CN108511803B - Secondary battery and preparation method thereof - Google Patents

Secondary battery and preparation method thereof Download PDF

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CN108511803B
CN108511803B CN201710101010.8A CN201710101010A CN108511803B CN 108511803 B CN108511803 B CN 108511803B CN 201710101010 A CN201710101010 A CN 201710101010A CN 108511803 B CN108511803 B CN 108511803B
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positive electrode
active material
electrolyte
potassium
secondary battery
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CN108511803A (en
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唐永炳
季必发
张帆
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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
    • H01M10/056—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
    • H01M10/0568—Liquid materials characterised by the solutes
    • 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
    • H01M10/058—Construction or manufacture
    • H01M10/0585—Construction or manufacture of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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

Abstract

The invention provides a secondary battery, which comprises a positive electrode, electrolyte, a negative electrode and a diaphragm; the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material comprises a material capable of embedding potassium salt anions; the electrolyte comprises potassium salt and a non-aqueous solvent; the negative electrode includes a metal foil which serves as both a negative electrode current collector and a negative electrode active material. The electrolyte of the secondary battery takes the sylvite as the electrolyte, solves the problem that the lithium resource storage capacity of the current commonly used lithium secondary battery is limited, reduces the cost of the secondary battery and is environment-friendly; in addition, the metal foil is simultaneously used as a negative electrode active material and a current collector, so that the weight and the volume of the battery are reduced, the energy density of the battery is further improved, and the production and manufacturing cost of the battery is saved.

Description

Secondary battery and preparation method thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a secondary battery and a preparation method thereof.
Background
A secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and used many times. Compared with a primary battery, the secondary battery has the advantages of low use cost and small environmental pollution. At present, the main secondary battery technologies include lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, lithium ion batteries, and the like, and particularly, the lithium ion batteries are most widely applied. However, lithium ion batteries face the problems of limited lithium resource reserves and high cost. Potassium ion batteries have gained increased attention in recent years as an energy storage technology that potentially replaces lithium ion batteries.
The working principle of the potassium ion battery is similar to that of the lithium ion battery, but the storage and release of the charge in the battery are realized through the migration of potassium ions. The core components of the potassium ion battery comprise a positive electrode, a negative electrode and electrolyte, and the storage and release of electric energy are realized through the oxidation-reduction reaction of ion transmission and electron transmission separation which occurs on the interfaces of the positive electrode, the negative electrode and the electrolyte. During charging, potassium ions are removed from the positive active material and are embedded into the negative active material; during discharge, potassium ions are extracted from the negative electrode active material and inserted into the positive electrode active material. Common potassium ion batteries use prussian blue and its analogs, iron phosphate, iron fluorosulfate, etc. as positive active materials, and carbon materials as negative active materials. However, the types of positive and negative electrode materials developed based on the potassium ion battery are very limited at present, the research is basically limited to the half-battery of the potassium sheet, the electrochemical performance of the potassium ion battery based on the developed materials is not ideal, and the preparation process is complex.
Disclosure of Invention
In view of this, the first aspect of the present invention provides a secondary battery, in which graphite or other materials capable of inserting potassium salt anions are used as a positive electrode active material, a metal foil is used as a negative electrode current collector and a negative electrode active material at the same time, and potassium salt is used as an electrolyte, and aims to solve the problems of limited lithium resource storage and high cost of the existing commonly used lithium secondary battery, and the problems of unsatisfactory electrochemical performance and complex process of the existing potassium ion battery.
Specifically, in a first aspect, the present invention provides a secondary battery comprising:
a positive electrode including a positive electrode current collector and a positive electrode active material, the positive electrode active material including a material in which a potassium salt anion can be embedded;
an electrolyte comprising a potassium salt and a non-aqueous solvent;
a negative electrode including a metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material;
and a separator interposed between the positive electrode and the negative electrode.
Wherein the positive electrode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials.
