CN108470908A - A kind of secondary cell and preparation method thereof - Google Patents
A kind of secondary cell and preparation method thereof Download PDFInfo
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- CN108470908A CN108470908A CN201710100651.1A CN201710100651A CN108470908A CN 108470908 A CN108470908 A CN 108470908A CN 201710100651 A CN201710100651 A CN 201710100651A CN 108470908 A CN108470908 A CN 108470908A
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M10/058—Construction or manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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 present invention provides a kind of secondary cells, including anode, cathode, electrolyte and diaphragm, the anode includes positive electrode active materials, and the positive electrode active materials include one or more in the compound of carbon material, sulfide, nitride, oxide, carbide and above-mentioned each material；The cathode includes negative electrode active material, and the negative electrode active material includes one or more in the compound of carbon material, sulfide, nitride, oxide, carbide and above-mentioned each material；The electrolyte includes sylvite and nonaqueous solvents.For the battery using sylvite as electrolyte, cost is relatively low, and operating voltage is high, and energy density is high, and cycle performance is excellent.The present invention also provides the preparation methods of the secondary cell.
Description
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 can not
The one-shot battery of reuse, secondary cell have the advantages that use cost is low, environmental pollution is small.Current main secondary electricity
Pool technology has lead-acid battery, Ni-Cr battery, Ni-MH battery, lithium ion battery etc..Wherein especially with lithium ion battery applications the most
Extensively.But lithium ion battery is faced with lithium resource limited, the of high cost disadvantage of reserves.As potential substitution lithium ion battery
Energy storage technology, kalium ion battery are 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, using materials such as carbon as positive electrode active materials
And negative electrode active material, using sylvite as electrolyte, the battery avoid use the limited lithium salts of resource, by substantially reduce battery at
This, reduces influence of the battery to environment.In addition, there is the battery Dual-ion cell working mechanism, operating voltage to reach 4.65V,
Higher than traditional lithium ion battery, to improve energy density, and electrochemical cycle stability is good.
Specifically, in a first aspect, the present invention provides a kind of secondary cells, including：
Anode, including plus plate current-collecting body and the anode active material layer being arranged on the plus plate current-collecting body, the anode
Active material layer includes positive electrode active materials, and the positive electrode active materials include carbon material, sulfide, nitride, oxide, carbon
It is one or more in the compound of compound and above-mentioned each material；
Electrolyte, including sylvite and nonaqueous solvents；
Cathode, including negative current collector and the anode active material layer being arranged on the negative current collector, the cathode
Active material layer includes negative electrode active material, and the negative electrode active material includes carbon material, sulfide, nitride, oxide, carbon
It is one or more in the compound of compound and above-mentioned each material；
And diaphragm, the diaphragm is between the anode and the cathode.
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 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 material of the negative current collector 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%.
The additive include fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, in 1,3- propane sulfonic acid
Ester, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, propylene sulfite,
Dimethyl sulfite, diethyl sulfite, glycol sulfite, carbonochloridic acid formicester, dimethyl sulfoxide (DMSO), methyl phenyl ethers anisole, second
Amide, diazine, metadiazine, crown ether 12-crown-4, crown ether 18- crown-s 6,4- fluoroanisoles, fluoro chain ether, two fluoro
Methyl carbonic acid vinyl acetate, trifluoromethy ethylene carbonate, chlorocarbonic acid vinyl acetate, bromo ethylene carbonate, trifluoroethyl phosphine
Acid, 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, carbon dioxide,
It is one or more in sulfur dioxide, 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 tool provided by the invention
There is higher operating voltage, improves the energy density of battery, and battery 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 carbon materials
Material, sulfide, nitride, oxide, carbide and above-mentioned each material compound in it is one or more；
Negative current collector is provided, anode active material layer is prepared on the negative current collector, is cut into after dry, compacting
Required size, obtains cathode；The anode active material layer includes negative electrode active material, and the negative electrode active material includes carbon materials
Material, sulfide, nitride, oxide, carbide and above-mentioned each material compound in it is one or more；
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
As described below is the preferred embodiment of the embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise of not departing from principle of the embodiment of the present invention, several improvements and modifications can also be made, these improvement
The protection domain of the embodiment of the present invention is also considered as with retouching.
