CN108511803A - A kind of secondary cell and preparation method thereof - Google Patents

A kind of secondary cell and preparation method thereof Download PDF

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Publication number
CN108511803A
CN108511803A CN201710101010.8A CN201710101010A CN108511803A CN 108511803 A CN108511803 A CN 108511803A CN 201710101010 A CN201710101010 A CN 201710101010A CN 108511803 A CN108511803 A CN 108511803A
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potassium
secondary cell
carbon
electrode active
electrolyte
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CN108511803B (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

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

The present invention provides a kind of secondary cells, including anode, electrolyte, cathode and diaphragm；Wherein anode includes plus plate current-collecting body and the anode active material layer being arranged on the plus plate current-collecting body, and the anode active material layer includes positive electrode active materials, and the positive electrode active materials include the material that can be embedded in sylvite anion；Electrolyte includes sylvite and nonaqueous solvents；Cathode includes metal foil, and the metal foil is used as negative current collector and negative electrode active material simultaneously.The secondary cell electrolyte solves the problems, such as that lithium resource reserves existing for currently used lithium secondary battery are limited using sylvite as electrolyte, reduces secondary cell cost and environmental-friendly；Further, since metal foil is used as negative electrode active material and collector simultaneously so that battery weight and volume reduce, and then improve battery energy density, while having saved battery production manufacturing cost.

Description

A kind of secondary cell and preparation method thereof
Technical field
The present invention relates to secondary battery technologies, more particularly to a kind of secondary cell and preparation method thereof.
Background technology
Secondary cell is also referred to as rechargeable battery, is a kind of repeatable charge and discharge, using multiple battery.Compared to primary electricity Pond, secondary cell have the advantages that use cost is low, environmental pollution is small.Current main secondary cell technology has plumbic acid electric Pond, Ni-Cr battery, Ni-MH battery, lithium ion battery etc., wherein especially the most extensive with lithium ion battery applications.But lithium ion Battery is faced with the problem that lithium resource reserves are limited, of high cost.As the energy storage technology of potential substitution lithium ion battery, potassium ion Battery is of increasing concern in recent years.
The operation principle of kalium ion battery is similar with lithium ion battery, but the storage with release of charge are to pass through in battery The migration of potassium ion is realized.The core building block of kalium ion battery includes anode, cathode and electrolyte, it is by being happened at just On pole, cathode and electrolyte interface ion transmission with electron-transport phase separation redox reaction come realize power storage with Release.When charging, potassium ion is deviate from from positive electrode active materials, embedded negative electrode active material；When electric discharge, potassium ion is lived from cathode Property material abjection and be embedded into positive electrode active materials.Common kalium ion battery is with Prussian blue and the like, phosphoric acid Iron, fluorosulfuric acid iron etc. are positive electrode active materials, using carbon material as negative electrode active material.But it is developed currently based on kalium ion battery The positive and negative pole material type gone out is very limited, and research is only limited to the half-cell to potassium piece substantially, based on the potassium for having developed material The chemical property of ion battery is less desirable, and preparation process is also complex.
Invention content
In consideration of it, first aspect present invention provides a kind of secondary cell, the battery with graphite etc. can be embedded in sylvite the moon from The material of son is made using metal foil simultaneously as negative current collector and negative electrode active material with sylvite as positive electrode active materials For electrolyte, it is intended to solve the problem that lithium resource reserves are limited, of high cost existing for existing common lithium secondary battery, Yi Jixian There is kalium ion battery chemical property undesirable, the problem of complex process.
Specifically, in a first aspect, the present invention provides a kind of secondary cells, including：
Anode, including plus plate current-collecting body and positive electrode active materials, the positive electrode active materials include can be embedded in sylvite the moon from The material of son；
Electrolyte, including sylvite and nonaqueous solvents；
Cathode, including metal foil, the metal foil are used as negative current collector and negative electrode active material simultaneously；
And diaphragm, the diaphragm is between the anode and the cathode.
Wherein, the positive electrode active materials include carbon material, sulfide, nitride, oxide, carbide and above-mentioned It is one or more in the compound of each material.
