CN108630979B - Secondary battery based on calcium ions and preparation method thereof - Google Patents

Secondary battery based on calcium ions and preparation method thereof Download PDF

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CN108630979B
CN108630979B CN201710184368.1A CN201710184368A CN108630979B CN 108630979 B CN108630979 B CN 108630979B CN 201710184368 A CN201710184368 A CN 201710184368A CN 108630979 B CN108630979 B CN 108630979B
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calcium
carbonate
positive electrode
active material
electrolyte
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CN108630979A (en
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唐永炳
王蒙
王恒
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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
    • 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
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a secondary battery based on calcium ions, which comprises a positive electrode, electrolyte, a negative electrode and a diaphragm; the positive electrode comprises a positive electrode current collector and a positive electrode active material layer arranged on the positive electrode current collector, wherein the positive electrode active material layer comprises a positive electrode active material, and the positive electrode active material comprises 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; the electrolyte comprises a calcium salt and a non-aqueous solvent; the negative electrode includes a metal foil which serves as both a negative electrode current collector and a negative electrode active material. The secondary battery takes calcium salt as electrolyte, and has the advantages of low cost, high working voltage, high capacity and excellent cycle performance. The invention also provides a preparation method of the secondary battery.

Description

Secondary battery based on calcium ions and preparation method thereof
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a secondary battery based on calcium ions and a preparation method thereof.
Background
The secondary battery may also be called a rechargeable battery, which is a battery that can be repeatedly charged and discharged and used for many times. Compared with a primary battery which can not be repeatedly used, the secondary battery has the advantages of low use cost and small environmental pollution. Currently, the main secondary battery technologies include lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, lithium ion batteries, and the like. Among them, the lithium ion battery is most widely used, and is a main energy supply mode for portable electronic devices such as mobile phones, notebook computers, digital cameras, and the like. The core components of a lithium ion battery typically include a positive electrode, a negative electrode, and an electrolyte, through interfaces between the positive electrode, the negative electrode, and the electrolyteThe ion transmission and the electron transmission are separated from each other, so that the electric energy storage and release are realized. The positive electrode of conventional lithium ion batteries is typically made of transition metal oxide (LiCoO)2、LiNiMnCoO2、LiMn2O4) Or polyanionic metal compounds (LiFePO)4) The negative electrode is made of graphite materials, and the electrolyte is an organic solution containing lithium salt. Both the positive electrode and the electrolyte contain lithium ions. However, the reserve of lithium on the earth is limited and highly active, so that the price of the existing lithium ion battery is high and certain potential safety hazard exists. In addition, the voltage of the traditional lithium ion battery is generally low, the capacity promotion space is limited, the energy density of the lithium ion battery is low, and the requirement of the novel application field is difficult to meet. Therefore, the development of a novel energy storage device with high energy density, low manufacturing cost, safety and high efficiency is the focus of research in the industry at present. Recently, the group has studied and reported a novel bi-ion battery (patent application No. 201510856238.9) which uses graphite carbon as a positive electrode material, metal foil (such as aluminum foil) as a negative electrode material and a current collector, an electrolyte consists of lithium salt and a carbonate organic solvent, and a diaphragm is made of glass fiber paper, and the battery has the advantages of low cost, simple process, high working voltage (up to 5V), high energy density, environmental friendliness and the like. The battery still does not preclude the use of a lithium salt electrolyte. The reserve of lithium on the earth is limited, the price is high, the development cost is high, and the lithium is extremely active and has potential safety hazards.
Disclosure of Invention
In view of this, embodiments of the present invention provide a secondary battery based on calcium ions, in which graphite and other materials are used as a positive electrode active material, a metal foil is used as a negative electrode current collector and a negative electrode active material, and a calcium salt is used as an electrolyte, so as to solve the problems of limited lithium resource storage, high cost, low battery energy density, poor cycle stability, and potential safety hazard of the existing lithium secondary battery.
Specifically, in a first aspect, the present invention provides a calcium ion-based 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 calcium salt and a non-aqueous solvent;
a negative electrode including a metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material;
and a separator interposed between the positive electrode and the negative electrode.