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, anode active material layer 50, negative current collector 60；Wherein, the anode active material layer 20
Positive electrode active materials including sylvite anion can be embedded in, the positive electrode active materials include carbon material, sulfide, nitride,
It is one or more in the compound of oxide, carbide and above-mentioned each material；Anode active material layer 50 includes that can be embedded in
The negative electrode active material of potassium ion, the negative electrode active material include carbon material, sulfide, nitride, oxide, carbide,
And it is one or more in the compound of above-mentioned each material；Electrolyte 30 includes sylvite and nonaqueous solvents；Diaphragm 40 is between just
Between pole active material layer 20 and anode active material layer 50.
The operation principle of above-mentioned secondary cell provided in an embodiment of the present invention is：In charging process, the potassium in electrolyte
Salt anionic is migrated into anode and embedded positive electrode active materials, and potassium ion is migrated into cathode and embedded negative electrode active material；
In discharge process, sylvite anion enters from abjection in positive electrode active materials in electrolyte, and at the same time, potassium ion is de- from cathode
Go out to enter in electrolyte, to realize entire charge and discharge process.In this process, all sylvite of electrolyte in electrolyte,
It solves the problems, such as that existing lithium resource reserves are limited, significantly reduces secondary cell cost, alleviate influence of the battery to environment.
In embodiment of the present invention, the carbon material includes graphite-like carbon material, vitreous carbon, carbon carbon composite, carbon fiber
It is one or more in dimension, hard carbon, porous charcoal, carbon black, carbon nanotube, graphene.Specifically, the graphite-like carbon material includes
Natural graphite, expanded graphite, artificial graphite, carbonaceous mesophase spherules graphite, pyrolytic graphite, highly oriented graphite, three-dimensional graphite sponge
In it is one or more.
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 can select identical material with negative electrode active material,
Different materials can be selected.In embodiment of the present invention, the positive electrode active materials and negative electrode active material have layered crystal knot
Structure.
In embodiment of the present invention, the material of the plus plate current-collecting body includes in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese
Any one or the alloy containing at least one above-mentioned metallic element, or the composite wood containing at least one above-mentioned metallic element
Material.
In embodiment of the present invention, the material of the negative current collector includes in aluminium, copper, iron, tin, zinc, nickel, titanium, manganese
Any one or the alloy containing at least one above-mentioned metallic element, or the composite wood containing at least one above-mentioned metallic element
Material.
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 the secondary cell, is gone back in the electrolyte
Further comprise that additive, the additive can be one in esters, sulfone class, ethers, nitrile and olefines organic additive
Kind is a variety of.Specifically, the additive includes fluorinated ethylene carbonate, vinylene carbonate, vinylethylene carbonate, 1,3-
Propane sultone, 1,4- butyl sultones, sulfuric acid vinyl ester, sulfuric acid acrylic ester, ethyl sulfate, ethylene sulfite, sulfurous
Acid propylene ester, dimethyl sulfite, diethyl sulfite, glycol sulfite, 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, 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.
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 content of material is 60-90wt%, and the content of conductive agent is 5-30wt%, and the content of binder is 5-10wt%.Negative electrode active material
The bed of material further includes conductive agent and binder, and the wherein content of negative electrode active material is 60-90wt%, and the content of conductive agent is 5-
The content of 30wt%, binder are 5-10wt%.The embodiment of the present invention is not particularly limited conductive agent and binder, uses
It is commonly used in the art.Conductive agent can be conductive black, conductive carbon ball, electrically conductive graphite, carbon nanotube, conductive carbon fibre,
It is one or more in graphene, redox graphene.Binder can be Kynoar, polytetrafluoroethylene (PTFE), polyethylene
It is one or more in alcohol, carboxymethyl cellulose, SBR rubber, polyolefins.