The carbon material comprises one or more of graphite carbon material, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nano tube and graphene.
The graphite carbon material comprises one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbeads graphite, pyrolytic graphite, highly oriented graphite and three-dimensional graphite sponge.
The sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide; the carbide is one or more selected from titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
The material of the metal foil comprises any one of tin, zinc, lead, antimony, cadmium, gold, bismuth and germanium, or an alloy containing at least one of the metal elements, or a composite material containing at least one of the metal elements.
The material of the positive current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium and manganese, or an alloy containing at least one of the metal elements, or a composite material containing at least one of the metal elements.
The potassium salt comprises one or more of 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 and potassium trifluoromethanesulfonate. In the electrolyte, the concentration of the sylvite is 0.1-10 mol/L.
The non-aqueous solvent comprises an organic solvent and ionic liquid, wherein the organic solvent comprises one or more of ester, sulfone, ether and nitrile organic solvents.
The organic solvent includes Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), gamma-butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), Propylene Sulfite (PS), One or more of dimethyl sulfite (DMS), diethyl sulfite (DES) and crown ether (12-crown-4).
The ionic liquid comprises 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, a salt of a compound of formula (I), One or more of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt.
The electrolyte also comprises an additive, wherein the additive comprises one or more of ester, sulfone, ether, nitrile and olefin organic additives, and the mass fraction of the additive in the electrolyte is 0.1-20%. Specifically, the additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl 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, fluorinated chain ether, difluoromethyl vinyl carbonate, trifluoromethyl vinyl carbonate, chloroethyl vinyl carbonate, bromovinyl carbonate, trifluoroethyl phosphonic acid, bromobutyrolactone, fluoroacetoethane, 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 one or more of lithium carbonate.
The diaphragm is an insulating porous polymer film or an inorganic porous film.
According to the secondary battery provided by the first aspect of the invention, the potassium salt is used as the electrolyte, so that the problem that the lithium resource storage capacity of the existing lithium secondary battery is limited is solved, the battery cost is reduced, and the secondary battery is environment-friendly; in addition, the secondary battery provided by the invention directly uses the metal foil as a negative electrode active material and a current collector, so that the weight and the volume of the battery are effectively reduced, the energy density of the battery is improved, and the secondary battery has good charge-discharge cycle performance.
In a second aspect, the present invention provides a method for manufacturing a secondary battery, comprising the steps of:
providing a positive current collector, preparing a positive active material layer on the positive current collector, drying, pressing and cutting into required sizes to obtain a positive electrode; the positive electrode active material layer includes a positive electrode active material including a material in which a potassium salt anion can be intercalated;
cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode; the metal foil is simultaneously used as a negative current collector and a negative active material;
and providing an electrolyte and a diaphragm, wherein the electrolyte comprises potassium salt and a non-aqueous solvent, the negative electrode, the diaphragm and the positive electrode are sequentially and tightly stacked in an inert gas or anhydrous environment, the electrolyte is added to completely soak the diaphragm, and then the stacked part is packaged into a battery shell to obtain the secondary battery.
The preparation method of the secondary battery provided by the second aspect of the invention has simple process and is suitable for large-scale production.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
Fig. 1 is a schematic structural view of a secondary battery provided in an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a secondary battery including a positive electrode current collector 10, a positive electrode active material layer 20, an electrolyte 30, a separator 40, and a negative electrode 50; the positive electrode current collector 10 and a positive electrode active material layer 20 arranged on the positive electrode current collector 10 jointly form a battery positive electrode, and the positive electrode active material layer 20 comprises a positive electrode active material capable of being embedded with potassium salt anions; the negative electrode 50 includes a metal foil, which serves as both a negative electrode current collector and a negative electrode active material; the electrolyte 30 includes a potassium salt and a nonaqueous solvent; the separator 40 is interposed between the positive electrode and the negative electrode 50.