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, spherical graphite, crystalline flake 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 metal foil comprises any one of tin, aluminum, copper, iron, zinc, nickel, titanium, manganese, magnesium and antimony, or an alloy containing at least one of the metal elements, or a composite material containing at least one of the metal elements.
The calcium salt comprises calcium hexafluorophosphate (Ca (PF)6)2) Calcium tetrafluoroborate (Ca (BF)4)2) Calcium chloride, calcium carbonate, calcium fluorosilicate, calcium hexafluoroarsenate, calcium bis (oxalato) borate, calcium sulfate, calcium nitrate, calcium fluoride, calcium triflate (Ca (CF)3SO3)2) Calcium perchlorate (Ca (ClO)4)2) One or more of; in the electrolyte, the concentration of the calcium salt 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 comprises one or more of propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N-dimethylacetamide, fluoroethylene carbonate, methyl propionate, ethyl acetate, gamma-butyrolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, dimethoxymethane, 1, 2-dimethoxypropane, triethylene glycol dimethyl ether, dimethyl sulfone, dimethyl ether, ethylene sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite 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, 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 based on calcium ions, provided by the invention, the calcium salt is used as the electrolyte, and compared with the existing common commercial lithium ion secondary battery, the secondary battery based on calcium ions has the advantages of lower cost, higher working voltage, higher capacity, more excellent cycle performance and more outstanding safety performance.
In a second aspect, the present invention provides a method for preparing a secondary battery based on calcium ions, 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;
cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode; the metal foil is simultaneously used as a negative current collector and a negative active material;
and providing an electrolyte and a diaphragm, wherein the electrolyte comprises calcium salt and a non-aqueous solvent, the negative electrode, the diaphragm and the positive electrode are sequentially and tightly stacked under an inert gas and 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 based on calcium ions.
The preparation method of the secondary battery based on calcium ions 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 calcium ion-based secondary battery according to an embodiment of the present invention;
fig. 2 is a charge and discharge graph of a calcium ion-based secondary battery according to example 1 of the present invention;
fig. 3 is a graph showing rate performance of a calcium ion-based secondary battery according to example 1 of the present invention;
fig. 4 is a graph showing cycle performance of a calcium ion-based secondary battery according to example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and specific embodiments. While the following is a description of the preferred embodiments of the present invention, it should be noted that those skilled in the art can make various modifications and improvements without departing from the principle of the embodiments of the present invention, and such modifications and improvements are considered to be within the scope of the embodiments of the present invention.
Referring to fig. 1, an embodiment of the present invention provides a secondary battery including a positive electrode current collector 10, a positive electrode active material layer 20, an electrolyte 30, a separator 40, and a negative electrode 50; wherein the positive electrode current collector 10 and the positive electrode active material layer 20 disposed on the positive electrode current collector 10 together constitute a battery positive electrode, and the positive electrode active material layer 20 includes a positive electrode active material; the negative electrode 50 includes a metal foil, which serves as both a negative electrode current collector and a negative electrode active material; the electrolyte 30 includes a calcium salt and a non-aqueous solvent; the separator 40 is interposed between the positive electrode and the negative electrode 50.
The working principle of the secondary battery based on calcium ions provided by the embodiment of the invention is as follows: in the charging process, calcium salt anions in the electrolyte migrate to the positive electrode and are embedded into the positive electrode active material, and calcium ions migrate to the negative electrode and form a calcium-metal alloy with the negative electrode; in the discharging process, anions are removed from the positive active material and return to the electrolyte, and calcium ions are removed from the negative electrode and alloyed and return to the electrolyte, so that the whole charging and discharging process is realized. And since calcium ions are divalent ions, 2 moles of electron transport can be provided per mole of calcium ions by reaction, thereby contributing to the improvement of the capacity of the secondary battery. Therefore, the calcium ion-based secondary battery according to the embodiment of the present invention has a higher capacity than the existing lithium ion-based dual ion battery.
According to the secondary battery based on calcium ions, the positive electrode active material is graphite and other materials, the negative electrode is cheap metal foil, the electrolyte is calcium salt, and all the materials are rich in reserves, cheap and easily available, so that the production cost of the secondary battery can be effectively reduced. And the metal foil is simultaneously used as a negative active material and a negative current collector, so that the production process of the battery is simplified, the dead weight and the volume of the battery are reduced, the mass energy density and the volume energy density of the battery are improved, and the cost is reduced.
