CN112490421B - Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof - Google Patents
Cesium-doped potassium vanadium fluorophosphate/carbon cathode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 58
- QYPYOKIRTZEXEF-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[K+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[K+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F QYPYOKIRTZEXEF-UHFFFAOYSA-H 0.000 title claims abstract description 49
- 239000010406 cathode material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims abstract description 27
- 239000012002 vanadium phosphate Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 26
- 239000002243 precursor Substances 0.000 claims abstract description 23
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 20
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 20
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 19
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011591 potassium Substances 0.000 claims abstract description 18
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 10
- 239000011574 phosphorus Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 9
- 238000000576 coating method Methods 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 238000011065 in-situ storage Methods 0.000 claims abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011737 fluorine Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 18
- 229910001414 potassium ion Inorganic materials 0.000 claims description 17
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 16
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000000227 grinding Methods 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000011698 potassium fluoride Substances 0.000 claims description 9
- 235000003270 potassium fluoride Nutrition 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 239000003273 ketjen black Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 5
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 5
- 239000004254 Ammonium phosphate Substances 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 4
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 4
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 4
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 4
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Chemical compound [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 18
- 239000007774 positive electrode material Substances 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000003860 storage Methods 0.000 abstract description 2
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000005303 weighing Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- -1 cesium potassium vanadium fluorophosphate Chemical compound 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- QZRLETONGKUVFA-UHFFFAOYSA-N [K].[Cs] Chemical compound [K].[Cs] QZRLETONGKUVFA-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010532 solid phase synthesis reaction Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910021135 KPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention provides a cesium-doped potassium vanadium fluorophosphate/carbon cathode material and a preparation method and application thereof, wherein a vanadium source, a phosphorus source and a carbon source are subjected to wet ball milling and are uniformly mixed, the mixture is dried, ground and tabletted, and an obtained vanadium phosphate precursor is heated to 650-800 ℃ in an inert atmosphere to obtain vanadium phosphate; uniformly ball-milling and mixing vanadium phosphate, a cesium source, a potassium source and a fluorine source, and drying to obtain a cesium-doped potassium vanadium fluorophosphate precursor; heating the cesium-doped potassium vanadium fluorophosphate precursor to 550-700 ℃ in an inert atmosphere to obtain a cesium-doped potassium vanadium fluorophosphate/carbon positive electrode material; carbon source was used as reducing agent, V5+Reduction to V3+The reducing agent is excessive to reduce the pentavalent vanadium into 10-30% of the required amount of the trivalent vanadium, and the excessive carbon source is used for in-situ carbon coating. The material solves the problem of poor intrinsic electronic conductivity and ionic conductivity of potassium vanadium fluorophosphate by in-situ carbon coating and cesium ion doping modification, and effectively improves the potassium storage performance of the material.
Description
Technical Field
The invention relates to the field of potassium ion battery anode materials, in particular to a cesium-doped potassium vanadium fluorophosphate/carbon anode material as well as a preparation method and application thereof.
Background
Since the commercial application of the lithium ion battery in the 90 s of the 20 th century, the lithium ion battery is widely applied to electronic products, electric automobiles and large-scale energy storage systems, so that the shortage of lithium resources is aggravated, and the price of the lithium ion battery is increased. Therefore, the development of a novel energy storage battery with low cost and high performance is urgent. Potassium ion batteries have a relatively high energy density due to the proximity of potassium to the low standard redox potential of lithium (-2.93V versus standard electrode potential); and the potassium storage capacity in the earth's crust is abundant, resulting in a low cost of the potassium ion battery, and the potassium ion battery has rapid ion transport kinetics in the electrolyte, which all make the potassium ion battery have a superior prospect. In addition, aluminum foil can be used as a current collector in a potassium ion battery instead of copper foil in a lithium ion battery, which not only can significantly reduce the price of the potassium ion battery, but also can reduce the weight of the current collector and solve the over-discharge problem. Most importantly, the graphite can be used as a negative electrode of the potassium ion battery to embed potassium, which greatly accelerates the commercialization of the potassium ion battery. Then, as a key material in batteries, a high-performance positive electrode potassium storage material is important to be researched.
The potassium vanadium fluorophosphate has a stable open framework structure, can allow potassium ions to be reversibly de-intercalated and has small structural change, has high theoretical capacity and high working voltage, and is a promising potassium ion battery cathode material. But the electrochemical performance of the potassium vanadium fluorophosphate is seriously influenced due to the lower electronic conductivity and ionic conductivity of the potassium vanadium fluorophosphate, so that the potassium vanadium fluorophosphate is difficult to implement on a commercialized road.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a cesium-doped potassium vanadium fluorophosphate/carbon positive electrode material, and a preparation method and application thereof.
