CN110600731A - Potassium ion battery positive electrode material, potassium ion battery and preparation method - Google Patents

Potassium ion battery positive electrode material, potassium ion battery and preparation method Download PDF

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CN110600731A
CN110600731A CN201910841426.2A CN201910841426A CN110600731A CN 110600731 A CN110600731 A CN 110600731A CN 201910841426 A CN201910841426 A CN 201910841426A CN 110600731 A CN110600731 A CN 110600731A
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potassium
ion battery
potassium ion
carbonate
electrolyte
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CN110600731B (en
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唐永炳
何海燕
姚文娇
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Shenzhen Institute of Advanced Technology of CAS
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Shenzhen Institute of Advanced Technology of CAS
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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
    • 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
    • H01M10/056—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
    • H01M10/0569—Liquid materials characterised by the solvents
    • 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
    • H01M10/058—Construction or manufacture
    • 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
    • H01M4/582—Halogenides
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Manufacturing & Machinery (AREA)
  • Inorganic Chemistry (AREA)
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  • General Physics & Mathematics (AREA)
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  • Secondary Cells (AREA)

Abstract

The invention provides a KVOF (KVOF) positive electrode material of a potassium ion battery3Due to KVOF3The material synthesis process is simple, the synthesized potassium ion battery anode material has high purity, the structure is kept stable in the process of potassium ion embedding/de-embedding, the potassium ion battery anode material can be used in the potassium ion battery, and the prepared potassium ion battery has high capacity, good cycle stability, higher charge-discharge voltage platform and higher energy density. In addition, the invention also provides a preparation method of the potassium ion battery, which is simple and easy to operate, has low cost and low requirement on equipment, and is suitable for large-scale industrial production.

Description

Potassium ion battery positive electrode material, potassium ion battery and preparation method
Technical Field
The invention relates to the technical field of batteries, in particular to a potassium ion battery positive electrode material, a potassium ion battery and a preparation method.
Background
The secondary battery is a battery which can be repeatedly charged and discharged and used for many times. Compared with a primary battery which can not be repeatedly used, the secondary battery has the advantages of low cost and small environmental pollution. The main secondary battery technologies at present include lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, lithium ion batteries, and novel secondary ion batteries derived from lithium ion batteries, such as sodium ion batteries and potassium ion batteries. The lithium ion battery has the advantages of high energy density, high energy efficiency, long cycle life, no memory effect, quick charge and discharge and the like, and has huge market demands in the fields of movable electronic products, electric vehicles, power grid peak shaving, energy storage power supplies, aerospace and the like. However, with the increasing consumption of lithium resources, the cost of lithium raw materials is rising sharply, which limits the widespread use of lithium-based energy storage devices in the future. Therefore, it is important to develop a next-generation low-cost, high-performance energy storage system.
Sodium ion batteries and potassium ion batteries, which are abundant in natural resources and relatively inexpensive, have attracted great attention of researchers. Compared with sodium ion batteries, the standard electrode potential of potassium is closer to that of lithium, so that a high energy density energy storage system is more easily obtained; in addition, the stokes radius of the solvated potassium ions is smaller, and the potassium-based electrolyte has higher ion conductivity, which enables the potassium ions to be inserted into the electrode at an ultrahigh rate; in addition, the potassium ion battery can use cheap graphite as a negative electrode, so that the production cost is further reduced. Based on the advantages, the potassium ion battery and the related energy storage equipment have good development potential.
At present, the electrochemical performance of the potassium ion battery based on the developed materials is not ideal, and the preparation process is complex, mainly because the types and the performances of the related positive electrode materials are very limited.
The Chinese invention patent application No. CN201710429318.5 proposes that the potassium ion battery anode material of the Prussian blue analogue has unstable structure due to the unstable crystal water; the Chinese patent application No. CN201811228311.8 proposes that the morphology modification based on the Prussian blue compound causes difficulty in large-scale production and manufacturing due to the complex and repeatable low synthetic method; the Chinese invention patent application No. CN 105826521A proposes that the energy density of the positive electrode material of the potassium ion battery of polyanion compound is lower and is not suitable for industrial application; chinese patent application No. CN201611217148.6 proposes a metal oxide positive electrode material for a potassium ion battery, which is not favorable for industrial production due to its low actual density.