The working principle of the secondary battery provided by the embodiment of the invention is as follows: during charging, anions in the electrolyte migrate to the positive electrode and are embedded into the positive electrode active material, and potassium ions migrate to the negative electrode and form a potassium-metal alloy with the negative electrode; during the discharging process, anions are removed from the positive active material and returned to the electrolyte, and potassium ions are removed from the negative electrode and alloyed and returned to the electrolyte, so that the whole charging and discharging process is realized. In the charging and discharging processes, the electrolyte adopts potassium salt as electrolyte, so that the problem of limited lithium resource reserve is solved, the cost of the secondary battery is reduced, and the influence of the battery on the environment is reduced; in addition, the negative metal foil is simultaneously used as a negative active material and a current collector, so that the weight and the volume of the battery are reduced, the capacity of the battery is improved, the energy density of the battery is further improved, and the production and manufacturing cost of the battery is saved.
In an embodiment of the present invention, the positive electrode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials. Wherein the carbon material comprises one or more of graphite carbon material, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotube and graphene. Specifically, the graphite-based carbon material comprises one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbeads, pyrolytic graphite, highly oriented graphite and three-dimensional graphite sponge.
In an embodiment of the present invention, the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide; the carbide is one or more selected from titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
In an embodiment of the present invention, the positive electrode active material and the negative electrode active material have a layered crystal structure.
In an embodiment of the invention, the material of the metal foil includes any one of tin, zinc, lead, antimony, cadmium, gold, bismuth, and germanium, or an alloy containing at least one of the above metal elements, or a composite material containing at least one of the above metal elements.
In an embodiment of the present invention, the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
In the embodiment of the present invention, the potassium salt as the electrolyte may be one or more of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluoroborate, 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 methanesulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide, and potassium trifluoromethanesulfonate. In the electrolyte, the concentration of the potassium salt can be 0.1-10 mol/L. Further, the concentration of the potassium salt may be 0.1 to 2 mol/L.
In the embodiment of the present invention, the nonaqueous solvent in the electrolytic solution is not particularly limited as long as the electrolyte can be dissociated into potassium ions and anions, and the potassium ions and the anions can freely migrate. Specifically, the non-aqueous solvent comprises an organic solvent and an ionic liquid, wherein the organic solvent can be one or more of ester, sulfone, ether and nitrile organic solvents. More specifically, the organic solvent may be Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethylsulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), Ethylene Carbonate (EC), methyl propionate (EA), Ethyl Acetate (EA), gamma-butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2, One or more of Propylene Sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES) and crown ether (12-crown-4). The ionic liquid comprises 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, a salt of a compound of formula (I), One or more of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt.
In the embodiment of the invention, in order to prevent the negative electrode from being damaged due to volume change during charging and discharging, keep the structure of the negative electrode stable, and improve the service life and the performance of the negative electrode so as to improve the cycle performance of the secondary battery, the electrolyte further comprises an additive, and the additive can be one or more of ester, sulfone, ether, nitrile and olefin organic additives. Specifically, the additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl 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, fluorinated chain ether, difluoromethyl vinyl carbonate, trifluoromethyl vinyl carbonate, chloroethyl vinyl carbonate, bromovinyl carbonate, trifluoroethyl phosphonic acid, bromobutyrolactone, fluoroacetoethane, 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 one or more of lithium carbonate. The additive added in the electrolyte can form a stable solid electrolyte membrane on the surface of a negative current collector (metal foil), so that the metal foil is not damaged when being used as a negative active material, and the service life of the battery is prolonged.
In the embodiment of the present invention, the mass fraction of the additive in the electrolyte is 0.1 to 20%, and further 2 to 5%.
In the embodiment of the present invention, the separator may be an insulating porous polymer film or an inorganic porous film, and specifically may be one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, and a porous ceramic separator.