In an embodiment of the present invention, the positive electrode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials. Wherein the carbon material comprises one or more of graphite carbon material, glassy carbon, carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotube and graphene. Specifically, the graphite-based carbon material comprises one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbeads, pyrolytic graphite, highly oriented graphite and three-dimensional graphite sponge.
In an embodiment of the present invention, the sulfide is selected from one or more of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, and manganese sulfide; the nitride is selected from one or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from one or more of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide and manganese oxide; the carbide is one or more selected from titanium carbide, tantalum carbide, molybdenum carbide and silicon carbide.
In an embodiment of the present invention, the positive electrode active material has a layered crystal structure. Calcium salt anions are subjected to intercalation reaction through an interlayer structure of the positive active material by intercalation-deintercalation, and the reaction of the positive electrode is completed.
In an embodiment of the invention, the material of the metal foil includes any one of tin, aluminum, copper, iron, zinc, nickel, titanium, manganese, magnesium, and antimony, or an alloy containing at least one of the above metal elements, or a composite material containing at least one of the above metal elements.
In an embodiment of the present invention, the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, and manganese, or an alloy containing at least one of the foregoing metal elements, or a composite material containing at least one of the foregoing metal elements.
In the embodiment of the present invention, the calcium salt as the electrolyte may be one or more of calcium hexafluorophosphate, calcium tetrafluoroborate, calcium chloride, calcium carbonate, calcium fluorosilicate, calcium hexafluoroarsenate, calcium bis (oxalato) borate, calcium sulfate, calcium nitrate, calcium fluoride, calcium trifluoromethanesulfonate, and calcium perchlorate; in the electrolyte, the concentration of the calcium salt is 0.1-10 mol/L. Further, the concentration of the calcium 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 calcium ions and anions, and the calcium 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, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and one or more of lithium carbonate. The additive added in the electrolyte can form a stable solid electrolyte membrane on the surface of a negative current collector (metal foil), so that the metal foil is not damaged when being used as a negative active material, and the service life of the battery is prolonged.
In the embodiment of the present invention, the mass fraction of the additive in the electrolyte is 0.1 to 20%, and further 2 to 5%.
In the embodiment of the present invention, the separator may be an insulating porous polymer film or an inorganic porous film, and specifically may be one or more of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, and a porous ceramic separator.
In the embodiment of the invention, the positive active material layer further comprises a conductive agent and a binder, wherein the mass content of the positive active material is 60-90%, the mass content of the conductive agent is 5-30%, and the mass content of the binder is 5-10%. Further, the mass content of the positive electrode active material is 70-85%. The embodiment of the present invention is not particularly limited to the conductive agent and the binder, and any one commonly used in the art may be used. The conductive agent can be one or more of conductive carbon black, conductive carbon spheres, conductive graphite, carbon nanotubes, conductive carbon fibers, graphene and reduced graphene oxide. The binder can be one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl cellulose, SBR rubber and polyolefin.
Correspondingly, the embodiment of the invention also provides a preparation method of the secondary battery, which comprises the following steps:
(1) preparing a positive electrode: providing a positive current collector with a clean surface, weighing a positive active material, a conductive agent and a binder according to a certain proportion, and adding a proper solvent to fully mix to form uniform slurry; then uniformly coating the slurry on the surface of a positive electrode current collector to form a positive electrode active material layer, and pressing and cutting after complete drying to obtain a battery positive electrode with the required size;
(2) preparing a negative electrode: cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode;
(3) preparing an electrolyte: and weighing a certain amount of calcium salt electrolyte, adding the calcium salt electrolyte into the non-aqueous solvent, and fully stirring and dissolving to obtain the required electrolyte.
(4) Preparing a diaphragm: cutting the porous polymer film or the inorganic porous film into required sizes, and cleaning to obtain the required diaphragm.
(5) Assembling the battery: and tightly stacking the prepared battery cathode, diaphragm and anode in turn under inert gas and anhydrous environment, adding the electrolyte to completely infiltrate the diaphragm, then packaging the stacked part into a battery shell, and completing assembly to obtain the secondary battery based on calcium ions.
