CN108470908B - Secondary battery and preparation method thereof - Google Patents
Secondary battery and preparation method thereof Download PDFInfo
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- CN108470908B CN108470908B CN201710100651.1A CN201710100651A CN108470908B CN 108470908 B CN108470908 B CN 108470908B CN 201710100651 A CN201710100651 A CN 201710100651A CN 108470908 B CN108470908 B CN 108470908B
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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
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Abstract
The invention provides a secondary battery, which comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode comprises a positive active material, and the positive active material comprises one or more of carbon materials, sulfides, nitrides, oxides, carbides and composites of the materials; the negative electrode comprises a negative electrode active material comprising one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials; the electrolyte includes a potassium salt and a non-aqueous solvent. The battery takes the sylvite as electrolyte, and has the advantages of low cost, high working voltage, high energy density and excellent cycle performance. The invention also provides a preparation method of the secondary battery.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a secondary battery and a preparation method thereof.
Background
A secondary battery is also called a rechargeable battery, and is a battery that can be repeatedly charged and discharged and used many times. Compared with a primary battery which can not be repeatedly used, the secondary battery has the advantages of low use cost and small environmental pollution. The main secondary battery technologies at present are lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, lithium ion batteries, and the like. Among them, lithium ion batteries are most widely used. However, lithium ion batteries face the disadvantages of limited lithium resource reserves and high cost. Potassium ion batteries have gained increased attention in recent years as an energy storage technology that potentially replaces lithium ion batteries.
The working principle of the potassium ion battery is similar to that of the lithium ion battery, but the storage and release of the charge in the battery are realized through the migration of potassium ions. The core components of the potassium ion battery comprise a positive electrode, a negative electrode and electrolyte, and the storage and release of electric energy are realized through the oxidation-reduction reaction of ion transmission and electron transmission separation which occurs on the interfaces of the positive electrode, the negative electrode and the electrolyte. During charging, potassium ions are removed from the positive active material and are embedded into the negative active material; during discharge, potassium ions are extracted from the negative electrode active material and inserted into the positive electrode active material. Common potassium ion batteries use prussian blue and its analogs, iron phosphate, iron fluorosulfate, etc. as positive active materials, and carbon materials as negative active materials. However, the types of positive and negative electrode materials developed based on the potassium ion battery are very limited at present, the research is basically limited to the half-battery of the potassium sheet, the electrochemical performance of the potassium ion battery based on the developed materials is not ideal, and the preparation process is complex.
Disclosure of Invention
In view of the above, the first aspect of the present invention provides a secondary battery, which uses carbon or the like as a positive electrode active material and a negative electrode active material, and uses potassium salt as an electrolyte, and which avoids the use of a lithium salt with limited resources, thereby significantly reducing the cost of the battery and reducing the environmental impact of the battery. In addition, the battery has a double-ion battery working mechanism, the working voltage reaches 4.65V, and the battery is higher than that of a traditional lithium ion battery, so that the energy density is improved, and the electrochemical cycling stability is good.
Specifically, in a first aspect, the present invention provides a secondary battery comprising:
the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material comprises one or more of carbon materials, sulfides, nitrides, oxides, carbides and composites of the carbon materials, the sulfides, the nitrides, the oxides and the carbides;
an electrolyte comprising a potassium salt and a non-aqueous solvent;
a negative electrode including a negative electrode current collector and a negative electrode active material layer disposed on the negative electrode current collector, the negative electrode active material layer including a negative electrode active material including one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials;
and a separator interposed between the positive electrode and the negative electrode.
The carbon material comprises one or more of graphite carbon material, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nano tube and graphene.
The graphite carbon material comprises one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbeads graphite, pyrolytic graphite, highly oriented graphite and three-dimensional graphite sponge.
The sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide; the carbide is one or more selected from titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
The material of the positive current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium and manganese, or an alloy containing at least one of the metal elements, or a composite material containing at least one of the metal elements.