The carbon material includes graphite-like carbon material, vitreous carbon, carbon carbon composite, carbon fiber, hard carbon, porous charcoal, charcoal It is one or more in black, carbon nanotube, graphene.
The graphite-like carbon material includes natural graphite, expanded graphite, artificial graphite, carbonaceous mesophase spherules graphite, pyrolysis It is one or more in graphite, highly oriented graphite, three-dimensional graphite sponge.
The sulfide be selected from molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, ferrous disulfide, ferrous sulfide, It is one or more in nickel sulfide, zinc sulphide, cobalt sulfide, manganese sulfide；The nitride is selected from hexagonal boron nitride, carbon adulterates six sides It is one or more in boron nitride；The oxide is selected from molybdenum trioxide, tungstic acid, vanadic anhydride, vanadium dioxide, dioxy Change one or more in titanium, zinc oxide, copper oxide, nickel oxide, manganese oxide；The carbide is selected from titanium carbide, ramet, carbon Change one or more in molybdenum, silicon carbide.
The material of the metal foil includes any one in tin, zinc, lead, antimony, cadmium, gold, bismuth, germanium, or containing at least A kind of alloy of above-mentioned metallic element, or the composite material containing at least one above-mentioned metallic element.
The material of the plus plate current-collecting body includes any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese, or containing extremely A kind of few alloy of above-mentioned metallic element, or the composite material containing at least one above-mentioned metallic element.
The sylvite includes Potassium Hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, difluoro Oxalic acid potassium borate, potassium pyrophosphate, Potassium dodecylbenzenesulfonate, dodecyl sulphate potassium, citric acid tri potassium, potassium metaborate, boric acid Potassium, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, Potassiumiodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, aluminium Sour potassium, pyrovinic acid potassium, potassium acetate, potassium bichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium hyperchlorate, fluoroform sulphonyl are sub- It is one or more in amine potassium, trifluoromethane sulfonic acid potassium.In the electrolyte, a concentration of 0.1-10mol/L of sylvite.
The nonaqueous solvents includes organic solvent and ionic liquid, and the organic solvent includes esters, sulfone class, ethers, nitrile It is one or more in class organic solvent.
The organic solvent includes propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid two Methyl esters (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), DMAC N,N' dimethyl acetamide (DMA), fluorine For ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), gamma-butyrolacton (GBL), tetrahydrochysene Furans (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-dioxy pentamethylene (4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene fat (PS), two formicester of sulfurous acid (DMS), sulfurous acid It is one or more in diethyl fat (DES), crown ether (12-crown-4).
The ionic liquid includes 1- ethyl-3-methylimidazoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoro boron Hydrochlorate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- third Base -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- methyl Imidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoroborate, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulphonyl The double fluoroforms of inferior amine salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls sulfimide salt, 1- butyl -1- methylpyrrolidin- Base sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis trifluoromethyl sulfimide salt, N- first, the bis- fluoroforms of propylpiperdine- Base sulfimide salt, N- first, it is one or more in butyl piperidine-bis trifluoromethyl sulfimide salt.
Further include additive in the electrolyte, the additive, which includes esters, sulfone class, ethers, nitrile and olefines, to be had One or more in machine additive, mass fraction of the additive in the electrolyte is 0.1-20%.Specifically, institute It includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3- propane sultones, 1,4- fourths to state additive Sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl are sub- Sulfuric ester, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole, acetamide, phenodiazine Miscellaneous benzene, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain ether, difluoromethyl carbonic acid Vinyl acetate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo fourth Lactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, cyclobutyl sulfone, 1,3- dioxies Pentamethylene, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, titanium dioxide It is one or more in sulphur, lithium carbonate.
The diaphragm is the porous polymer film of insulation or inorganic porous film.
The secondary cell that first aspect present invention provides solves existing lithium secondary battery and deposits using sylvite as electrolyte The limited problem of lithium resource reserves, reduce battery cost and environmental-friendly；In addition, secondary cell provided by the invention is straight It connects metal foil while being used as negative electrode active material and collector, significantly reduce the weight and volume of battery, improve The energy density of battery, and the secondary cell has good charge-discharge performance.