It should be noted that although the above steps (1) to (4) describe the operations of the method for manufacturing a secondary battery based on calcium ions according to the present invention in a specific order, it is not necessary to perform the operations in the specific order. The operations of steps (1) - (4) may be performed simultaneously or in any order.
The raw materials used in the above preparation method of the embodiment of the present invention are as described in the foregoing embodiments, and are not described herein again.
The following examples are provided to further illustrate the preparation of the above-described secondary battery based on calcium ions.
Example 1
(1) Preparing a battery cathode: taking a tin foil with the thickness of 0.1mm, cutting the tin foil into a wafer with the diameter of 12mm, cleaning the wafer with ethanol, and airing the wafer to be used as a negative electrode for later use;
(2) preparing a diaphragm: cutting the Celgard 2400 porous polymer film into round pieces with the diameter of 16mm, cleaning the round pieces with acetone, and airing the round pieces to be used as a diaphragm for later use;
(3) preparing an electrolyte: weighing 1.32g of calcium hexafluorophosphate, adding the calcium hexafluorophosphate into 0.8mL of Ethylene Carbonate (EC), 0.8mL of Propylene Carbonate (PC), 1.2mL of dimethyl carbonate (DMC) and 1.2mL of Ethyl Methyl Carbonate (EMC), and stirring until the calcium hexafluorophosphate is completely dissolved to be used as an electrolyte for later use;
(4) preparing a battery positive electrode: adding 0.8g of artificial graphite, 0.1g of conductive carbon black and 0.1g of polyvinylidene fluoride into 2mL of nitrogen methyl pyrrolidone solution, and fully grinding to obtain uniform slurry; the slurry was then uniformly coated on the aluminum foil surface (i.e., the positive current collector) and vacuum dried for 12 h. Cutting the dried electrode slice into a wafer with the diameter of 10mm, and compacting the wafer to be used as a battery anode for standby;
(5) assembling the battery: and (3) in a glove box protected by inert gas, tightly stacking the prepared cathode, the diaphragm and the anode in sequence, dripping electrolyte to completely soak the diaphragm, packaging the stacked part into a button cell shell, and completing cell assembly to obtain the secondary cell based on calcium ions.
The secondary battery obtained in example 1 of the present invention was subjected to a constant current charge and discharge test with a current density of 100mA/g and a voltage range of 3 to 5V (the same test methods were used in subsequent examples of the present invention to perform electrochemical performance tests). Fig. 2 is a graph showing charge and discharge curves of a calcium ion-based secondary battery according to an embodiment of the present invention; fig. 3 is a graph of rate performance of a calcium ion-based secondary battery according to an embodiment of the present invention; fig. 4 is a graph showing cycle performance of a calcium ion-based secondary battery according to an embodiment of the present invention. It can be seen from the figure that the secondary battery based on calcium ions of the present invention has high discharge voltage, high capacity, excellent rate capability and excellent cycle performance. The secondary battery of the embodiment 1 of the invention has the working average voltage of more than 4.2V, the specific capacity of 85.8mAh/g, the energy density of 168Wh/kg and the cycle number of 300 times when the capacity is attenuated to 90 percent.
The double-ion secondary battery using the calcium 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, environmental friendliness and high safety.
Examples 2 to 11
Examples 2 to 11 were prepared by the same procedure and using the same materials as in example 1 except that the materials used in the preparation of the negative electrode for the battery were different, and the secondary batteries of examples 2 to 11 were subjected to the electrochemical performance test of the battery and compared with the performance of example 1 of the present invention, and the negative electrode materials used in examples 2 to 11 and their electrochemical performance were specifically shown in table 1.
TABLE 1
Figure BDA0001254435280000101
Figure BDA0001254435280000111
As can be seen from table 1, in the embodiment of the present invention, when the tin foil is used as the negative electrode, the specific capacity of the battery is higher, the cycle performance is better, and the energy density is highest.
Examples 12 to 34
The secondary batteries of examples 12 to 34 were fabricated by the same procedure and using the same materials as those used in the fabrication of the positive electrode of the battery, except that the processes for fabricating the secondary batteries of example 1 were different from those of the positive electrode active material used in the fabrication of the positive electrode of the battery, and the secondary batteries of examples 12 to 34 were simultaneously subjected to the electrochemical performance test of the battery and compared with the performance of example 1 of the present invention, specifically referring to table 2.