At present, the research on the positive electrode material of the potassium ion battery is still in the initial stage, and the development of a novel high-performance positive electrode material of the potassium ion battery is urgently needed.
Disclosure of Invention
In view of the above, there is a need to provide a positive electrode material for a potassium ion battery, which has high capacity, good cycling stability, high charging and discharging voltage plateau, and high energy density, in order to overcome the defects in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a potassium ion battery positive electrode material, which comprises KVOF3。
On the other hand, the invention also provides a potassium ion battery, which comprises a battery cathode, a diaphragm, electrolyte and a battery anode which are sequentially arranged, wherein the battery cathode comprises a cathode current collector layer and an anode active material layer, the electrolyte comprises electrolyte potassium salt and a solvent, the battery anode comprises an anode active material layer and an anode current collector layer, the anode active material layer comprises the potassium ion battery anode material, and the potassium ion battery anode material comprises KVOF3。
In some preferred embodiments, the negative current collector layer comprises a metal conductive material, and the metal conductive material comprises one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy of the above metals or a composite material comprising the above metals.
In some preferred embodiments, the negative active material layer includes a negative active material that is at least one of artificial graphite, natural graphite, spherulitic graphite, crystalline flake graphite, MCMB, soft carbon, hard carbon, graphite fluoride, mesocarbon microbeads, petroleum coke, carbon brazes, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys, carbon nanotubes, nanoalloy materials, nanooxide materials, triiron tetroxide, trimong tetroxide, alpha-ferric oxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide, and vanadium sulfide.
In some preferred embodiments, the negative active material layer further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
In some preferred embodiments, the content of the negative active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
In some preferred embodiments, the electrolyte potassium salt comprises potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonylimide, KCF3SO3、KN(SO2CF3)2At least one of the above, the concentration range of the electrolyte potassium salt is 0.1-10 mol/L.
In some preferred embodiments, the solvent comprises propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, dimethyl carbonate, methyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethylmethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, salt, One or more of N-methyl-N-propyl pyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt and N-methyl, butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
In some preferred embodiments, the electrolyte further comprises an additive comprising fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromo butyrolactone, fluoroacetoxyethane, fluoro alkyl ether, and mixtures thereof, Phosphate, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and lithium carbonate, wherein the additive is added into the electrolyte in an amount of 0.1-20 wt%.
In some preferred embodiments, the positive active material layer further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefins.
In some preferred embodiments, the content of the potassium ion battery positive electrode material is 60-90 wt%, the content of the conductive agent is 5-30 wt%, and the content of the binder is 5-10 wt%.
In some preferred embodiments, the positive current collector layer includes a metal conductive material, and the metal conductive material includes one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy of the above metals or a composite material including the above metals.
In some preferred embodiments, the separator is an insulating porous polymer film or an inorganic porous film, the porous polymer film is one or more of a porous polypropylene film, a porous polyethylene film or a porous composite polymer film, and the inorganic porous film is one or more of a glass fiber paper or a porous ceramic separator.
In addition, the invention also provides a preparation method of the potassium ion battery, which is characterized by comprising the following steps:
uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting after the negative electrode active material layer is dried to obtain a battery negative electrode;
drying the diaphragm and then cutting to obtain a diaphragm with a certain size;
dissolving the electrolyte potassium salt in a solvent to form the electrolyte solution;
cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is dried to obtain a battery positive electrode;
assembling the battery cathode, the electrolyte, the diaphragm and the battery anode to obtain the potassium ion battery;
the positive active material layer comprises the potassium ion battery positive material, and the potassium ion battery positive material comprises KVOF3。
The invention adopts the technical scheme that the method has the advantages that:
the potassium ion battery anode material provided by the invention comprises KVOF3Due to KVOF3The material synthesis process is simple, the synthesized potassium ion battery anode material has high purity, the structure is kept stable in the process of potassium ion intercalation/deintercalation, the potassium ion battery anode material can be used in the potassium ion battery, and the prepared potassium ion battery has high capacity, good cycle stability, high charge-discharge voltage platform and high energy density.