The material of the negative current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium and manganese, or an alloy containing at least one of the metal elements, or a composite material containing at least one of the metal elements.
The potassium salt comprises one or more of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluorooxalato borate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methylsulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonylimide and potassium trifluoromethanesulfonate; in the electrolyte, the concentration of the sylvite is 0.1-10 mol/L.
The non-aqueous solvent comprises an organic solvent and ionic liquid, wherein the organic solvent comprises one or more of ester, sulfone, ether and nitrile organic solvents.
The organic solvent includes Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), gamma-butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), Propylene Sulfite (PS), One or more of dimethyl sulfite (DMS), diethyl sulfite (DES) and crown ether (12-crown-4).
The ionic liquid comprises 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, a salt of a compound of formula (I), One or more of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt.
The electrolyte also comprises an additive, wherein the additive comprises one or more of ester, sulfone, ether, nitrile and olefin organic additives, and the mass fraction of the additive in the electrolyte is 0.1-20%.
The additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, ethylene sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, difluoro methyl vinyl carbonate, trifluoro methyl vinyl carbonate, chloro vinyl carbonate, bromo vinyl carbonate, trifluoroethyl phosphonic acid, butyrolactone bromide, fluoroacetoxyethane, phosphate ester, phosphite ester, phosphazene, ethanolamine, dimethylamine carbide, One or more of cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and lithium carbonate.
The diaphragm is an insulating porous polymer film or an inorganic porous film.
According to the secondary battery provided by the first aspect of the invention, the potassium salt is used as the electrolyte, so that the problem that the lithium resource storage capacity of the existing lithium secondary battery is limited is solved, the battery cost is reduced, and the secondary battery is environment-friendly; in addition, the secondary battery provided by the invention has higher working voltage, the energy density of the battery is improved, and the battery has good charge-discharge cycle performance.
In a second aspect, the present invention provides a method for manufacturing a secondary battery, comprising the steps of:
providing a positive current collector, preparing a positive active material layer on the positive current collector, drying, pressing and cutting into required sizes to obtain a positive electrode; the positive electrode active material layer includes a positive electrode active material including one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials;
providing a negative current collector, preparing a negative active material layer on the negative current collector, drying, pressing and cutting into required sizes to obtain a negative electrode; the negative electrode active material layer includes a negative electrode active material including one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials;
and providing an electrolyte and a diaphragm, wherein the electrolyte comprises potassium salt and a non-aqueous solvent, the negative electrode, the diaphragm and the positive electrode are sequentially and tightly stacked in an inert gas or anhydrous environment, the electrolyte is added to completely soak the diaphragm, and then the stacked part is packaged into a battery shell to obtain the secondary battery.
The preparation method of the secondary battery provided by the second aspect of the invention has simple process and is suitable for large-scale production.
Advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the invention.
Drawings
Fig. 1 is a schematic structural view of a secondary battery provided in an embodiment of the present invention.
Detailed Description
While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a secondary battery including a positive electrode current collector 10, a positive electrode active material layer 20, an electrolyte 30, a separator 40, a negative electrode active material layer 50, and a negative electrode current collector 60; wherein the positive electrode active material layer 20 includes a positive electrode active material in which a potassium salt anion can be inserted, the positive electrode active material including one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials; the negative electrode active material layer 50 includes a negative electrode active material that can intercalate potassium ions, the negative electrode active material including one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials; the electrolyte 30 includes a potassium salt and a nonaqueous solvent; the separator 40 is interposed between the positive electrode active material layer 20 and the negative electrode active material layer 50.
The working principle of the secondary battery provided by the embodiment of the invention is as follows: during charging, potassium salt anions in the electrolyte migrate to the positive electrode and are embedded in the positive electrode active material, and potassium ions migrate to the negative electrode and are embedded in the negative electrode active material; during the discharging process, potassium salt anions are separated from the positive electrode active material and enter the electrolyte, and meanwhile, potassium ions are separated from the negative electrode and enter the electrolyte, so that the whole charging and discharging process is realized. In the process, all electrolytes in the electrolyte are sylvite, so that the problem of limited reserve of the conventional lithium resource is solved, the cost of the secondary battery is obviously reduced, and the influence of the battery on the environment is reduced.