In the embodiment of the invention, the positive active material layer further comprises a conductive agent and a binder, wherein the mass content of the positive active material is 60-90%, the mass content of the conductive agent is 5-30%, and the mass content of the binder is 5-10%. Further, the mass content of the positive electrode active material is 70-85%. The embodiment of the present invention is not particularly limited to the conductive agent and the binder, and any one commonly used in the art may be used. The conductive agent can be one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide. The binder can be one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
Correspondingly, the embodiment of the invention also provides a preparation method of the secondary battery, which comprises the following steps:
(1) preparing a positive electrode: providing a positive current collector with a clean surface, weighing a positive active material, a conductive agent and a binder according to a certain proportion, and adding a proper solvent to fully mix to form uniform slurry; then uniformly coating the slurry on the surface of a positive electrode current collector to form a positive electrode active material layer, and pressing and cutting after complete drying to obtain a battery positive electrode with the required size;
(2) preparing a negative electrode: cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode;
(3) preparing an electrolyte: and weighing a certain amount of potassium salt electrolyte, adding the potassium salt electrolyte into the non-aqueous solvent, and fully stirring and dissolving to obtain the required electrolyte.
(4) Preparing a diaphragm: cutting the porous polymer film or the inorganic porous film into required sizes, and cleaning to obtain the required diaphragm.
(5) Assembling the battery: and tightly stacking the prepared battery cathode, diaphragm and anode in turn in an inert gas or anhydrous environment, adding the electrolyte to completely soak the diaphragm, packaging the stacked part into a battery shell, and completing assembly to obtain the secondary battery.
It is to be noted that although the above-described steps (1) to (4) describe the operations of the secondary battery production method of the present invention in a specific order, it is not necessary to perform these operations in the specific order. The operations of steps (1) - (4) may be performed simultaneously or in any order.
The raw materials used in the above preparation method of the embodiment of the present invention are as described in the foregoing embodiments, and are not described herein again.
The following examples are provided to further illustrate the method of manufacturing the above secondary battery.
Example 1
A method for manufacturing a secondary battery, comprising the steps of:
(1) preparing a battery cathode: taking a tin foil with the thickness of 0.02mm, cutting the tin foil into a wafer with the diameter of 12mm, cleaning the surface of the tin foil by using ethanol, and airing the tin foil to be used as a negative electrode for later use;
(2) preparing a diaphragm: cutting the glass fiber film into a wafer with the diameter of 16mm, and using the wafer as a diaphragm for later use;
(3) preparing an electrolyte: 3g of potassium hexafluorophosphate (KPF) was weighed6) 5mL of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate (volume ratio of the three components)Stirring until potassium hexafluorophosphate is completely dissolved in the mixed solvent of 4:3:2), then adding fluoroethylene carbonate with the mass fraction of 5% as an additive, and fully and uniformly stirring to obtain electrolyte for later use;
(4) preparing a battery positive electrode: adding 0.8g of expanded graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 5mL of nitrogen methyl pyrrolidone solution, and fully mixing to obtain uniform slurry; and then uniformly coating the slurry on the surface of the aluminum foil current collector 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 later use;
(5) assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared cathode, the diaphragm and the anode in sequence, dripping electrolyte to completely soak the diaphragm, packaging the stacked part into a button cell shell, and completing cell assembly to obtain the secondary cell.