In addition, the preparation method of the potassium ion battery provided by the invention is simple and easy to operate, low in cost, low in equipment requirement and suitable for large-scale industrial production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 shows an embodiment of the invention providing a KVOF3A comparison of the XRD pattern of the sample with a standard XRD pattern.
FIG. 2 shows an embodiment of the invention providing a KVOF3Optical photograph of the sample.
FIG. 3 shows an embodiment of the invention providing KVOF3Thermogravimetric plot of the sample.
FIG. 4 shows an embodiment of the invention providing KVOF3Infrared vibration spectrum of the sample.
Fig. 5 is a schematic structural diagram of a potassium ion battery according to an embodiment of the present invention.
Fig. 6 is a flowchart illustrating steps of a method for manufacturing a potassium ion battery according to an embodiment of the present invention.
Fig. 7 is a charge-discharge curve diagram of the potassium ion battery prepared in the embodiment of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The potassium ion battery anode material provided by the invention comprises KVOF3Due to KVOF3The material synthesis process is simple, the purity of the synthesized potassium ion battery anode material is high, the structure is kept stable in the process of potassium ion embedding/de-embedding, and the prepared potassium ion battery is high in capacity, good in cycling stability, high in charge-discharge voltage platform and high in energy density.
Please refer to fig. 1, which illustrates a kvaf according to an embodiment of the present invention3Comparison of the XRD pattern of the sample with the standard XRD pattern, it can be seen from FIG. 1 that the KVOF provided by the example of the present invention3The purity of the sample is very high.
Please refer to fig. 2, which illustrates a kvaf according to an embodiment of the present invention3Optical photograph of the sample, KVOF can be seen in FIG. 23The sample is a regular elongated crystal with high purity.
Please refer to fig. 3, which illustrates a kvaf according to an embodiment of the present invention3Thermogravimetric plot of the sample, as can be seen from FIG. 3, KVOF3The samples had better thermal stability, and the samples started to decompose only after the temperature reached 420 ℃.
Please refer to fig. 4, which illustrates a kvaf according to an embodiment of the present invention3Infrared vibration spectrum of the sample. As can be seen from FIG. 4, several strong absorption peaks are generated by the vibration of the V-O, V-F, K-F, K-O bond, respectively, and KVOF3The sample structure corresponds.
Referring to fig. 5, the present invention also provides a potassium ion battery,including the negative current collector layer 110, the negative active material layer 120, electrolyte 130, the positive active material layer 140 and the positive current collector layer 150 that set gradually, be equipped with diaphragm 160 in the electrolyte, electrolyte 130 includes the electrolyte, the electrolyte includes the electrolyte potassium salt, the positive active material layer 140 includes potassium ion battery cathode material, potassium ion battery cathode material includes KVOF3。
The working principle of the potassium ion battery provided by the embodiment of the invention is as follows: in the charging process, potassium ions in the positive electrode are transferred to the electrolyte, and potassium ions in the electrolyte are transferred to the negative electrode; in the discharging process, potassium ions return to the anode material from the electrolyte, and simultaneously, the potassium ions are separated from the cathode and return to the electrolyte, so that the whole charging and discharging process is realized.
In some preferred embodiments, the negative current collector layer 110 comprises a metal conductive material including one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy thereof, or a composite thereof.
In some preferred embodiments, the positive current collector layer 150 comprises a metal conductive material including one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy thereof, or a composite thereof.
Further, in the full cell, the negative current collector layer 110 is preferably metallic copper, and the positive current collector layer 150 is preferably aluminum; in a half cell, the negative electrode is preferably a potassium or lithium plate, no current collector is required, and the positive current collector layer 150 is preferably aluminum.