Second aspect, the present invention provides a kind of preparation methods of secondary cell, include the following steps：
Plus plate current-collecting body is provided, anode active material layer is prepared on the plus plate current-collecting body, is cut into after dry, compacting Required size, obtains anode；The anode active material layer includes positive electrode active materials, and the positive electrode active materials include can be embedding Enter the material of sylvite anion；
Metal foil is cut into required size, after surface clean, drying, obtains cathode；The metal foil is same Shi Zuowei negative current collectors and negative electrode active material；
Electrolyte and diaphragm are provided, the electrolyte includes sylvite and nonaqueous solvents, under inert gas or water-less environment, By the cathode, diaphragm, anode successively Close stack, the electrolyte, which is added, makes the diaphragm complete wetting, then will be above-mentioned Stacking portion is encapsulated into battery case, obtains secondary cell.
The preparation method for the secondary cell that second aspect of the present invention provides, it is simple for process, it is suitable for large-scale production.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification , or can be through the embodiment of the present invention implementation and know.
Description of the drawings
Fig. 1 is the structural schematic diagram of secondary cell provided in an embodiment of the present invention.
Specific implementation mode
Invention is further described in detail with reference to the accompanying drawings and detailed description.As described below is of the invention real Apply the preferred embodiment of example, it is noted that for those skilled in the art, of the invention real not departing from Under the premise of applying a principle, several improvements and modifications can also be made, these improvements and modifications are also considered as the embodiment of the present invention Protection domain.
Referring to Fig.1, an embodiment of the present invention provides a kind of secondary cells, including plus plate current-collecting body 10, positive electrode active materials Layer 20, electrolyte 30, diaphragm 40, cathode 50；Wherein, plus plate current-collecting body 10 and the positive-active being arranged on plus plate current-collecting body 10 Material layer 20 collectively forms anode, and the anode active material layer 20 includes that can be embedded in the positive-active material of sylvite anion Material；Cathode 50 includes metal foil, which is used as negative current collector and negative electrode active material simultaneously；Electrolyte 30 includes Sylvite and nonaqueous solvents；Diaphragm 40 is between positive electrode and negative electrode 50.
The operation principle of above-mentioned secondary cell provided in an embodiment of the present invention is：In charging process, the moon in electrolyte In Ion transfer to anode and embedded positive electrode active materials, potassium ion migrates to cathode and forms potassium-metal alloy with cathode；It puts Anion is returned to from abjection in positive electrode active materials in electrolyte in electric process, and potassium ion returns to electrolyte from cathode removal alloying In, to realize entire charge and discharge process.In above-mentioned charge and discharge process, electrolyte is all using sylvite as electrolyte, solution It has determined the limited problem of lithium resource reserves, has reduced secondary cell cost, alleviate influence of the battery to environment；Further, since Negative metal paillon is used as negative electrode active material and collector simultaneously so that and battery weight and volume reduce, and battery capacity improves, And then battery energy density is improved, and saved battery production manufacturing cost.
In embodiment of the present invention, the positive electrode active materials include carbon material, sulfide, nitride, oxide, carbonization It is one or more in the compound of object and above-mentioned each material.Wherein, the carbon material includes graphite-like carbon material, glass It is one or more in carbon, carbon carbon composite, carbon fiber, hard carbon, porous charcoal, carbon black, carbon nanotube, graphene.Specifically, The graphite-like carbon material includes that natural graphite, expanded graphite, artificial graphite, carbonaceous mesophase spherules graphite, pyrolytic graphite, height take It is one or more into graphite, three-dimensional graphite sponge.
In embodiment of the present invention, the sulfide is selected from molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, two It is one or more in iron sulfide, ferrous sulfide, nickel sulfide, zinc sulphide, cobalt sulfide, manganese sulfide；The nitride is selected from six sides It is one or more in boron nitride, carbon doping hexagonal boron nitride；The oxide is selected from molybdenum trioxide, tungstic acid, five oxidations It is one or more in two vanadium, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, manganese oxide；The carbide choosing From one or more in titanium carbide, ramet, molybdenum carbide, silicon carbide.
In embodiment of the present invention, the positive electrode active materials and negative electrode active material have layered crystal structure.