In an embodiment of the present invention, the carbon material includes one or more of graphite-based carbon material, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotube, and graphene. Specifically, the graphite-based carbon material comprises one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbeads, pyrolytic graphite, highly oriented graphite and three-dimensional graphite sponge.
In an embodiment of the present invention, the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide; the carbide is one or more selected from titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
In the embodiment of the present invention, the positive electrode active material may be the same material as the negative electrode active material, or may be a different material. In an embodiment of the present invention, the positive electrode active material and the negative electrode active material have a layered crystal structure.
In an embodiment of the present invention, the material of the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
In an embodiment of the present invention, the material of the negative electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
In the embodiment of the present invention, the potassium salt as the electrolyte may be one or more of potassium hexafluorophosphate, potassium chloride, potassium fluoride, potassium sulfate, potassium carbonate, potassium phosphate, potassium nitrate, potassium difluoroborate, potassium pyrophosphate, potassium dodecylbenzenesulfonate, potassium dodecylsulfate, tripotassium citrate, potassium metaborate, potassium borate, potassium molybdate, potassium tungstate, potassium bromide, potassium nitrite, potassium iodate, potassium iodide, potassium silicate, potassium lignosulfonate, potassium oxalate, potassium aluminate, potassium methanesulfonate, potassium acetate, potassium dichromate, potassium hexafluoroarsenate, potassium tetrafluoroborate, potassium perchlorate, potassium trifluoromethanesulfonimide, and potassium trifluoromethanesulfonate. In the electrolyte, the concentration of the potassium salt can be 0.1-10 mol/L. Further, the concentration of the potassium salt may be 0.1 to 2 mol/L.
In the embodiment of the present invention, the nonaqueous solvent in the electrolytic solution is not particularly limited as long as the electrolyte can be dissociated into potassium ions and anions, and the potassium ions and the anions can freely migrate. Specifically, the non-aqueous solvent comprises an organic solvent and an ionic liquid, wherein the organic solvent can be one or more of ester, sulfone, ether and nitrile organic solvents. More specifically, the organic solvent may be Propylene Carbonate (PC), Ethylene Carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Methyl Formate (MF), Methyl Acetate (MA), N-Dimethylacetamide (DMA), fluoroethylene carbonate (FEC), Methyl Propionate (MP), Ethyl Propionate (EP), Ethyl Acetate (EA), γ -butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1, 3-Dioxolane (DOL), 4-methyl-1, 3-dioxolane (4MeDOL), Dimethoxymethane (DMM), 1, 2-Dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethylsulfone (MSM), dimethyl ether (DME), Ethylene Sulfite (ES), Ethylene Carbonate (EC), methyl propionate (EA), Ethyl Acetate (EA), gamma-butyrolactone (GBL), Tetrahydrofuran (THF), 2-methyltetrahydrofuran (2, One or more of Propylene Sulfite (PS), dimethyl sulfite (DMS), diethyl sulfite (DES) and crown ether (12-crown-4). The ionic liquid comprises 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonyl imide salt, a salt of a compound of formula (I), One or more of N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl-N-propylpyrrolidine-bistrifluoromethylsulfonyl imide salt, N-methyl, propylpiperidine-bistrifluoromethylsulfonyl imide salt, N-methyl, butylpiperidine-bistrifluoromethylsulfonyl imide salt.