In some preferred embodiments, the negative active material layer 120 includes a negative active material that is at least one of artificial graphite, natural graphite, spherulitic graphite, crystalline flake graphite, MCMB, soft carbon, hard carbon, graphite fluoride, mesocarbon microbeads, petroleum coke, carbon fibrils, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys, carbon nanotubes, nano-alloy materials, nano-oxide materials, triiron tetroxide, trimong tetroxide, alpha-ferric oxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide, and vanadium sulfide.
In some preferred embodiments, the negative active material layer 120 further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
Further, the content of the negative active material is 60-90 wt%, the content of the conductive agent is 5-30 wt%, and the content of the binder is 5-10 wt%.
In some preferred embodiments, the electrolyte potassium salt comprises potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonylimide, KCF3SO3、KN(SO2CF3)2At least one of the above, the concentration range of the electrolyte potassium salt is 0.1-10 mol/L.
Further, the electrolyte potassium salt is potassium hexafluorophosphate.
In some preferred embodiments, the solvent comprises propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, dimethyl carbonate, methyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethylmethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, salt, One or more of N-methyl-N-propyl pyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt and N-methyl, butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
In some preferred embodiments, the electrolyte further comprises an additive comprising fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethylcarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromo butyrolactone, fluoroacetoxyethane, fluoro alkyl ether, and mixtures thereof, Phosphate, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and lithium carbonate, wherein the additive is added into the electrolyte in an amount of 0.1-20 wt%.
It is understood that the additive added in the electrolyte 130 may form a stable solid electrolyte film on the surface of the anode, improving the cycle life of the battery.
In some preferred embodiments, the positive active material layer further includes a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefins.
In some preferred embodiments, the content of the potassium ion battery positive electrode material is 60-90 wt%, the content of the conductive agent is 5-30 wt%, and the content of the binder is 5-10 wt%.
In some preferred embodiments, the separator 160 is an insulating porous polymer film or an inorganic porous film, the porous polymer film is one or more of a porous polypropylene film, a porous polyethylene film or a porous composite polymer film, and the inorganic porous film is one or more of a glass fiber paper or a porous ceramic separator.
Understandably, due to KVOF3The material synthesis process is simple, the purity of the synthesized potassium ion battery anode material is high, the structure is kept stable in the process of potassium ion embedding/de-embedding, and the prepared potassium ion battery is high in capacity, good in cycling stability, high in charge-discharge voltage platform and high in energy density.
Referring to fig. 6, the present invention further provides a method for manufacturing the potassium ion battery, including the following steps:
step S110: uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting after the negative electrode active material layer is dried to obtain a battery negative electrode;
step S120: drying the diaphragm and then cutting to obtain a diaphragm with a certain size;
step S130: dissolving the electrolyte potassium salt in a solvent to form the electrolyte with a certain concentration;
it will be appreciated that suitable additives may also be added to the electrolyte as required.
Step S140: cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is dried to obtain a battery positive electrode;
step S150: assembling the battery cathode, the diaphragm, the electrolyte and the battery anode to obtain the potassium ion battery;
the electrolyte comprises electrolyte, the electrolyte comprises electrolyte sylvite, the positive active material layer comprises the potassium ion battery positive electrode material, the potassium ion battery positive electrode material comprises KVOF3。
It should be noted that, although the above steps S110 to S130 describe the operations of the preparation method of the present invention in a specific order, this does not require or imply that these operations must be performed in this specific order. The preparation of steps S110-130 may be performed simultaneously or in any order.
The preparation method of the potassium ion battery provided by the invention is simple and easy to operate, low in cost, low in equipment requirement and suitable for large-scale industrial production.
The potassium ion battery prepared by the invention can be applied to the fields of electric vehicles, energy storage batteries, power batteries, energy storage power stations and the like.
The technical solution is described in detail below with reference to specific examples.