Correspondingly, the embodiment of the present invention additionally provides the preparation method of the secondary cell in above-described embodiment, including following
Step：
Step 1 prepares anode：The plus plate current-collecting body for providing clean surface, weighs positive-active material by a certain percentage
Material, conductive agent and binder are added appropriate solvent and are thoroughly mixed to form uniform sizing material；Then the slurry is evenly applied to
Plus plate current-collecting body surface forms anode active material layer, is cut after being completely dried, obtaining the battery of required size just
Pole；
Step 2 prepares battery cathode：The negative current collector for providing clean surface, weighs negative electrode active material by a certain percentage
Material, conductive agent and binder are added appropriate solvent and are thoroughly mixed to form uniform sizing material；Then the slurry is evenly applied to
Negative current collector surface forms anode active material layer, is cut after being completely dried, and the battery for obtaining required size is negative
Pole；
Step 3 prepares electrolyte：It weighs a certain amount of sylvite electrolyte to be added in nonaqueous solvents, is sufficiently stirred dissolving, obtains
To required electrolyte.
Step 4 prepares diaphragm：Porous polymer film or inorganic porous film are cut into required size, cleaned up
Afterwards, required diaphragm is obtained.
Step 5, battery assembling：Under inert gas or water-less environment, by battery cathode obtained above, diaphragm, anode
Close stack successively, the electrolyte, which is added, makes the diaphragm complete wetting, and above-mentioned stacking portion is then encapsulated into battery case
Body completes assembling, obtains secondary cell.
It should be noted that although above-mentioned steps 1-4 is to describe secondary cell preparation method of the present invention with particular order
Operation, still, this, which does not require that or implies, to execute these operations according to the particular order.The preparation of step 1-4 can
Successively to execute simultaneously or arbitrarily.
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：
Step 1 prepares battery cathode：0.8g expanded graphites, 0.1g carbon blacks, 0.1g Kynoar are added to 4mL nitrogen
In methylpyrrolidone solution, it is sufficiently mixed acquisition uniform sizing material；Then slurry is evenly applied to copper foil current collector surface simultaneously
Vacuum drying.Dry the electrode obtained piece is cut into the disk of diameter 12mm, it is spare as battery cathode after compacting.
Step 2 prepares diaphragm：It is used as diaphragm spare after all-glass paper to be cut into the disk of diameter 16mm.
Step 3 prepares electrolyte：It is 4 to weigh 3g Potassium Hexafluorophosphates and be added to 5mL volume ratios:3:2 ethylene carbonate,
The in the mixed solvent of diethyl carbonate and methyl ethyl carbonate, stirring are completely dissolved to Potassium Hexafluorophosphate, and mass fraction is then added
For 5% fluorinated ethylene carbonate as additive, after stirring as electrolyte it is spare.
Step 4 prepares anode：0.8g expanded graphites, 0.1g carbon blacks, 0.1g Kynoar are added to 4mL nitrogen
In methylpyrrolidone solution, it is sufficiently mixed acquisition uniform sizing material；Then slurry is evenly applied to aluminum foil current collector surface simultaneously
Vacuum drying.Dry the electrode obtained piece is cut into the disk of diameter 10mm, it is spare as anode after compacting.
Step 5, battery assembling：In the glove box of inert gas shielding, by the above-mentioned battery cathode prepared, diaphragm,
Close stack, dropwise addition electrolyte make diaphragm complete wetting to anode successively, and above-mentioned stacking portion is then encapsulated into button electricity
Pond shell completes battery assembling, obtains secondary cell.