In embodiment of the present invention, the material of the metal foil includes appointing in tin, zinc, lead, antimony, cadmium, gold, bismuth, germanium It anticipates alloy a kind of or containing at least one above-mentioned metallic element, or the composite material containing at least one above-mentioned metallic element.
In embodiment of the present invention, the plus plate current-collecting body includes any one in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese Kind or the alloy containing at least one above-mentioned metallic element, or the composite material containing at least one above-mentioned metallic element.
In embodiment of the present invention, the sylvite as electrolyte can be Potassium Hexafluorophosphate, potassium chloride, potassium fluoride, sulfuric acid Potassium, potassium carbonate, potassium phosphate, potassium nitrate, difluoro oxalate potassium borate, potassium pyrophosphate, Potassium dodecylbenzenesulfonate, dodecyl sulphate Potassium, citric acid tri potassium, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, Potassiumiodate, potassium iodide, silicon Sour potassium, potassium lignosulfonate, potassium oxalate, potassium aluminate, pyrovinic acid potassium, potassium acetate, potassium bichromate, potassium hexafluoroarsenate, tetrafluoro boron It is one or more in sour potassium, potassium hyperchlorate, trifluoromethanesulfonimide potassium, trifluoromethane sulfonic acid potassium.In the electrolyte, potassium The concentration of salt can be 0.1-10mol/L.Further, the concentration of sylvite can be 0.1-2mol/L.
In embodiment of the present invention, the nonaqueous solvents in electrolyte is not particularly limited, as long as electrolyte can be made to dissociate At potassium ion and anion, and potassium ion and anion can be with free migrations.Specifically, the nonaqueous solvents includes organic Solvent and ionic liquid, the organic solvent can be one or more in esters, sulfone class, ethers, nitrile organic solvent.More Specifically, the organic solvent can be propene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid two Methyl esters (DMC), methyl ethyl carbonate (EMC), methyl formate (MF), methyl acetate (MA), DMAC N,N' dimethyl acetamide (DMA), fluorine For ethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), ethyl acetate (EA), gamma-butyrolacton (GBL), tetrahydrochysene Furans (THF), 2- methyltetrahydrofurans (2MeTHF), 1,3- dioxolanes (DOL), 4- methyl-1,3-dioxy pentamethylene (4MeDOL), dimethoxymethane (DMM), 1,2- diformazans Ethylene Oxide (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), ethylene sulfite (ES), sulfurous acid propylene fat (PS), two formicester of sulfurous acid (DMS), sulfurous acid It is one or more in diethyl fat (DES), crown ether (12-crown-4).The ionic liquid includes 1- ethyl-3-methylimidazoles-six Fluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoroborate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulfimide salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- propyl -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methylimidazoles - Bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoro boric acid Salt, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyl sulphonyl Inferior amine salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyls sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis- fluoroforms Base sulfimide salt, N- first, propylpiperdine-bis trifluoromethyl sulfimide salt, N- first, butyl piperidine-bis trifluoromethyl sulphonyl It is one or more in inferior amine salt.
In embodiment of the present invention, destruction of the cathode in charge and discharge caused by volume change in order to prevent keeps negative Pole stable structure improves the service life and performance of cathode, to improve the cycle performance of secondary cell, in the electrolyte also into One step includes additive, and the additive can be one kind in esters, sulfone class, ethers, nitrile and olefines organic additive Or it is a variety of.Specifically, the additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3- third Sultones, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, sulfurous acid Acrylic ester, dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide (DMSO), benzene Methyl ether, acetamide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain Ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, three Fluoro ethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, Cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, alundum (Al2O3), magnesia, barium monoxide, sodium carbonate, calcium carbonate, It is one or more in carbon dioxide, sulfur dioxide, lithium carbonate.Increased additive is in negative current collector (gold in the electrolytic solution Belong to paillon) surface can form stable solid electrolyte film so that when metal foil is reacted as negative electrode active material not by It destroys, improves the service life of battery.
In embodiment of the present invention, mass fraction of the additive in the electrolyte is 0.1-20%, further Ground can be 2-5%.
In embodiment of the present invention, diaphragm can be the porous polymer film of insulation or inorganic porous film, specifically may be used With select porous polypropylene film, porous polyethylene film, porous compound polymer film, all-glass paper, porous ceramics every It is one or more in film.