In the embodiment of the invention, in order to prevent the negative electrode from being damaged due to volume change during charging and discharging, keep the structure of the negative electrode stable, and improve the service life and the performance of the negative electrode so as to improve the cycle performance of the secondary battery, the electrolyte further comprises an additive, and the additive can be one or more of ester, sulfone, ether, nitrile and olefin organic additives. Specifically, the additive comprises fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, vinyl sulfate, propylene sulfate, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluorophenylmethyl ether, fluorinated chain ether, difluoromethyl vinyl carbonate, trifluoromethyl vinyl carbonate, chloroethyl vinyl carbonate, bromovinyl carbonate, trifluoroethyl phosphonic acid, bromobutyrolactone, fluoroacetoethane, phosphate ester, phosphite ester, phosphazene, ethanolamine, Carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, long-chain olefin, aluminum oxide, magnesium oxide, barium oxide, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and one or more of lithium carbonate.
In the embodiment of the present invention, the mass fraction of the additive in the electrolyte is 0.1 to 20%, and further 2 to 5%.
In the embodiment of the present invention, the separator may be an insulating porous polymer film or an inorganic porous film, and specifically may be one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, and a porous ceramic separator.
In the embodiment of the invention, the positive active material layer further comprises a conductive agent and a binder, wherein the content of the positive active material is 60-90 wt%, the content of the conductive agent is 5-30 wt%, and the content of the binder is 5-10 wt%. The negative active material layer further comprises a conductive agent and a binder, wherein the content of the negative active material is 60-90 wt%, the content of the conductive agent is 5-30 wt%, and the content of the binder is 5-10 wt%. The embodiment of the present invention is not particularly limited to the conductive agent and the binder, and any one commonly used in the art may be used. The conductive agent can be one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide. The binder can be one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
Correspondingly, an embodiment of the present invention further provides a method for manufacturing the secondary battery in the above embodiment, including the following steps:
step 1, preparing a battery anode: providing a positive current collector with a clean surface, weighing a positive active material, a conductive agent and a binder according to a certain proportion, and adding a proper solvent to fully mix to form uniform slurry; then uniformly coating the slurry on the surface of a positive electrode current collector to form a positive electrode active material layer, and cutting after completely drying to obtain a battery positive electrode with a required size;
step 2, preparing a battery cathode: providing a negative current collector with a clean surface, weighing a negative active material, a conductive agent and a binder according to a certain proportion, and adding a proper solvent to fully mix to form uniform slurry; then uniformly coating the slurry on the surface of a negative current collector to form a negative active material layer, and cutting after completely drying to obtain the battery negative electrode with the required size;
step 3, preparing electrolyte: and weighing a certain amount of potassium salt electrolyte, adding the potassium salt electrolyte into the non-aqueous solvent, and fully stirring and dissolving to obtain the required electrolyte.
Step 4, preparing the diaphragm: cutting the porous polymer film or the inorganic porous film into required sizes, and cleaning to obtain the required diaphragm.
Step 5, assembling the battery: and tightly stacking the prepared battery cathode, diaphragm and anode in turn in an inert gas or anhydrous environment, adding the electrolyte to completely soak the diaphragm, packaging the stacked part into a battery shell, and completing assembly to obtain the secondary battery.
It should be noted that although the above steps 1 to 4 describe the operations of the secondary battery production method of the present invention in a specific order, this does not require or imply that these operations must be performed in this specific order. The preparation of steps 1-4 may be performed simultaneously or in any order.
The following examples are provided to further illustrate the method of manufacturing the above secondary battery.
Example 1
A method for manufacturing a secondary battery, comprising the steps of:
step 1, preparing a battery cathode: adding 0.8g of expanded graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 4mL of nitrogen methyl pyrrolidone solution, and fully mixing to obtain uniform slurry; and then uniformly coating the slurry on the surface of the copper foil current collector and performing vacuum drying. And cutting the dried electrode slice into a circular slice with the diameter of 12mm, and compacting the circular slice to be used as a battery cathode for standby.
Step 2, preparing the diaphragm: the glass fiber paper was cut into a circular sheet having a diameter of 16mm and used as a separator.
