electrolyte of claim 1, wherein the mass ratio of the metal salt solute, the carbonate solvent and the redox mediator additive is 1:1-19:0.002-2.
7. Use of the electrolyte according to any one of claims 1 to 6 in a metal ion battery, wherein the metal ion battery comprises any one of a sodium ion battery, a lithium ion battery or a potassium ion battery.
8. A metal ion battery comprising the electrolyte having a metal compensating effect according to any one of claims 1 to 6.
9. The metal-ion battery of claim 8, wherein the metal-ion battery further comprises a positive electrode, a negative electrode, and a separator.
10. The metal ion battery according to claim 8, wherein when the metal ion battery is a sodium ion battery, the positive electrode material is any one or more of sodium vanadium phosphate, sodium vanadium fluorophosphate, sodium iron pyrophosphate, sodium nickel manganese titanate or sodium nickel manganese iron titanate, the negative electrode is a sodium sheet, and the separator is a glass fiber separator;
when the metal ion battery is a lithium ion battery, the positive electrode material is any one or more of lithium iron phosphate, lithium iron manganese phosphate, lithium cobaltate or lithium manganate, the negative electrode is a sodium sheet, and the diaphragm is a glass fiber diaphragm;
when the metal ion battery is a potassium ion battery, the positive electrode material is any one or more of vanadium potassium phosphate, potassium manganate or potassium iron phosphate, the negative electrode is a sodium sheet, and the diaphragm is a glass fiber diaphragm.
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