The invention is realized by the following technical scheme:
a preparation method of a cesium-doped potassium vanadium fluorophosphate/carbon cathode material comprises the following steps:
1) taking a vanadium source and a phosphorus source according to the ratio V to P being 1:1, and taking a carbon source;
2) adding the vanadium source, the phosphorus source and the carbon source in the step 1) into a ball milling tank, adding a solvent, and performing wet ball milling and mixing uniformly; drying the obtained mixture, grinding and tabletting to obtain a vanadium phosphate precursor;
3) heating the vanadium phosphate precursor in the step 2) to 650-800 ℃ at a heating rate of 2-10 ℃/min under an inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to obtain vanadium phosphate;
4) taking vanadium phosphate, cesium source, potassium source and fluorine source according to V, Cs, K, F, x, 1:1, performing wet ball milling, and uniformly mixing; drying the obtained mixture to obtain a cesium-doped potassium vanadium fluorophosphate precursor, and grinding and tabletting; wherein x is less than or equal to 0.1 and is not 0;
5) heating the cesium-doped potassium vanadium fluorophosphate precursor in the step 4) to 550-700 ℃ at a heating rate of 2-10 ℃/min under an inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to obtain the cesium-doped potassium vanadium fluorophosphate cathode material;
step 3) carbon source is used as reducing agent, V5+Reduction to V3+The reducing agent is excessive to reduce the pentavalent vanadium into 10-30% of the required amount of the trivalent vanadium, and the excessive carbon source is used for in-situ carbon coating.
Preferably, the vanadium source in the step 1) is one or two of ammonium metavanadate and vanadium pentoxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the carbon source is one or more of Super P, Ketjen black and acetylene black.
Preferably, the solvent used in the wet ball milling in step 2) and step 4) is one or both of ethanol and water.
Preferably, the ball milling speed in the step 2) and the step 4) is 300-600 r/min, and the ball milling time is 4-24 h.
Preferably, the cesium source in step 4) is one or more of cesium fluoride, cesium chloride and cesium bromide; the potassium source is one or more of potassium fluoride, potassium chloride, potassium bromide, potassium carbonate, potassium hydroxide and potassium nitrate; the fluorine source is one or more of potassium fluoride, ammonium fluoride, sodium fluoride and cesium fluoride.
Preferably, the inert atmosphere in step 3) and step 5) is one or both of argon and nitrogen.
The cesium-doped potassium vanadium fluorophosphate/carbon cathode material prepared by the preparation method.
The cesium-doped potassium vanadium fluorophosphate/carbon cathode material is applied to a potassium ion battery.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention adopts a strategy of simultaneously improving the electronic conductivity and the ionic conductivity of the material, and prepares the cesium-doped potassium vanadium fluorophosphate/carbon composite material by a high-temperature solid-in-situ carbon coating and potassium-cesium doping method. 1) The cesium-doped potassium vanadium fluorophosphate material disclosed by the invention is high in purity, uniform in granularity and excellent in electrochemical performance. Cs and potassium are elements of the same main group and have many similar properties, and Cs is adopted+(0.167nm) Ionic partial substitution of K+Ions (0.137nm) can change diffusion channels of the material, enlarge the distance between layers, cause the expansion of ion migration channels, and effectively reduce K in the material+Transition potential barrier of ion, enhanced K+The rate of ion diffusion. 2) According to the invention, the electron conductivity of the material is improved through in-situ carbon coating; 3) the preparation method of the cesium-doped potassium vanadium fluorophosphate has the advantages of simple process, low production cost and easy realization of large-scale production, and has important significance for commercialization of potassium ion batteries.
According to the cesium-doped potassium vanadium fluorophosphate/carbon composite material prepared by the method, the crystal structure of the potassium vanadium fluorophosphate is not influenced by trace cesium doping through X-ray diffraction test, X-ray photoelectron spectroscopy also shows that cesium is successfully doped, and meanwhile, an electrochemical performance test result shows that the electrochemical performance of the material can be effectively improved by trace cesium doping, and the cycle performance is remarkably enhanced.