TABLE 2
Figure BDA0001254435280000112
Figure BDA0001254435280000121
As can be seen from table 2, in the embodiment of the present invention, when the graphite-based carbon material is used as the positive electrode active material, the battery has a higher specific capacity, a higher energy density, and a better cycle performance.
Examples 35 to 43
The secondary batteries of examples 35 to 43 were tested for electrochemical properties of batteries according to examples 35 to 43, and compared with those of example 1 according to the present invention, and the electrolyte materials used in examples 35 to 43 and the electrochemical properties of the batteries were specifically shown in table 3.
TABLE 3
Figure BDA0001254435280000122
As can be seen from Table 3, in the examples of the present invention, the electrolyte was Ca (PF)6)2、Ca(BF4)2、Ca(CF3SO3)2、Ca(ClO4)2、CaF2The electrochemical performance of the battery is relatively better.
Examples 44 to 48
The secondary batteries of examples 44 to 48 were tested for electrochemical properties of batteries according to examples 44 to 48 while the secondary batteries of examples 44 to 48 were identical to those of example 1 except that the electrolyte concentration used in preparing the electrolyte was different from that used in preparing the electrolyte, and the electrolyte concentrations used in examples 44 to 48 and the electrochemical properties of the batteries were compared with those of example 1 according to the present invention, and specifically, see table 4.
TABLE 4
Figure BDA0001254435280000131
As can be seen from Table 4, in the examples of the present invention, when the electrolyte concentration is 1mol/L, the specific capacity of the battery is high, the energy density is high, and the cycle performance is more excellent.
Examples 49 to 61
Examples 49-61 secondary batteries of examples 49-61 were tested for electrochemical properties and compared with those of example 1 of the present invention while the secondary batteries of examples 49-61 were subjected to the same procedure and the same materials except that the solvents used in the preparation of the electrolyte solutions were different, and the solvents used in examples 49-61 and their electrochemical properties were specifically shown in table 5.
TABLE 5
Figure BDA0001254435280000132
Figure BDA0001254435280000141
As can be seen from table 5, in the examples of the present invention, the solvent is ethylene carbonate: propylene carbonate, dimethyl carbonate: ethyl methyl carbonate: (volume ratio 2:2:3:3) the mixed solution has high specific capacity of the battery, high energy density and better cycle performance.
Examples 62 to 70
The secondary batteries of examples 62 to 70 were tested for electrochemical properties of batteries while the secondary batteries of examples 62 to 70 were identical in all steps and materials except for the kinds and amounts of additives used in preparing the electrolyte, and compared with those of example 1 of the present invention, the solvent materials used in examples 62 to 70 and their electrochemical properties are specifically shown in table 6.
TABLE 6
Figure BDA0001254435280000142
Figure BDA0001254435280000151
As can be seen from table 6, in the examples of the present invention, some additives are beneficial to increase the energy density or the cycle stability of the battery, but the types and the addition amounts of the additives need to be further optimized to obtain the best battery performance.
Examples 71 to 74
Examples 71-74 were prepared by the same procedure and using the same materials as in example 1 except that the materials of the separator used in the preparation of the separator were different, and the electrochemical properties of the batteries of examples 71-74 were measured and compared with those of example 1 according to the present invention, and the materials of the separators used in examples 71-74 and their electrochemical properties were specifically shown in table 7.
TABLE 7
Figure BDA0001254435280000152
As can be seen from table 7, the selection of different separator materials did not have a significant effect on the electrochemical performance of the secondary battery.
Examples 75 to 81
The secondary batteries of examples 75 to 81 were fabricated by the same procedure and using the same materials as those of example 1 except that the types and mass fractions of the conductive agent and the binder used in fabricating the positive electrodes of the batteries were different, and the secondary batteries of examples 75 to 81 were subjected to the electrochemical performance test of the batteries and compared with the performance of example 1 of the present invention, and the types and mass fractions of the conductive agent and the binder used in examples 75 to 81 are specifically shown in table 8.
TABLE 8
Figure BDA0001254435280000161
As can be seen from table 8, the selection of different conductive agents, binder types, and different amounts of addition had no significant effect on the cycle number, energy density, and other properties of the secondary battery.