The working mechanism of the secondary battery of embodiment 1 of the present invention is: negative electrode:
Figure BDA0001231735110000091
and (3) positive electrode:
Figure BDA0001231735110000092
comparative example 1
Aluminum foil is used as a positive electrode current collector, natural graphite is used as a positive electrode active material, aluminum foil is used as a negative electrode (the aluminum foil is simultaneously used as a negative electrode active material and a current collector), and LiPF6An aluminum-graphite bi-ion battery was assembled in the same manner as in example 1, except that ethyl methyl carbonate was used as an electrolyte solvent and an additive of vinylene carbonate (2%) was added to the electrolyte. The working mechanism of the battery is as follows: negative electrode:
Figure BDA0001231735110000101
and (3) positive electrode:
Figure BDA0001231735110000102
Figure BDA0001231735110000103
comparative example 2
Aluminum foil is used as a positive electrode current collector, Prussian blue is used as a positive electrode active material, potassium foil is used as a counter electrode, and KBF is4A potassium secondary battery half cell was assembled in the manner described in example 1 as an electrolyte. The working mechanism of the battery is as follows: negative electrode:
Figure BDA0001231735110000104
and (3) positive electrode:
Figure BDA0001231735110000105
Figure BDA0001231735110000106
comparative example 3
Aluminum foil is used as a positive electrode current collector, lithium cobaltate is used as a positive electrode active material, copper foil is used as a negative electrode current collector, graphite is used as a negative electrode active material, LiPF6For the electrolyte, a conventional lithium ion battery was assembled in the manner of example 1. The working mechanism of the battery is as follows: negative electrode:
Figure BDA0001231735110000107
and (3) positive electrode:
Figure BDA0001231735110000108
Figure BDA0001231735110000109
the secondary battery obtained in example 1 of the present invention was subjected to a constant current charge/discharge test with the batteries of comparative examples 1 to 3, at a current density of 100mA/g and a voltage range of 3 to 5V (the same test methods were used in the subsequent examples of the present invention to obtain electrochemical performance results). The test results and other parameters are shown in table 1.
TABLE 1
Figure BDA00012317351100001010
As can be seen from table 1, the bi-ion secondary battery of example 1 of the present invention, which uses potassium salt as an electrolyte, graphite as a positive electrode active material, and tin foil as a negative electrode active material and a current collector, has a higher operating voltage than the batteries of comparative examples 1 to 3, and the negative electrode does not contain active graphite, and is low in raw material cost and process cost, environmentally friendly, and excellent in cycle stability.
Examples 2 to 10
Examples 2 to 10 differ from example 1 only in the selection of the negative electrode material, and specifically, as shown in table 2, the secondary batteries obtained in examples 2 to 12 were subjected to the constant current charge/discharge test, and the results thereof are shown in table 2:
TABLE 2
Figure BDA0001231735110000111
As can be seen from Table 2, when the tin foil is selected as the negative electrode, the specific capacity of the battery is higher, the cycle performance is better, and the energy density is highest.
Examples 11 to 48
Examples 11 to 48 differ from example 1 only in that the positive electrode active material was different, and specifically, as shown in table 3, the secondary batteries obtained in examples 11 to 48 were subjected to the constant current charge and discharge test, and the test results thereof are shown in table 3:
TABLE 3
Figure BDA0001231735110000112
Figure BDA0001231735110000121
As can be seen from table 3, when the graphite-based carbon material is used as the positive electrode active material, the specific capacity of the battery is higher, the energy density is higher, and the cycle performance is better.
Examples 49 to 76
Examples 49 to 76 differ from example 1 only in that, unlike the electrolyte salt, specifically, as shown in table 4, the secondary batteries obtained in the above examples were subjected to the constant current charge and discharge test, and the test results are shown in table 4:
TABLE 4
Figure BDA0001231735110000131
As can be seen from Table 4, KPF was selected as the electrolyte6、KBF4、KClO4And potassium hexafluoroarsenate, potassium trifluoromethanesulfonylimide, potassium trifluoromethanesulfonate and the like, the battery has higher specific capacity, higher energy density and better cycling stability.
Examples 77 to 78
Examples 77 to 78 differ from example 1 only in the electrolyte concentration, and specifically, as shown in table 5, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the test results are shown in table 5:
TABLE 5
Figure BDA0001231735110000141
As can be seen from Table 5, the specific capacity of the battery is high, the energy density is high, and the cycle performance is more excellent at an electrolyte concentration of 1 mol/L.