In embodiment of the present invention, anode active material layer further includes conductive agent and binder, wherein positive-active material The mass content of material is 60-90%, and the mass content of conductive agent is 5-30%, and the mass content of binder is 5-10%.Into one The mass content on step ground, positive electrode active materials is 70-85%.The embodiment of the present invention does not limit conductive agent and binder particularly System, using commonly used in the art.Conductive agent can be conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, conduction It is one or more in carbon fiber, graphene, redox graphene.Binder can be Kynoar, polytetrafluoroethylene (PTFE), It is one or more in polyvinyl alcohol, carboxymethyl cellulose, SBR rubber, polyolefins.
Correspondingly, the embodiment of the present invention additionally provides a kind of preparation method of above-mentioned secondary cell, includes the following steps：
(1) anode is prepared：The plus plate current-collecting body for providing clean surface, weighs positive electrode active materials, conduction by a certain percentage Agent and binder are added appropriate solvent and are thoroughly mixed to form uniform sizing material；Then the slurry is evenly applied to positive collection Flow surface forms anode active material layer, suppresses and cut after being completely dried, obtain the anode of required size；
(2) cathode is prepared：Metal foil is cut into required size, after surface clean, drying, obtains cathode；
(3) electrolyte is prepared：It weighs a certain amount of sylvite electrolyte to be added in nonaqueous solvents, is sufficiently stirred dissolving, obtains Required electrolyte.
(4) diaphragm is prepared：Porous polymer film or inorganic porous film are cut into required size, after cleaning up, Obtain required diaphragm.
(5) battery assembles：Under inert gas or water-less environment, successively by battery cathode obtained above, diaphragm, anode Close stack, the electrolyte, which is added, makes the diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into battery case, complete At assembling, secondary cell is obtained.
It should be noted that although above-mentioned steps (1)-(4) are to describe secondary cell preparation side of the present invention with particular order The operation of method, still, it is not necessary to execute these operations according to the particular order.The operation of step (1)-(4) can be simultaneously Or arbitrary successively execution.
The raw material being applied in the above-mentioned preparation method of the embodiment of the present invention as described in the previous embodiment, herein no longer It repeats.
The preparation method that specific embodiment further illustrates above-mentioned secondary cell is set forth below.
Embodiment 1
A kind of preparation method of secondary cell, includes the following steps：
(1) battery cathode is prepared：It is the tinfoil paper of 0.02mm to take thickness, cuts into the disk of a diameter of 12mm, clear with ethyl alcohol Tinfoil paper surface is washed, is dried spare as cathode；
(2) diaphragm is prepared：It is used as diaphragm spare after glass fiber membrane to be cut into the disk of diameter 16mm；
(3) electrolyte is prepared：Weigh 3g Potassium Hexafluorophosphates (KPF6) be added to 5mL ethylene carbonates, dimethyl carbonate and (three's volume ratio is 4 to methyl ethyl carbonate:3:2) in the mixed solvent, stirring are completely dissolved to Potassium Hexafluorophosphate, and matter is then added It is spare that the fluorinated ethylene carbonate that amount score is 5% as additive, after stirring obtains electrolyte；
(4) anode is prepared：0.8g expanded graphites, 0.1g carbon blacks, 0.1g Kynoar are added to 5mL N-methyls In pyrrolidone solution, it is sufficiently mixed acquisition uniform sizing material；Then slurry is evenly applied to aluminum foil current collector surface and vacuum It is dry.Dry the electrode obtained piece is cut into the disk of a diameter of 10mm, it is spare as anode after compacting；
(5) battery assembles：In the glove box of inert gas shielding, successively by the above-mentioned cathode prepared, diaphragm, anode Close stack, electrolyte, which is added dropwise, makes diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into button cell shell, completes electricity Pond assembles, and obtains secondary cell.