The working mechanism of the secondary cell of the embodiment of the present invention 1 is：Cathode：Anode：
The secondary cell of the embodiment of the present invention 1 is subjected to constant current charge-discharge test, current density 100mA/g, voltage
Ranging from 3-5V (subsequent embodiment of the present invention is all made of same test method and obtains chemical property result).It obtains after tested
Know, the operating voltage of the secondary cell of the embodiment of the present invention 1 is 4.65V, and battery specific capacity is 66mAh/g, and energy density is
145Wh/kg, capacity attenuation to cycle-index when 85% are 200 times.The embodiment of the present invention 1 using sylvite as double stones of electrolyte
Black secondary cell, operating voltage is high, and energy density is high, has extended cycle life, and cost of material and process costs are low, and environment
It is friendly.
Embodiment 2-51
Embodiment 2-51 is differed only in embodiment 1, and negative electrode active material is different, specific as shown in table 1, will be above-mentioned
Secondary cell obtained by embodiment carries out constant current charge-discharge test, and the results are shown in Table 1：
Table 1
From table 1 it follows that when negative electrode active material selects graphite-like carbon material, battery specific capacity is high, energy density
Height, cycle performance is also more preferably.
Embodiment 52-101
Embodiment 52-101 is differed only in embodiment 1, and positive electrode active materials are different, specific as shown in table 2, will be upper
It states the secondary cell obtained by embodiment and carries out constant current charge-discharge test, the results are shown in Table 2：
Table 2
From Table 2, it can be seen 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 102-130
Embodiment 102-130 is differed only in embodiment 1, and electrolytic salt is different, specific as shown in table 3, will be above-mentioned
Secondary cell obtained by embodiment carries out constant current charge-discharge test, and the results are shown in Table 3：
Table 3
From table 3 it is observed that electrolyte selects KPF6、KBF4、KClO4, potassium hexafluoroarsenate, trifluoromethanesulfonimide
When potassium, trifluoromethane sulfonic acid potassium, battery specific capacity higher, energy density higher, cyclical stability is more preferable.
Embodiment 130-132
Embodiment 130-132 is differed only in embodiment 1, and electrolyte concentration is different, specific as shown in table 4, will be upper
It states the secondary cell obtained by embodiment and carries out constant current charge-discharge test, the results are shown in Table 4：
Table 4
As can be seen from Table 4, when electrolyte concentration is 1mol/L, battery specific capacity higher, energy density higher, and follow
Ring is had excellent performance.
Embodiment 133-184
Embodiment 133-184 is differed only in embodiment 1, and additive types are different in electrolyte, 5 institute of specific table
Show, the secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, the results are shown in Table 5：
Table 5
As can be seen from Table 5, electrolysis additive is fluorinated ethylene carbonate, the energy density higher of battery, and is followed
Ring performance is better.
Embodiment 185-188
Embodiment 185-188 is differed only in embodiment 1, and the mass content of additive is different in electrolyte, specifically
As shown in table 6, the secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, the results are shown in Table 6：
Table 6
As can be seen from Table 6, when the mass content of electrolysis additive is 5wt%, battery energy density is high, and recycles
It has excellent performance.
Embodiment 189-238
Embodiment 189-238 is differed only in embodiment 1, the difference of electrolyte solvent type, specifically such as 7 institute of table
Show, the secondary cell obtained by above-described embodiment is subjected to constant current charge-discharge test, the results are shown in Table 7：
Table 7
As can be seen from Table 7, when electrolyte solvent is ethylene carbonate+methyl ethyl carbonate+dimethyl carbonate, battery
Energy density higher, and cycle performance is excellent.
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 of the embodiment of the present invention is using sylvite as electrolyte, with double ion electricity
Pond working mechanism, operating voltage reach 4.65V, higher than traditional lithium ion battery, to improve energy density, and electrochemistry
Good cycling stability, while the battery manufacturing cost is relatively low, has broad prospects in secondary cell field.