Drawings
FIG. 1 is a microscopic SEM image of a sample of example 1 of the present invention;
FIG. 2 is an XRD pattern of a sample of example 1 of the present invention;
FIG. 3 is an XPS spectrum of a sample of example 1 of the present invention;
FIG. 4 is a graph of electrochemical performance of undoped samples of examples 1, 2, 3 of the present invention and comparative examples.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The preparation method of the cesium-doped potassium vanadium fluorophosphate/carbon cathode material is prepared by adopting a high-temperature solid phase method through the following steps of:
1) weighing equal moles of a vanadium source compound, a phosphorus source compound and a certain amount of a carbon source;
2) adding the vanadium source, the phosphorus source and the carbon source in the step 1) into a ball milling tank, adding a solvent, and uniformly mixing the mixture at a certain rotating speed; drying the mixture in an oven at 60-120 ℃ for 10-24 h, grinding and tabletting to obtain a vanadium phosphate precursor;
3) transferring the vanadium phosphate precursor in the step 2) to a tubular furnace, heating to 650-800 ℃ at a heating rate of 2-10 ℃/min under an inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to obtain vanadium phosphate;
4) weighing vanadium phosphate, a cesium source compound, a potassium source compound and a fluorine source compound in the step 3) according to a molar ratio of V: P: Cs: K: F ═ 1:1: x:1:1(x is less than or equal to 0.1), transferring the materials to a ball milling pot, adding a solvent, and uniformly mixing; drying the mixture in an oven at the temperature of 60-120 ℃ for 10-24 h to obtain a cesium-doped potassium vanadium fluorophosphate precursor, and grinding and tabletting;
5) transferring the flaky cesium-doped potassium vanadium fluorophosphate precursor in the step 4) into a tube furnace, heating to 550-700 ℃ at the heating rate of 2-10 ℃/min under the inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to finally obtain the cesium-doped potassium vanadium fluorophosphate/carbon cathode material.
In the step 1), the vanadium source compound is one or more of ammonium metavanadate and vanadium pentoxide; the phosphorus source compound is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the carbon source is one or more of Super P, Ketjen black and acetylene black.
The solvent used for ball milling mixing in the step 2) and the step 4) is one or two of ethanol and water.
In the step 2) and the step 4), the running speed of the ball mill is 300-600 r/min, and the ball milling time is 4-24 h.
The cesium source compound in the step 4) is one or more of cesium fluoride, cesium chloride and cesium bromide; the potassium source compound is one or more of potassium fluoride, potassium chloride, potassium bromide, potassium carbonate, potassium hydroxide and potassium nitrate; the fluorine source compound is one or more of potassium fluoride, ammonium fluoride, sodium fluoride and cesium fluoride.
And in the step 3) and the step 5), the inert atmosphere is one or more of argon and nitrogen.
The carbon source in step 1) is used as a reducing agent, V5+Reduction to V3+The reducing agent should be excessive to reduce pentavalent vanadium to trivalent vanadium by 10-30%, and the excessive carbon source is used for in-situ carbon coating.
Example 1
The positive electrode material of the cesium potassium vanadium fluorophosphate type potassium battery in the embodiment has the following expression: k0.98Cs0.02VPO4F/C。
Weighing 0.1mol of vanadium pentoxide, 0.2mol of diammonium hydrogen phosphate and 0.25mol of acetylene black, adding the weighed materials into a ball milling tank, adding 15ml of water, starting a planetary ball mill, ball milling for 12 hours at 600r/min to uniformly mix the mixture, drying the mixture in a drying oven at 100 ℃ for 12 hours, grinding and tabletting, transferring a vanadium phosphate precursor into a tube furnace, heating to 750 ℃ at a heating rate of 4 ℃/min under an argon atmosphere, keeping the temperature for 4 hours, and naturally cooling to room temperature to obtain the vanadium phosphate/carbon composite material. Transferring the obtained vanadium phosphate/carbon composite material, 0.004mol of cesium fluoride, 0.196mol of potassium chloride and 0.196mol of ammonium fluoride to a ball milling tank, starting a planetary ball mill, uniformly mixing the mixture in a ball milling process for 24h at 400r/min, drying the mixture in an oven at 80 ℃ for 12h, grinding and tabletting, transferring a cesium-doped potassium vanadium fluorophosphate precursor to a tubular furnace, heating to 650 ℃ at a heating rate of 4 ℃/min under an argon atmosphere, keeping the temperature for 6h, naturally cooling to room temperature, and finally obtaining K0.98Cs0.02VPO4F/C cathode material.