The working mechanism of the secondary cell of the embodiment of the present invention 1 is：Cathode：Anode：
Comparative example 1
Using aluminium foil as plus plate current-collecting body, natural graphite is as positive electrode active materials, and aluminium foil as cathode, (make simultaneously by aluminium foil For negative electrode active material and collector), LiPF6For electrolyte, methyl ethyl carbonate is electrolyte solvent, and is added in electrolyte The additive of 2% vinylene carbonate is assembled into aluminium-graphite Dual-ion cell with reference to the mode of embodiment 1.The work of the battery Mechanism is：Cathode：Anode：
Comparative example 2
It is Prussian blue to be used as positive electrode active materials using aluminium foil as plus plate current-collecting body, using potassium foil as to electrode, KBF4For electrolyte, potassium secondary cell half-cell is assembled into reference to the mode of embodiment 1.The working mechanism of the battery is： Cathode：Anode：
Comparative example 3
Using aluminium foil as plus plate current-collecting body, cobalt acid lithium is made as positive electrode active materials, copper foil as negative current collector, graphite For negative electrode active material, LiPF6For electrolyte, conventional lithium ion battery is assembled into reference to the mode of embodiment 1.The work of the battery It is as mechanism：Cathode：Anode：
Battery in 1 gained secondary cell of the above embodiment of the present invention and comparative example 1-3 is subjected to constant current charge-discharge survey Examination, current density 100mA/g, voltage range are that (subsequent embodiment of the present invention is all made of same test method and obtains 3-5V Chemical property result).Test result and other parameters are as shown in table 1.
Table 1
As known from Table 1, the embodiment of the present invention 1 using sylvite as electrolyte, using graphite as positive electrode active materials, it is same with tinfoil paper The double ion secondary cell of Shi Zuowei negative electrode active materials and collector, operating voltage are higher than the battery of comparative example 1-3, and cathode Without Activated Graphite, cost of material and process costs are low, and environmental-friendly, and cyclical stability is excellent.
Embodiment 2-10
Embodiment 2-10 is differed only in embodiment 1, and the selection of cathode is different, specific as shown in table 2, by embodiment Secondary cell obtained by 2-12 carries out constant current charge-discharge test, and the results are shown in Table 2：
Table 2
As known from Table 2, when cathode selects tinfoil paper, battery specific capacity higher, cycle performance is more preferable, energy density highest.
Embodiment 11-48
Embodiment 11-48 is differed only in embodiment 1, and positive electrode active materials are different, specific as shown in table 3, will be real It applies the secondary cell obtained by a 11-48 and carries out constant current charge-discharge test, test result is as shown in table 3：
Table 3
From table 3 it is observed that when positive electrode active materials select graphite-like carbon material, battery specific capacity higher, energy is close Higher is spent, cycle performance is also more preferably.
Embodiment 49-76
Embodiment 49-76 is differed only in embodiment 1, and electrolytic salt is different, specific as shown in table 4, by above-mentioned reality It applies the secondary cell obtained by example and carries out constant current charge-discharge test, test result is as shown in table 4：
Table 4
As can be seen from Table 4, electrolyte selects KPF6、KBF4、KClO4, potassium hexafluoroarsenate, trifluoromethanesulfonimide Whens potassium, trifluoromethane sulfonic acid potassium etc., battery specific capacity higher, energy density higher, cyclical stability is more preferable.
Embodiment 77-78
Embodiment 77-78 is differed only in embodiment 1, and electrolyte concentration is different, specific as shown in table 5, will be above-mentioned Secondary cell obtained by embodiment carries out constant current charge-discharge test, and test result is as shown in table 5：
Table 5
As can be seen from Table 5, when electrolyte concentration is 1mol/L, battery specific capacity is high, and energy density is high, cycle performance It is better.
Embodiment 79-122
Embodiment 79-122 is differed only in embodiment 1, and the additive types in electrolyte are different, 6 institute of specific table Show, the secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, test result is as shown in table 6：
Table 6
As can be seen from Table 6, when electrolysis additive is fluorinated ethylene carbonate, the energy density higher of battery, and Cycle performance is better.
Embodiment 123-126
Embodiment 123-126 is differed only in embodiment 1, and the additive mass content in electrolyte is different, specifically Shown in table 7, the secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, test result is as shown in table 7：
Table 7
As can be seen from Table 7, additive mass content is at 5%, the energy density higher of battery, and cycle performance is more It is excellent.