Examples 79 to 122
Examples 79 to 122 differ from example 1 only in the kind of additives in the electrolyte, and specifically, as shown in table 6, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the test results are shown in table 6:
TABLE 6
Figure BDA0001231735110000142
Figure BDA0001231735110000151
As can be seen from table 6, when the electrolyte additive was fluoroethylene carbonate, the energy density of the battery was higher and the cycle performance was more excellent.
Example 123-
Example 123-126 differs from example 1 only in that the mass content of the additive in the electrolyte is different, and specifically, as shown in table 7, the secondary battery obtained in the above example is subjected to constant current charge and discharge test, and the test results are shown in table 7:
TABLE 7
Figure BDA0001231735110000152
As can be seen from table 7, when the additive content by mass is 5%, the energy density of the battery is higher and the cycle performance is more excellent.
Example 127-
The example 127-177 is different from the example 1 only in the kind of the electrolyte solvent, specifically shown in table 8, and the secondary battery obtained in the above example was subjected to the constant current charge and discharge test, and the test results are shown in table 8:
TABLE 8
Figure BDA0001231735110000161
Figure BDA0001231735110000171
As can be seen from table 8, when the electrolyte solvent is ethylene carbonate + ethyl methyl carbonate + dimethyl carbonate, the energy density of the battery is higher and the cycle performance is more excellent.
The secondary battery according to the embodiment of the present invention may be designed in the form of a flat battery, a cylindrical battery, or the like, according to the core components, without being limited to a button battery. The secondary battery provided by the embodiment of the invention has the advantages that the main active component is a material for releasing and embedding potassium salt anions, and a negative active material is not needed in a battery system, so that the self weight and the preparation cost of the battery can be obviously reduced, the energy density of the battery is improved, and meanwhile, the battery has excellent cycle stability and wide application prospects in the field of secondary batteries.

Claims (6)

1. A secondary battery, characterized by comprising:
the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material is expanded graphite;
the electrolyte comprises a potassium salt, a non-aqueous solvent and an additive, wherein the potassium salt is potassium hexafluorophosphate, the non-aqueous solvent comprises an organic solvent, the organic solvent comprises ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate, the concentration of the potassium salt in the electrolyte is 1mol/L, the non-aqueous solvent is fluoroethylene carbonate, and the mass fraction of the additive in the electrolyte is 5%;
the negative electrode comprises a metal foil, the metal foil is used as a negative electrode current collector and a negative electrode active material at the same time, and the metal foil is a tin foil;
and a separator interposed between the positive electrode and the negative electrode.
2. The secondary battery according to claim 1, wherein the material of the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
3. The secondary battery according to claim 1, wherein the nonaqueous solvent further comprises an ionic liquid.
4. The secondary battery of claim 3, wherein the ionic liquid comprises 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, a salt of a carboxylic acid or a sulfonic acid, a salt of a carboxylic acid or a salt of a carboxylic acid, One or more of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt.
5. The secondary battery according to claim 1, wherein the separator is an insulating porous polymer film or an inorganic porous film.
6. A method for manufacturing a secondary battery, comprising the steps of:
providing a positive current collector, preparing a positive active material layer on the positive current collector, drying, pressing and cutting into required sizes to obtain a positive electrode; the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material is expanded graphite;
cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode; the metal foil is simultaneously used as a negative current collector and a negative active material, and the metal foil is tin foil;
providing an electrolyte and a diaphragm, wherein the electrolyte comprises a potassium salt, a non-aqueous solvent and an additive, the potassium salt is potassium hexafluorophosphate, the non-aqueous solvent comprises an organic solvent, the organic solvent comprises ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate, the concentration of the potassium salt in the electrolyte is 1mol/L, the non-aqueous solvent is fluoroethylene carbonate, and the mass fraction of the additive in the electrolyte is 5%;
and tightly stacking the negative electrode, the diaphragm and the positive electrode in sequence under an inert gas or anhydrous environment, adding the electrolyte to completely soak the diaphragm, and then packaging the stacked part into a battery shell to obtain the secondary battery.
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