Example 2
The positive electrode material of the cesium potassium vanadium fluorophosphate type potassium battery in the embodiment has the following expression: k0.95Cs0.05VPO4F/C。
0.1mol of vanadium pentoxide and 0.2mol of ammonium phosphate are weighed, andadding 0.22mol of Ketjen black into a ball milling tank, adding 15ml of ethanol, starting a planetary ball mill, ball milling for 24h at 400r/min, uniformly mixing the mixture, drying the mixture in an oven at 80 ℃ for 20h, grinding and tabletting, transferring a vanadium phosphate precursor into a tube furnace, heating to 700 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping the temperature for 6h, and naturally cooling to room temperature to obtain the vanadium phosphate/carbon composite material. Transferring the obtained vanadium phosphate/carbon composite material, 0.01mol of cesium chloride, 0.1mol of potassium fluoride and 0.09mol of ammonium fluoride to a ball milling tank, starting a planetary ball mill, uniformly mixing the mixture in a ball milling way for 24 hours at 300r/min, drying the mixture in an oven at 80 ℃ for 12 hours, grinding and tabletting, transferring a cesium-doped potassium vanadium fluorophosphate precursor to a tubular furnace, heating to 650 ℃ at a heating rate of 3 ℃/min under an argon atmosphere, keeping the temperature for 4 hours, naturally cooling to room temperature, and finally obtaining K0.95Cs0.05VPO4F/C cathode material.
Example 3
The positive electrode material of the cesium potassium vanadium fluorophosphate type potassium battery in the embodiment has the following expression: k0.92Cs0.08VPO4F/C。
Weighing 0.2mol of ammonium metavanadate, 0.2mol of ammonium dihydrogen phosphate and 0.23mol of Ketjen black, adding into a ball milling tank, adding 15ml of ethanol, starting a planetary ball mill, ball milling for 24h at 400r/min, uniformly mixing the mixture, drying the mixture in an oven at 80 ℃ for 12h, grinding and tabletting, transferring a vanadium phosphate precursor into a tube furnace, heating to 750 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the vanadium phosphate/carbon composite material. Transferring the obtained vanadium phosphate/carbon composite material, 0.016mol of cesium fluoride and 0.184mol of potassium fluoride to a ball milling tank, starting a planetary ball mill, uniformly mixing the mixture after ball milling for 20h at 500r/min, drying the mixture in an oven at 80 ℃ for 10h, grinding and tabletting, transferring a cesium-doped potassium vanadium fluorophosphate precursor to a tube furnace, heating to 650 ℃ at a heating rate of 4 ℃/min under an argon atmosphere, keeping the temperature for 8h, naturally cooling to room temperature, and finally obtaining K0.92Cs0.08VPO4F/C cathode material.
Comparative example
The anode material of the potassium vanadium fluorophosphate type potassium battery has the following expression: KVPO4F/C。
Weighing 0.2mol of ammonium metavanadate, 0.2mol of ammonium dihydrogen phosphate and 0.25mol of Ketjen black, adding into a ball milling tank, adding 15ml of ethanol, starting a planetary ball mill, ball milling for 24h at 400r/min, uniformly mixing the mixture, drying the mixture in an oven at 80 ℃ for 12h, grinding and tabletting, transferring a vanadium phosphate precursor into a tube furnace, heating to 750 ℃ at a heating rate of 2 ℃/min under an argon atmosphere, keeping the temperature for 4h, and naturally cooling to room temperature to obtain the vanadium phosphate/carbon composite material. Transferring the obtained vanadium phosphate/carbon composite material and 0.2mol of potassium fluoride to a ball milling tank, starting a planetary ball mill, uniformly mixing the mixture by ball milling for 20h at 500r/min, drying the mixture for 10h in an oven at 80 ℃, grinding and tabletting, transferring a potassium vanadium fluorophosphate precursor to a tube furnace, heating to 650 ℃ at the heating rate of 4 ℃/min under the argon atmosphere, keeping the temperature for 8h, naturally cooling to room temperature, and finally obtaining the cesium-undoped KVPO4F/C cathode material.
For K prepared in example 10.95Cs0.05VPO4A series of physical property characterizations are carried out on the F/C material, and the results are shown in the figure. Wherein FIG. 1 is K0.95Cs0.05VPO4SEM image of F/C material, which shows that the prepared material is micron-sized. FIG. 2 is K0.95Cs0.05VPO4The XRD pattern of the F/C material shows that trace cesium doping does not affect the crystal structure of the potassium vanadium fluorophosphate through the X-ray diffraction test result, and the X-ray photoelectron spectroscopy (figure 3XPS) also shows that cesium is successfully doped to KVPO4And F, performing the following steps.