Embodiment 127-177
Embodiment 127-177 is differed only in embodiment 1, the difference of electrolyte solvent type, shown in specific table 8, Secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, test result is as shown in table 8：
Table 8
As can be seen from Table 8, when electrolyte solvent is ethylene carbonate+methyl ethyl carbonate+dimethyl carbonate, battery Energy density higher, and cycle performance is better.
The present embodiments relate to secondary cell form be not limited to button cell, can be also designed to according to core component The forms such as flat plate cell, cylindrical battery.The secondary cell main active of the embodiment of the present invention is de- for sylvite anion Go out the material with insertion, and be not necessarily to negative electrode active material in battery system, thus battery dead weight and manufacturing cost can be significantly reduced, Battery energy density is promoted, while the battery has excellent stable circulation performance, there is wide answer in secondary cell field Use foreground.

Claims (15)

1. a kind of secondary cell, which is characterized in that including：
Anode, including plus plate current-collecting body and the anode active material layer being arranged on the plus plate current-collecting body, the positive-active Material layer includes positive electrode active materials, and the positive electrode active materials include the material that can be embedded in sylvite anion；
Electrolyte, including sylvite and nonaqueous solvents；
Cathode, including metal foil, the metal foil are used as negative current collector and negative electrode active material simultaneously；
And diaphragm, the diaphragm is between the anode and the cathode.
2. secondary cell as described in claim 1, which is characterized in that the positive electrode active materials include carbon material, sulfide, Nitride, oxide, carbide and above-mentioned each material compound in it is one or more.
3. secondary cell as claimed in claim 2, which is characterized in that the carbon material include graphite-like carbon material, vitreous carbon, It is one or more in carbon carbon composite, carbon fiber, hard carbon, porous charcoal, carbon black, carbon nanotube, graphene.
4. secondary cell as claimed in claim 3, which is characterized in that the graphite-like carbon material includes natural graphite, expansion Graphite, artificial graphite, carbonaceous mesophase spherules graphite, pyrolytic graphite, highly oriented graphite, one kind in three-dimensional graphite sponge or more Kind.
5. secondary cell as claimed in claim 2, which is characterized in that the sulfide is selected from molybdenum disulfide, tungsten disulfide, two It is one or more in vanadic sulfide, titanium disulfide, ferrous disulfide, ferrous sulfide, nickel sulfide, zinc sulphide, cobalt sulfide, manganese sulfide； The nitride is one or more in hexagonal boron nitride, carbon doping hexagonal boron nitride；The oxide is selected from three oxidations One kind in molybdenum, tungstic acid, vanadic anhydride, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, manganese oxide Or it is a variety of；The carbide is one or more in titanium carbide, ramet, molybdenum carbide, silicon carbide.
6. secondary cell as described in claim 1, which is characterized in that the material of the metal foil include tin, zinc, lead, antimony, Any one in cadmium, gold, bismuth, germanium, or the alloy containing at least one above-mentioned metallic element, or contain at least one above-mentioned gold Belong to the composite material of element.
7. secondary cell as described in claim 1, which is characterized in that the material of the plus plate current-collecting body include aluminium, copper, iron, Any one in tin, zinc, nickel, titanium, manganese, or the alloy containing at least one above-mentioned metallic element, or containing at least one State the composite material of metallic element.
8. secondary cell as described in claim 1, which is characterized in that the sylvite includes Potassium Hexafluorophosphate, potassium chloride, fluorination Potassium, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, difluoro oxalate potassium borate, potassium pyrophosphate, Potassium dodecylbenzenesulfonate, 12 Alkylsurfuric acid potassium, citric acid tri potassium, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, Potassiumiodate, iodine Change potassium, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, pyrovinic acid potassium, potassium acetate, potassium bichromate, potassium hexafluoroarsenate, It is one or more in potassium tetrafluoroborate, potassium hyperchlorate, trifluoromethanesulfonimide potassium, trifluoromethane sulfonic acid potassium；The electrolysis In liquid, a concentration of 0.1-10mol/L of sylvite.
9. secondary cell as described in claim 1, which is characterized in that the nonaqueous solvents includes organic solvent and ionic liquid Body, the organic solvent include one or more in esters, sulfone class, ethers, nitrile organic solvent.