The secondary battery according to the present invention may be designed in the form of a rectangular battery, a cylindrical battery, a pouch battery, or the like, according to the core components, without being limited to a button battery.
The secondary battery provided by the invention has the advantages that the main active components are materials with a layered crystal structure, such as graphite, the electrolyte is calcium salt with abundant resource reserves, the secondary battery is environment-friendly, the cost is low, and the battery capacity is high. Meanwhile, the metal foil in the secondary battery system of the invention is used as a negative current collector and a negative active material at the same time, thereby obviously reducing the dead weight and the cost of the battery and improving the energy density of the battery. The average working voltage of the secondary battery provided by the invention is more than 4.2V.

Claims (6)

1. A calcium ion-based 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, artificial graphite, spherical graphite, mesocarbon microbeads graphite, a mixture of natural graphite and artificial graphite or a mixture of natural graphite and mesocarbon microbeads graphite;
the electrolyte comprises a calcium salt and a non-aqueous solvent, wherein the calcium salt is calcium hexafluorophosphate, calcium tetrafluoroborate, calcium trifluoromethanesulfonate or a mixture of calcium hexafluorophosphate and calcium tetrafluoroborate, the non-aqueous solvent is ethylene carbonate, propylene carbonate, a mixture of dimethyl carbonate and ethyl methyl carbonate or a mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, and the concentration of the electrolyte is 0.8mol/L or 4 mol/L;
a negative electrode including a metal foil, the metal foil simultaneously serving as a negative electrode current collector and a negative electrode active material; the metal foil is tin foil, aluminum tin alloy or copper tin alloy;
and a separator interposed between the positive electrode and the negative electrode.
2. The calcium ion-based secondary battery according to claim 1, wherein the material of 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 calcium ion-based secondary battery according to claim 1, wherein the electrolyte further comprises an additive, the additive comprises one or more of esters, sulfones, ethers, nitriles and olefin organic additives, and the mass fraction of the additive in the electrolyte is 0.1-20%.
4. The calcium ion-based secondary battery according to claim 3, wherein 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, methyl chloroformate, dimethyl sulfoxide, anisole, acetamide, diazabenzene, m-diazabenzene, 12-crown-4, 18-crown-6, 4-fluorophenylmethyl ether, fluoro chain ether, vinyl difluoromethyl carbonate, vinyl trifluoromethycarbonate, vinyl chlorocarbonate, vinyl bromocarbonate, trifluoroethyl phosphonic acid, bromo butyrolactone, fluoroacetoxyethane, phosphate, phosphite, One or more of phosphazene, ethanolamine, carbonized dimethylamine, cyclobutyl sulfone, 1, 3-dioxolane, acetonitrile, sodium carbonate, calcium carbonate, carbon dioxide, sulfur dioxide and lithium carbonate.
5. The calcium ion-based secondary battery according to claim 1, wherein the separator is an insulating porous polymer film or an inorganic porous film.
6. A preparation method of a secondary battery based on calcium ions 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, artificial graphite, mesocarbon microbead graphite, a mixture of natural graphite and artificial graphite, or a mixture of natural graphite and mesocarbon microbead graphite;
cutting the metal foil into required size, and cleaning and drying the surface to obtain the cathode; the metal foil is simultaneously used as a negative current collector and a negative active material; the metal foil is tin foil, aluminum tin alloy or copper tin alloy;
and providing an electrolyte and a diaphragm, wherein the electrolyte comprises a calcium salt and a non-aqueous solvent, the negative electrode, the diaphragm and the positive electrode are sequentially and tightly stacked under an inert gas and anhydrous environment, the electrolyte is added to completely infiltrate the diaphragm, then the stacked parts are packaged into a battery shell to obtain the secondary battery based on calcium ions, the calcium salt is calcium hexafluorophosphate, calcium tetrafluoroborate, calcium trifluoromethanesulfonate or a mixture of calcium hexafluorophosphate and calcium tetrafluoroborate, the non-aqueous solvent is ethylene carbonate, propylene carbonate, a mixture of dimethyl carbonate and ethyl methyl carbonate or a mixture of ethylene carbonate, dimethyl carbonate and ethyl methyl carbonate, and the concentration of the electrolyte is 0.8mol/L or 4 mol/L.
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