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WO2018170925A1 - Pile rechargeable au calcium-ion et son procédé de fabrication - Google Patents

Pile rechargeable au calcium-ion et son procédé de fabrication Download PDF

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Publication number
WO2018170925A1
WO2018170925A1 PCT/CN2017/078203 CN2017078203W WO2018170925A1 WO 2018170925 A1 WO2018170925 A1 WO 2018170925A1 CN 2017078203 W CN2017078203 W CN 2017078203W WO 2018170925 A1 WO2018170925 A1 WO 2018170925A1
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Prior art keywords
calcium
positive electrode
secondary battery
carbon
carbonate
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PCT/CN2017/078203
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English (en)
Chinese (zh)
Inventor
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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    • 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

Definitions

  • the present invention relates to the field of secondary battery technology, and in particular to a secondary battery based on calcium ions and a preparation method thereof.
  • a secondary battery which can also be called a rechargeable battery, is a rechargeable battery that can be repeatedly charged and discharged. Compared with a non-reusable primary battery, the secondary battery has the advantages of low cost of use and low environmental pollution.
  • the main secondary battery technologies include lead-acid batteries, nickel-chromium batteries, nickel-hydrogen batteries, and lithium-ion batteries. Among them, lithium-ion batteries are the most widely used, and they are the main energy supply methods for portable electronic devices such as mobile phones, notebook computers, and digital cameras.
  • the core component of a lithium ion battery usually comprises a positive electrode, a negative electrode and an electrolyte, and the electrical energy storage and release is achieved by a redox reaction in which ion transport and electron transport phase separation occurs at the interface between the positive electrode, the negative electrode and the electrolyte.
  • the positive electrode of a conventional lithium ion battery is usually composed of a transition metal oxide (LiCoO 2 , LiNiMnCoO 2 , LiMn 2 O 4 ) or a polyanionic metal compound (LiFePO 4 ), the negative electrode is composed of a graphite-based material, and the electrolyte is a lithium salt-containing material. Organic solution. Lithium ions are contained in both the positive electrode and the electrolyte.
  • the battery It is composed of lithium salt and carbonate organic solvent, and the separator is glass fiber paper.
  • the battery has the advantages of low cost, simple process, high working voltage (up to 5V), high energy density and environmental friendliness. However, the battery still does not exclude the use of lithium salt electrolyte. The reserves of lithium on the earth are limited, the price is high, the development cost is large, and it is extremely lively and has potential safety hazards.
  • an embodiment of the present invention provides a secondary battery based on calcium ions, which uses a material such as graphite as a positive electrode active material, a metal foil as a negative electrode current collector and a negative electrode active material, and a calcium salt as an electrolyte.
  • the invention aims to solve the problems that the existing lithium secondary battery has limited lithium resource reserves, high cost, low battery energy density, poor cycle stability performance, and safety hazards.
  • the present invention provides a calcium ion-based secondary battery comprising:
  • a positive electrode comprising a positive electrode current collector and a positive electrode active material layer disposed on the positive electrode current collector, the positive electrode active material layer including a positive electrode active material including a carbon material, a sulfide, a nitride, an oxide, One or more of a carbide, and a composite of the above materials;
  • An electrolyte including a calcium salt and a non-aqueous solvent
  • a negative electrode comprising a metal foil, the metal foil simultaneously serving as a negative current collector and a negative active material;
  • the carbon material includes one or more of a graphite-based carbon material, a glassy carbon, a carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotubes, and graphene.
  • the graphite-based carbon material includes one or more of natural graphite, expanded graphite, artificial graphite, spherical graphite, flake graphite, mesocarbon microbead graphite, pyrolytic graphite, highly oriented graphite, and three-dimensional graphite sponge.
  • the sulfide is selected from the group consisting of molybdenum disulfide, tungsten disulfide, vanadium disulfide, titanium disulfide, iron disulfide, ferrous sulfide, nickel sulfide, zinc sulfide, cobalt sulfide, manganese sulfide; Nitride selected from One or more of hexagonal boron nitride and carbon-doped hexagonal boron nitride; the oxide is selected from the group consisting of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, vanadium dioxide, titanium dioxide, zinc oxide, copper oxide One or more of nickel oxide and manganese oxide; the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide, and silicon carbide.
  • the material of the positive electrode current collector includes any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese, or an alloy containing at least one of the above metal elements, or a composite containing at least one of the above metal elements. material.
  • the material of the metal foil includes any one of tin, aluminum, copper, iron, zinc, nickel, titanium, manganese, magnesium, bismuth, or an alloy containing at least one of the above metal elements, or at least one of the above A composite of metal elements.