Example 1: based on KVOF3Positive potassium ion half cell
Preparing a battery cathode: rolling the metal potassium block into metal potassium sheets, cutting the metal potassium sheets into round sheets with the diameter of 12mm, and using the round sheets as negative electrodes for standby.
Preparing a diaphragm: the glass fiber diaphragm is cut into a circular piece with the diameter of 16mm, and the circular piece is dried to be used as the diaphragm for standby.
Preparing a battery positive electrode: 0.6g of ball-milled KVOF3Adding the crystal powder, 0.3g of conductive carbon black and 0.1g of polyvinylidene fluoride into 3mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; then theAnd (3) uniformly coating the slurry on the surface of the carbon-coated aluminum foil and performing vacuum drying. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a positive electrode for standby.
Preparing an electrolyte: 1.8g of potassium hexafluorophosphate was weighed and added to 10mL of a mixed solvent of trimethylacetyl chloride and dimethyl carbonate (volume ratio: 1), stirred until the potassium hexafluorophosphate was completely dissolved, and sufficiently and uniformly stirred to be used as an electrolyte (electrolyte concentration: 1M).
Assembling the battery: and (3) tightly stacking the prepared battery cathode, the diaphragm and the battery anode in turn in a glove box protected by inert gas, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button cell shell to finish the battery assembly.
Referring to fig. 7, it can be seen from fig. 7 that the stable charging and discharging curve of the potassium ion battery prepared in this embodiment at 100mA/g is shown, the capacity of the potassium ion battery is high, the cycling stability is good, the charging and discharging voltage plateau is high, and the energy density is high.
Example 2: based on KVOF3Positive potassium ion full cell
Preparing a battery cathode: adding 0.8g of MCMB, 0.1g of conductive carbon black and 0.1g of polyvinylidene fluoride into 3ml of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; the slurry was then uniformly coated on the aluminum foil surface (i.e., the negative current collector) and vacuum dried. And cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery cathode for standby.
Preparing a diaphragm: the glass fiber diaphragm is cut into a circular piece with the diameter of 16mm, and the circular piece is dried to be used as the diaphragm for standby.
Preparing a battery positive electrode: 0.6g of ball-milled KVOF3Adding the crystal powder, 0.3g of conductive carbon black and 0.1g of polyvinylidene fluoride into 3mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; then the slurry is evenly coated on the surface of the carbon-coated aluminum foil and dried in vacuum. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a positive electrode for standby.
Preparing an electrolyte: 1.8g of potassium hexafluorophosphate was weighed and added to 10mL of a mixed solvent of trimethylacetyl chloride and dimethyl carbonate (volume ratio: 1), stirred until the potassium hexafluorophosphate was completely dissolved, and sufficiently and uniformly stirred to be used as an electrolyte (electrolyte concentration: 1M).
Assembling the battery: and (3) tightly stacking the prepared battery cathode, the diaphragm and the battery anode in turn in a glove box protected by inert gas, dripping electrolyte to completely soak the diaphragm, and packaging the stacked part into a button cell shell to finish the battery assembly.
Example 3
A potassium ion battery, wherein the positive electrode active material KVOF30.7g of crystal powder and 0.2g of conductive carbon black, and other components are the same as those in example 2 and are not described again.
Example 4
A potassium ion battery, wherein the positive electrode active material KVOF3The crystal powder was 0.75g, and the conductive carbon black was 0.15g, and the rest was the same as in example 2, and thus, the description thereof is omitted.
Example 5
A potassium ion battery, wherein the solvent used in the electrolyte is trimethyl acetyl chloride, and the rest is the same as the example 2, and the description is omitted.
Example 6
A potassium ion battery is disclosed, wherein the electrolyte uses ethyl methyl carbonate, dimethyl carbonate and ethylene carbonate (volume ratio 1:1:1), and the rest is the same as example 2, and the description is omitted.
Example 7
A potassium ion battery, wherein the solvent used in the electrolyte is trimethyl acetyl chloride, and fluoroethylene carbonate is added as an additive (volume ratio 9:1), the rest is the same as example 2, and the description is omitted.