Claims (14)
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 carbon material, sulfide, nitride, oxide, carbonization
It is one or more in the compound of object and above-mentioned each material；
Electrolyte, including sylvite and nonaqueous solvents；
Cathode, including negative current collector and the anode active material layer being arranged on the negative current collector, the negative electrode active
Material layer includes negative electrode active material, and the negative electrode active material includes carbon material, sulfide, nitride, oxide, carbonization
It is one or more in the compound of object and above-mentioned each material；
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 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.
3. secondary cell as claimed in claim 2, 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.
4. secondary cell as described in claim 1, 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.
5. 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.
6. secondary cell as described in claim 1, which is characterized in that the material of the negative current collector 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.
7. 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.
8. 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.
9. secondary cell as claimed in claim 8, 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.
10. secondary cell as claimed in claim 8, 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.
11. 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.
12. secondary cell as claimed in claim 11, 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.
13. secondary cell as described in claim 1, which is characterized in that the diaphragm be insulation porous polymer film or
Inorganic porous film.
14. 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, the positive electrode active materials include carbon material,
Sulfide, nitride, oxide, carbide and above-mentioned each material compound in it is one or more；
Negative current collector is provided, anode active material layer is prepared on the negative current collector, is cut into after dry, compacting required
Size obtains cathode；The anode active material layer includes negative electrode active material, the negative electrode active material include carbon material,
Sulfide, nitride, oxide, carbide and above-mentioned each material compound in it is one or more；
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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| CN109616699A (en) * | 2018-11-27 | 2019-04-12 | 恩力能源科技有限公司 | A kind of battery electrolyte and water system ion battery and preparation method thereof |
| CN110265636A (en) * | 2019-05-16 | 2019-09-20 | 武汉纳米客星科技有限公司 | Three-dimensional drape graphene composite Nano curing nickel material and its preparation method and application |
| CN110854378A (en) * | 2019-10-22 | 2020-02-28 | 同济大学 | Nonmetal-sulfur secondary battery |
| CN111422906A (en) * | 2020-02-29 | 2020-07-17 | 合肥国轩高科动力能源有限公司 | Preparation method of silylene and molybdenum disulfide lithium battery cathode composite material |
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| CN105849839A (en) * | 2013-12-26 | 2016-08-10 | 住友电气工业株式会社 | Alkali metal ion capacitor |
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| CN105849839A (en) * | 2013-12-26 | 2016-08-10 | 住友电气工业株式会社 | Alkali metal ion capacitor |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109616699A (en) * | 2018-11-27 | 2019-04-12 | 恩力能源科技有限公司 | A kind of battery electrolyte and water system ion battery and preparation method thereof |
| CN109616699B (en) * | 2018-11-27 | 2021-07-16 | 恩力能源科技有限公司 | Battery electrolyte, aqueous ion battery and preparation method thereof |
| CN110265636A (en) * | 2019-05-16 | 2019-09-20 | 武汉纳米客星科技有限公司 | Three-dimensional drape graphene composite Nano curing nickel material and its preparation method and application |
| CN110265636B (en) * | 2019-05-16 | 2022-08-19 | 武汉纳米客星科技有限公司 | Three-dimensional folded graphene composite nano nickel disulfide material and preparation method and application thereof |
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| WO2021125980A1 (en) * | 2019-12-20 | 2021-06-24 | Victoria Link Limited | A cathode |
| CN111422906A (en) * | 2020-02-29 | 2020-07-17 | 合肥国轩高科动力能源有限公司 | Preparation method of silylene and molybdenum disulfide lithium battery cathode composite material |
| CN112500795A (en) * | 2020-10-23 | 2021-03-16 | 福建比美特环保集团有限公司 | Preparation process of wall covering with formaldehyde removing function |
| CN112500795B (en) * | 2020-10-23 | 2023-10-03 | 福建比美特环保集团有限公司 | Preparation process of wall clothing with formaldehyde removal function |
| CN113193198A (en) * | 2021-04-30 | 2021-07-30 | 陕西科技大学 | Cobalt-doped vanadium disulfide micron sheet and preparation method thereof |
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