  • the calcium salt includes calcium hexafluorophosphate (Ca(PF 6 ) 2 ), calcium tetrafluoroborate (Ca(BF 4 ) 2 ), calcium chloride, calcium carbonate, calcium fluorosilicate, calcium hexafluoroarsenate, double One of calcium oxalate borate, calcium sulfate, calcium nitrate, calcium fluoride, calcium triflate (Ca(CF 3 SO 3 ) 2 ), calcium perchlorate (Ca(ClO 4 ) 2 ) or A plurality of; in the electrolyte, the concentration of the calcium salt is 0.1 - 10 mol / L.
  • the nonaqueous solvent includes an organic solvent and an ionic liquid, and the organic solvent includes one or more of an ester, a sulfone, an ether, and a nitrile organic solvent.
  • the organic solvent includes propylene carbonate, ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, methyl formate, methyl acetate, N,N-dimethylacetamide, fluoroethylene carbonate.
  • the ionic liquid includes 1-ethyl-3-methylimidazole-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoro Borate, 1-ethyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methyl Imidazole-tetrafluoroborate, 1-propyl-3-methylimidazole-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl 1-methylimidazole-tetrafluoroborate, 1-butyl-1-methylimidazole-bistrifluoromethylsulfonimide salt, N-butyl-N-methylpyrrolidine-double Fluoromethylsulfonimide salt, 1-butyl-1-methylpyrrolidine-bistrifluoromethyls
  • the electrolyte further includes an additive comprising one or more of an ester, a sulfone, an ether, a nitrile, and an olefin organic additive, and the mass fraction of the additive in the electrolyte is 0.1%-20%.
  • the additives include fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulphate, propylene sulfate, sulfuric acid Ethylene glycol, vinyl 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-fluoroanisole, fluorochain ether, difluoromethylethylene carbonate Ester, trifluoromethyl ethylene carbonate, chloroethylene carbonate, vinyl bromoacetate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacetoxyethane, phosphate, phos
  • the separator is an insulating porous polymer film or an inorganic porous film.
  • the calcium ion-based secondary battery provided by the first aspect of the present invention uses a calcium salt as an electrolyte, which is lower in cost, higher in operating voltage, higher in capacity, and higher in cycle performance than the conventional commercial lithium ion secondary battery. More excellent, more outstanding security.
  • the present invention provides a method for preparing a calcium ion-based secondary battery, comprising the steps of:
  • the positive electrode active material layer including a positive electrode active material, the positive electrode active material including carbon a material, a sulfide, a nitride, an oxide, a carbide, and one or more of a composite of the above materials;
  • the electrolyte and a separator comprising a calcium salt and a non-aqueous solvent
  • the anode, the separator and the cathode are sequentially closely packed in an inert gas and an anhydrous environment, and the electrolyte is added to completely infiltrate the separator Then, the above stacked portion is packaged into a battery case to obtain a calcium ion-based secondary battery.
  • the method for preparing a calcium ion-based secondary battery provided by the second aspect of the invention has a simple process and is suitable for large-scale production.
  • 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 graph showing charge and discharge curves of a calcium ion-based secondary battery according to Embodiment 1 of the present invention.
  • FIG. 3 is a graph showing the rate performance of a calcium ion-based secondary battery according to Embodiment 1 of the present invention.
  • Fig. 4 is a graph showing the cycle performance of a calcium ion-based secondary battery according to Example 1 of the present invention.
  • an embodiment of the present invention provides a secondary battery including a cathode current collector 10, a cathode active material layer 20, an electrolyte 30, a separator 40, and a cathode 50.
  • the cathode current collector 10 and the cathode current collector are disposed.
  • the positive electrode active material layer 20 on 10 collectively constitutes a battery positive electrode, 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 electrolytic solution 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 above calcium ion-based secondary battery is: during the charging process, the calcium salt anion in the electrolyte migrates to the positive electrode and is embedded in the positive active material, and the calcium ion migrates to the negative electrode and forms with the negative electrode. Calcium-metal alloy; during the discharge process, the anion is released from the positive active material back into the electrolyte, and the calcium ion is alloyed from the negative electrode back into the electrolyte to realize the entire charging and discharging process, compared with the conventional lithium ion battery.
  • the calcium ion-based dual ion battery has a higher operating voltage.
  • the calcium ion-based secondary battery of the embodiment of the present invention has a higher capacity than the existing lithium ion-based dual ion battery.
  • the positive electrode active material is a material such as graphite
  • the negative electrode is an inexpensive metal foil
  • the electrolyte is a calcium salt, and all materials are abundant in storage, cheap and easy to obtain, thereby effectively reducing the secondary battery. Cost of production.
  • the metal foil acts as both the negative active material and the negative current collector, which is advantageous for simplifying the production process of the battery, reducing the weight and volume of the battery, improving the energy density and volumetric energy density of the battery, and reducing the cost.