Step 3, preparing electrolyte: weighing 3g of potassium hexafluorophosphate, adding the potassium hexafluorophosphate into 5mL of a mixed solvent of ethylene carbonate, diethyl carbonate and ethyl methyl carbonate in a volume ratio of 4:3:2, stirring until the potassium hexafluorophosphate is completely dissolved, adding fluoroethylene carbonate with the mass fraction of 5% as an additive, and fully and uniformly stirring to obtain an electrolyte for later use.
Step 4, preparing the battery anode: adding 0.8g of expanded graphite, 0.1g of carbon black and 0.1g of polyvinylidene fluoride into 4mL of nitrogen methyl pyrrolidone solution, and fully mixing to obtain uniform slurry; and then uniformly coating the slurry on the surface of the aluminum foil current collector and performing vacuum drying. And cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as the battery anode for later use.
Step 5, assembling the battery: and tightly stacking the prepared battery cathode, the diaphragm and the battery anode in turn in a glove box protected by inert gas, dripping electrolyte to completely soak the diaphragm, packaging the stacked part into a button cell shell, and completing cell assembly to obtain the secondary battery.
The working mechanism of the secondary battery of embodiment 1 of the present invention is: negative electrode:
and (3) positive electrode:
the secondary battery of example 1 of the present invention was subjected to constant current charge and discharge test with a current density of 100mA/g and a voltage range of 3-5V (the same test methods were used in subsequent examples of the present invention to obtain electrochemical performance results). Tests show that the working voltage of the secondary battery in the embodiment 1 of the invention is 4.65V, the specific capacity of the battery is 66mAh/g, the energy density is 145Wh/kg, and the cycle number is 200 times when the capacity is attenuated to 85%. The double-graphite secondary battery using the potassium salt as the electrolyte in embodiment 1 of the invention has the advantages of high working voltage, high energy density, long cycle life, low raw material cost and process cost, and environmental friendliness.
Examples 2 to 51
Examples 2 to 51 differ from example 1 only in that the negative electrode active material was different, and specifically, as shown in table 1, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the results thereof are shown in table 1:
TABLE 1
As can be seen from table 1, when the graphite-based carbon material is used as the negative electrode active material, the battery has high specific capacity, high energy density, and better cycle performance.
Examples 52 to 101
Examples 52 to 101 differ from example 1 only in that the positive electrode active material was different, and specifically, as shown in table 2, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the results thereof are shown in table 2:
TABLE 2
As can be seen from table 2, when the graphite-based carbon material is used as the positive electrode active material, the specific capacity of the battery is higher, the energy density is higher, and the cycle performance is better.
Example 102-
Example 102-130 differs from example 1 only in that the electrolyte salt is different, and specifically as shown in table 3, the secondary battery obtained in the above example was subjected to a constant current charge and discharge test, and the results are shown in table 3:
TABLE 3
As can be seen from Table 3, KPF was selected as the electrolyte6、KBF4、KClO4And the potassium hexafluoroarsenate, the potassium trifluoromethanesulfonylimide and the potassium trifluoromethanesulfonate have the advantages of higher specific capacity, higher energy density and better cycling stability.
Example 130-
Example 130-132 differed from example 1 only in that the electrolyte concentration was different, and specifically as shown in table 4, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the results thereof are shown in table 4:
TABLE 4
As can be seen from table 4, the specific capacity of the battery is higher, the energy density is higher, and the cycle performance is excellent when the electrolyte concentration is 1 mol/L.
Example 133-
The embodiment 133-184 differs from the embodiment 1 only in the kind of the additive in the electrolyte, and specifically, as shown in table 5, the secondary battery obtained in the above embodiment was subjected to the constant current charge and discharge test, and the results thereof are shown in table 5:
TABLE 5
As can be seen from table 5, the electrolyte additive is fluoroethylene carbonate, the energy density of the battery is higher, and the cycle performance is more excellent.