10. secondary cell as claimed in claim 9, which is characterized in that the organic solvent includes propene carbonate, carbonic acid second Enester, diethyl carbonate, dimethyl carbonate, methyl ethyl carbonate, methyl formate, methyl acetate, DMAC N,N' dimethyl acetamide, fluoro Ethylene carbonate, methyl propionate, ethyl propionate, ethyl acetate, gamma-butyrolacton, tetrahydrofuran, 2- methyltetrahydrofurans, 1,3- Dioxolanes, 4- methyl-1,3-dioxies pentamethylene, dimethoxymethane, 1,2- diformazans Ethylene Oxide, triethylene glycol dimethyl ether, two Methyl sulfone, dimethyl ether, ethylene sulfite, sulfurous acid propylene fat, two formicester of sulfurous acid, sulfurous acid diethyl fat, crown ether (12- crown-s 4) one or more in.
11. secondary cell as claimed in claim 9, which is characterized in that the ionic liquid includes 1- ethyl -3- methyl miaows Azoles-hexafluorophosphate, 1- ethyl-3-methylimidazoles-tetrafluoroborate, 1- ethyl-3-methylimidazoles-bis trifluoromethyl sulphonyl are sub- Amine salt, 1- propyl -3- methylimidazoles-hexafluorophosphate, 1- propyl -3- methylimidazoles-tetrafluoroborate, 1- propyl -3- methyl Imidazoles-bis trifluoromethyl sulfimide salt, 1- butyl -1- methylimidazoles-hexafluorophosphate, 1- butyl -1- methylimidazoles-tetrafluoro Borate, 1- butyl -1- methylimidazoles-bis trifluoromethyl sulfimide salt, N- butyl-N- methylpyrrolidin- bis trifluoromethyls Sulfimide salt, 1- butyl -1- methylpyrrolidin- bis trifluoromethyls sulfimide salt, N- Methyl-N-propyls pyrrolidines-bis- three Methyl fluoride sulfimide salt, N- first, propylpiperdine-bis trifluoromethyl sulfimide salt, N- first, butyl piperidine-bis trifluoromethyl It is one or more in sulfimide salt.
12. secondary cell as described in claim 1, which is characterized in that further include additive in the electrolyte, the addition Agent includes one or more in esters, sulfone class, ethers, nitrile and olefines organic additive, and the additive is in the electricity It is 0.1-20% to solve the mass fraction in liquid.
13. secondary cell as claimed in claim 12, which is characterized in that the additive includes fluorinated ethylene carbonate, carbon Sour vinylene, vinylethylene carbonate, 1,3- propane sultones, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid propylene Ester, ethyl sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, sulfurous acid Ethyl, carbonochloridic acid formicester, dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole, acetamide, diazine, metadiazine, crown ether 12-crown-4, Crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain ether, difluoromethyl ethylene carbonate, trifluoromethy ethylene carbonate, Chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphonic acids, bromo butyrolactone, fluoroacetic base ethane, phosphate, Phosphite ester, phosphonitrile, ethanol amine, carbonization dimethylamine, cyclobutyl sulfone, 1,3- dioxolanes, acetonitrile, long-chain olefin, three oxidations It is one or more in two aluminium, magnesia, barium monoxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide, lithium carbonate.
14. secondary cell as described in claim 1, which is characterized in that the diaphragm be insulation porous polymer film or Inorganic porous film.
15. a kind of preparation method of secondary cell, which is characterized in that include the following steps：
Plus plate current-collecting body is provided, anode active material layer is prepared on the plus plate current-collecting body, is cut into after dry, compacting required Size obtains anode；The anode active material layer includes positive electrode active materials, and the positive electrode active materials include that can be embedded in potassium The material of salt anionic；
Metal foil is cut into required size, after surface clean, drying, obtains cathode；The metal foil is made simultaneously For negative current collector and negative electrode active material；
Electrolyte and diaphragm are provided, the electrolyte includes sylvite and nonaqueous solvents, under inert gas or water-less environment, by institute Cathode, diaphragm, anode Close stack successively are stated, the electrolyte, which is added, makes the diaphragm complete wetting, then by above-mentioned stacking Partial encapsulation enters battery case, obtains secondary cell.
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