The cesium-doped potassium vanadium fluorophosphate/carbon material prepared in examples 1 to 3, a conductive agent super P and a binder PVDF are mixed according to a mass ratio of 7:2:1 and then dissolved in NMP, the slurry is laid on an aluminum foil, dried and rolled, and then a cut piece is taken as a positive electrode, a metal potassium piece is taken as a negative electrode, a glass fiber membrane is taken as a diaphragm, a solute is 1M KPF6, a solvent is a mixture of EC (ethylene carbonate) and DEC (diethyl carbonate) (mass ratio of 1:1), an additive is FEC (forward-forward chemical) with a mass fraction of 2% is taken as an electrolyte, the aluminum foil is taken as a current collecting plate, a CR2025 button potassium ion battery is assembled, and an electrochemical performance curve test is carried out. As shown in fig. 4, the cesium-doped sample is subjected to a constant current charge and discharge test at a current density of 1C, and after trace cesium doping and in-situ carbon coating, the specific capacity and the cycling stability of the material are significantly improved. After circulating for 100 circles, the capacities of the comparative example and the examples 1, 2 and 3 are respectively maintained at 74.3mAh/g, 82.7mAh/g, 97.1mAh/g and 90.0mAh/g, which shows that the electrochemical performance of the material can be effectively improved by the trace cesium doping.
Aiming at the defects of potassium vanadium fluorophosphate and the current research situation, the invention adopts a strategy of simultaneously improving the electronic conductivity and the ionic conductivity of the material, and prepares the cesium-doped potassium vanadium fluorophosphate/carbon composite material by combining the in-situ carbon coating and the potassium cesium doping modification through a high-temperature solid phase method, thereby obviously improving the electrochemical performance of the potassium vanadium fluorophosphate and having important significance for the commercialization of potassium ion batteries.
Claims (8)
1. A preparation method of a cesium-doped potassium vanadium fluorophosphate/carbon cathode material is characterized by comprising the following steps of:
1) taking a vanadium source and a phosphorus source according to the ratio V to P being 1:1, and taking a carbon source;
2) adding the vanadium source, the phosphorus source and the carbon source in the step 1) into a ball milling tank, adding a solvent, and performing wet ball milling and mixing uniformly; drying the obtained mixture, grinding and tabletting to obtain a vanadium phosphate precursor;
3) heating the vanadium phosphate precursor in the step 2) to 650-800 ℃ at a heating rate of 2-10 ℃/min under an inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to obtain vanadium phosphate;
4) taking vanadium phosphate, cesium source, potassium source and fluorine source according to V, Cs, K, F, x, 1:1, performing wet ball milling, and uniformly mixing; drying the obtained mixture to obtain a cesium-doped potassium vanadium fluorophosphate precursor, and grinding and tabletting; wherein x is less than or equal to 0.1 and is not 0;
5) heating the cesium-doped potassium vanadium fluorophosphate precursor in the step 4) to 550-700 ℃ at a heating rate of 2-10 ℃/min under an inert atmosphere, keeping the temperature for 1-10 h, and naturally cooling to room temperature to obtain the cesium-doped potassium vanadium fluorophosphate/carbon cathode material;
step 3) carbon source is used as reducing agent, V5+Reduction to V3+The reducing agent is excessive to reduce the pentavalent vanadium into 10-30% of the required amount of the trivalent vanadium, and the excessive carbon source is used for in-situ carbon coating.
2. The preparation method of the cesium-doped potassium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein in step 1), the vanadium source is one or two of ammonium metavanadate and vanadium pentoxide; the phosphorus source is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate and ammonium phosphate; the carbon source is one or more of Super P, Ketjen black and acetylene black.
3. The method for preparing the cesium doped potassium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein a solvent used for wet ball milling in the step 2) and the step 4) is one or both of ethanol and water.
4. The preparation method of the cesium-doped potassium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the ball milling speed in the step 2) and the step 4) is 300-600 r/min, and the ball milling time is 4-24 h.
5. The method for preparing the cesium-doped potassium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein in the step 4), the cesium source is one or more of cesium fluoride, cesium chloride and cesium bromide; the potassium source is one or more of potassium fluoride, potassium chloride, potassium bromide, potassium carbonate, potassium hydroxide and potassium nitrate; the fluorine source is one or more of potassium fluoride, ammonium fluoride, sodium fluoride and cesium fluoride.
6. The preparation method of the cesium doped potassium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the inert atmosphere in the steps 3) and 5) is one or two of argon and nitrogen.
7. The cesium-doped potassium vanadium fluorophosphate/carbon cathode material produced by the production method described in any one of claims 1 to 6.
8. Use of the cesium doped potassium vanadium fluorophosphate/carbon cathode material of claim 7 in a potassium ion battery.
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