Example 185-
Example 185-188 differs from example 1 only in that the mass contents of the additives in the electrolyte are different, and specifically as shown in table 6, the secondary batteries obtained in the above examples were subjected to constant current charge and discharge tests, and the results are shown in table 6:
TABLE 6
As can be seen from table 6, when the electrolyte additive was contained in an amount of 5 wt%, the energy density of the battery was high and the cycle performance was excellent.
Example 189-
Example 189-238 differed from example 1 only in the type of electrolyte solvent, and specifically, as shown in table 7, the secondary batteries obtained in the above examples were subjected to constant current charge/discharge test, and the results thereof are shown in table 7:
TABLE 7
As can be seen from table 7, when the electrolyte solvent was ethylene carbonate + ethyl methyl carbonate + dimethyl carbonate, the energy density of the battery was higher and the cycle performance was excellent.
The secondary battery according to the embodiment of the present invention may be designed in the form of a flat battery, a cylindrical battery, or the like, according to the core components, without being limited to a button battery. The secondary battery of the embodiment of the invention takes the potassium salt as the electrolyte, has a working mechanism of a double-ion battery, has the working voltage of 4.65V which is higher than that of the traditional lithium ion battery, thereby improving the energy density, having good electrochemical cycle stability, and simultaneously having lower preparation cost and wide prospect in the field of secondary batteries.
Claims (5)
1. A bi-ion secondary battery, comprising:
the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material is natural graphite, expanded graphite, mesocarbon microbeads or a mixture of the expanded graphite and the mesocarbon microbeads;
the electrolyte comprises a potassium salt and a non-aqueous solvent, wherein the potassium salt is potassium hexafluorophosphate, the concentration of the potassium salt in the electrolyte is 1mol/L, the non-aqueous solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the electrolyte also comprises an additive, the additive is fluoroethylene carbonate, and the mass fraction of the additive in the electrolyte is 5%;
the negative electrode comprises a negative electrode current collector and a negative electrode active material layer arranged on the negative electrode current collector, wherein the negative electrode active material layer comprises a negative electrode active material, and the negative electrode active material is natural graphite, expanded graphite, mesocarbon microbead graphite or a mixture of the expanded graphite and the mesocarbon microbead graphite;
and a separator interposed between the positive electrode and the negative electrode.
2. The bi-ion secondary battery of claim 1, wherein the positive electrode current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
3. The bi-ion secondary battery of claim 1, wherein the negative current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
4. The bi-ion secondary battery of claim 1, wherein the separator is an insulating porous polymer film or an inorganic porous film.
5. A method for manufacturing a bi-ion secondary battery is characterized by comprising the following steps:
providing a positive current collector, preparing a positive active material layer on the positive current collector, drying, pressing and cutting into required sizes to obtain a positive electrode; the positive active material layer comprises a positive active material, and the positive active material is natural graphite, expanded graphite, mesocarbon microbead graphite or a mixture of the expanded graphite and the mesocarbon microbead graphite;
providing a negative current collector, preparing a negative active material layer on the negative current collector, drying, pressing and cutting into required sizes to obtain a negative electrode; the negative active material layer comprises a negative active material, and the negative active material is natural graphite, expanded graphite, mesocarbon microbead graphite or a mixture of the expanded graphite and the mesocarbon microbead graphite;
providing an electrolyte and a diaphragm, wherein the electrolyte comprises a potassium salt and a non-aqueous solvent, the potassium salt is potassium hexafluorophosphate, the concentration of the potassium salt in the electrolyte is 1mol/L, the non-aqueous solvent is a mixed solvent of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, the electrolyte further comprises an additive, the additive is fluoroethylene carbonate, and the mass fraction of the additive in the electrolyte is 5%;
and tightly stacking the negative electrode, the diaphragm and the positive electrode in sequence under an inert gas or anhydrous environment, adding the electrolyte to completely soak the diaphragm, and then packaging the stacked part into a battery shell to obtain the secondary battery.
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