Example 8
A potassium ion battery, wherein the electrolyte uses ethyl methyl carbonate and ethylene carbonate (volume ratio 1:1) as solvent, the others are the same as example 2, and the description is omitted here.
Example 9
A potassium ion battery, wherein the electrolyte uses dimethyl carbonate and ethylene carbonate (volume ratio 1:1), other is the same as example 2, and will not be repeated here.
Example 10
A potassium ion battery, wherein the electrolyte uses trimethyl acetyl chloride and ethylene carbonate (volume ratio 1:1), other is the same as example 2, and the description is omitted here.
Example 11
A potassium ion battery, wherein the electrolyte concentration is 0.5M, and the rest is the same as that of the embodiment 2, and the description is omitted.
Example 12
A potassium ion battery, wherein the electrolyte concentration is 0.8M, and the rest is the same as that of the embodiment 2, and the description is omitted.
Example 13
The other parts of the potassium ion battery are the same as those of the embodiment 2, and the description is omitted.
Example 14
A potassium ion battery, wherein the conductive agent in the positive active material layer adopts conductive graphite, and the rest is the same as the embodiment 2, and the description is omitted.
Example 15
A potassium ion battery, wherein the negative active material MCMB is 0.75g, the conductive carbon black is 0.15g, and other components are the same as those in example 2, and are not described again.
Example 16
A potassium ion battery, wherein the negative electrode current collector is copper foil, the rest is the same as the embodiment 2, and the description is omitted.
Example 17
The potassium ion battery adopts natural graphite as the active material of the negative electrode material, and the rest is the same as the embodiment 2, and the description is omitted.
Example 18
A potassium ion battery, wherein the conductive agent in the negative active material layer adopts conductive graphite, and the rest is the same as the embodiment 2, and the description is omitted.
Example 19
A potassium ion battery in which the electrolyte salt is potassium tetrafluoroborate, the rest being the same as in example 2, and will not be described herein.
Example 20
A potassium ion battery, wherein the diaphragm adopts a porous polypropylene film, and the rest is the same as the example 2, and the description is omitted.
Comparative example 1
A potassium ion battery is prepared from KMnO2In place of KVOF3The rest of the positive electrode active material was the same as in example 2.
Comparative example 2
A potassium ion battery, wherein K is adopted3V2(PO4)2F3In place of KVOF3The rest of the positive electrode active material was the same as in example 2.
The secondary battery according to the present invention may be designed in the form of a flat battery, a cylindrical battery, or the like, depending on the core components, without being limited to a button battery.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are only exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
The potassium ion batteries provided in examples 1 to 20 and comparative examples 1 to 2 were subjected to capacity and cycle stability tests, and the results are shown in table 1. The upper limit of the charging voltage is 4.8V, and the lower limit of the discharging voltage is 2.0V. The charge-discharge current density was 100 mA/g.
Table 1 table of electrochemical performance data of examples
It can be seen from the above examples 1-20 that the prepared potassium ion battery has high stable capacity, good cycling stability, high capacity retention ratio, and high charge-discharge voltage plateau.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
Of course, the positive electrode material of the potassium ion battery of the present invention may have various changes and modifications, and is not limited to the specific structure of the above-described embodiment. In conclusion, the scope of the present invention should include those changes or substitutions and modifications which are obvious to those of ordinary skill in the art.

Claims (14)

1. The potassium ion battery positive electrode material is characterized by comprising KVOF3。
2. The utility model provides a potassium ion battery, its characterized in that, including battery negative pole, diaphragm, electrolyte, the battery positive pole that sets gradually, the battery negative pole contains negative current collector layer and negative pole active material layer, electrolyte includes electrolyte potassium salt and solvent, the battery positive pole contains anodal active material layer and anodal current collector layer, anodal active material layer includes potassium ion battery cathode material, potassium ion battery cathode material includes KVOF3。
3. The potassium ion battery of claim 2, wherein the negative current collector layer comprises a metal conductive material comprising one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy thereof or a composite material thereof.
4. The potassium ion battery according to claim 2, wherein the negative active material layer includes a negative active material that is at least one of artificial graphite, natural graphite, spherulitic graphite, crystalline flake graphite, MCMB, soft carbon, hard carbon, fluorinated graphite, mesocarbon microbeads, petroleum coke, carbon brazes, pyrolytic resin carbon, tin-based alloys, silicon-based alloys, germanium-based alloys, aluminum-based alloys, antimony-based alloys, magnesium-based alloys, carbon nanotubes, nanoalloy materials, nano-oxide materials, triiron tetroxide, trimanganese tetroxide, α -iron trioxide, molybdenum oxide, tungsten oxide, vanadium oxide, cobalt oxide, manganese oxide, titanium nitride, vanadium nitride, tungsten oxynitride, nickel sulfide, and vanadium sulfide.
5. The potassium-ion battery of claim 4, wherein the negative active material layer further comprises a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene, and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, and polyolefins.
6. The potassium-ion battery according to claim 5, wherein the content of the negative active material is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
7. The potassium ion battery of claim 2, wherein the electrolyte potassium salt comprises potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonylimide, KCF3SO3、KN(SO2CF3)2At least one of the above, the concentration range of the electrolyte potassium salt is 0.1-10 mol/L.
8. The potassium ion battery according to claim 7, wherein the solvent comprises propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, γ -butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, crown ether, 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, salt, One or more of N-methyl-N-propyl pyrrolidine-bis (trifluoromethyl) sulfonyl imide salt, N-methyl, propyl piperidine-bis (trifluoromethyl) sulfonyl imide salt and N-methyl, butyl piperidine-bis (trifluoromethyl) sulfonyl imide salt.
9. The potassium ion battery of claim 7, wherein the electrolyte further comprises an additive comprising fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown 12-crown 4, crown 18-crown 6, 4-fluorophenylether, fluoro-chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethyl carbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, One or more of bromobutyrolactone, fluoroacetic acid ethyl, phosphate ester, phosphite ester, phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and lithium carbonate, wherein the additive amount in the electrolyte is 0.1-20 wt%.
10. The potassium-ion battery of claim 2, wherein the positive active material layer further comprises a conductive agent and a binder, the conductive agent is one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide, and the binder is one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefins.
11. The potassium-ion battery of claim 10, wherein the content of the positive electrode material of the potassium-ion battery is 60 to 90 wt%, the content of the conductive agent is 5 to 30 wt%, and the content of the binder is 5 to 10 wt%.
12. The potassium-ion battery of claim 2, wherein the positive current collector layer comprises a metal conductive material comprising one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, lead, antimony, cadmium, gold, bismuth, germanium, or an alloy thereof or a composite thereof.
13. The potassium ion battery of claim 2, wherein the separator is an insulating porous polymer film or an inorganic porous film, the porous polymer film is one or more of a porous polypropylene film, a porous polyethylene film or a porous composite polymer film, and the inorganic porous film is one or more of a glass fiber paper or a porous ceramic separator.
14. A method of manufacturing a potassium-ion battery according to any one of claims 1 to 13, comprising the steps of:
uniformly coating the negative electrode active material layer on the surface of the negative electrode current collector layer, and cutting after the negative electrode active material layer is dried to obtain a battery negative electrode;
drying the diaphragm and then cutting to obtain a diaphragm with a certain size;
dissolving the electrolyte potassium salt in a solvent to form the electrolyte with a certain concentration;
cleaning a positive current collector layer, uniformly coating the positive active material layer on the surface of the positive current collector layer, and cutting after the positive active material layer is dried to obtain a battery positive electrode;
assembling the battery cathode, the diaphragm, the electrolyte and the battery anode to obtain the potassium ion battery;
the positive active material layer comprises the potassium ion battery positive material, and the potassium ion battery positive material comprises KVOF3。
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