  • the cathode active material includes one or more of a carbon material, a sulfide, a nitride, an oxide, a carbide, and a composite of the above materials.
  • the carbon material comprises one or more of a graphite-based carbon material, a glassy carbon, a carbon-carbon composite material, carbon fiber, hard carbon, porous carbon, carbon black, carbon nanotubes, and graphene.
  • the graphite-based carbon material includes one or more of natural graphite, expanded graphite, artificial graphite, mesocarbon microbead graphite, pyrolytic graphite, highly oriented graphite, and three-dimensional graphite sponge.
  • the sulfide is selected from the group consisting 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 the group consisting of molybdenum trioxide, tungsten trioxide, vanadium pentoxide, One or more of vanadium dioxide, titanium dioxide, zinc oxide, copper oxide, nickel oxide, manganese oxide;
  • the carbide is selected from one or more of titanium carbide, tantalum carbide, molybdenum carbide, silicon carbide.
  • the cathode active material has a layered crystal structure.
  • the calcium salt anion undergoes an intercalation reaction by intercalating-deintercalating the interlayer structure of the positive electrode active material to complete the reaction of the positive electrode.
  • 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.
  • the cathode current collector comprises any one of aluminum, copper, iron, tin, zinc, nickel, titanium, manganese or an alloy containing at least one of the above metal elements, or contains at least one of the above metals The composite of the elements.
  • the calcium salt as the electrolyte may be calcium hexafluorophosphate, calcium tetrafluoroborate, calcium chloride, calcium carbonate, calcium fluorosilicate, calcium hexafluoroarsenate, calcium bis(carboxylate) borate, calcium sulfate.
  • the concentration of calcium salt The degree is 0.1-10 mol/L. Further, the concentration of the calcium salt may be from 0.1 to 2 mol/L.
  • 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 calcium ions and anions can be freely migrated.
  • the nonaqueous solvent includes an organic solvent and an ionic liquid, and the organic solvent may be one or more of an ester, a sulfone, an ether, and a nitrile organic solvent.
  • the organic solvent may be propylene carbonate (PC), ethylene carbonate (EC), diethyl carbonate (DEC), dimethyl carbonate (DMC), ethyl methyl carbonate (EMC), formic acid Ester (MF), methyl acetate (MA), N,N-dimethylacetamide (DMA), fluoroethylene carbonate (FEC), methyl propionate (MP), ethyl propionate (EP), Ethyl acetate (EA), ⁇ -butyrolactone (GBL), tetrahydrofuran (THF), 2-methyltetrahydrofuran (2MeTHF), 1,3-dioxocyclopentane (DOL), 4-methyl-1, 3-dioxocyclopentane (4MeDOL), dimethoxymethane (DMM), 1,2-dimethoxypropane (DMP), triethylene glycol dimethyl ether (DG), dimethyl sulfone (MSM), Dimethyl ether (DME),
  • the ionic liquid includes 1-ethyl-3-methylimidazolium-hexafluorophosphate, 1-ethyl-3-methylimidazole-tetrafluoroborate, 1-ethyl-3-methylimidazole-double Trifluoromethylsulfonimide salt, 1-propyl-3-methylimidazole-hexafluorophosphate, 1-propyl-3-methylimidazole-tetrafluoroborate, 1-propyl-3- Methylimidazole-bistrifluoromethylsulfonimide salt, 1-butyl-1-methylimidazole-hexafluorophosphate, 1-butyl-1-methylimidazole-tetrafluoroborate, 1- Butyl-1-methylimidazole-bistrifluoromethylsulfonimide salt, N-butyl-N-methylpyrrolidine-bistrifluoromethylsulfonimide salt, 1-butyl-1- Methylpyrrolidine
  • the structure of the negative electrode is kept stable, and the service life and performance of the negative electrode are improved to improve the cycle performance of the secondary battery, and the electrolyte further Including additives
  • the additives may be esters, sulfones, ethers, nitriles One or more of the class and olefinic organic additives.
  • the additive includes fluoroethylene carbonate, vinylene carbonate, ethylene carbonate, 1,3-propane sultone, 1,4-butane sultone, vinyl sulfate, propylene sulfate Ester, ethylene sulfate, vinyl sulfite, propylene sulfite, dimethyl sulfite, diethyl sulfite, ethylene sulfite, methyl chloroformate, dimethyl sulfoxide, benzene Methyl ether, acetamide, diazabenzene, m-diazabenzene, crown ether 12-crown-4, crown ether 18-crown-6, 4-fluoroanisole, fluorochain ether, difluoromethyl Ethylene carbonate, trifluoromethyl ethylene carbonate, vinyl chlorocarbonate, vinyl bromoacetate, trifluoroethylphosphonic acid, bromobutyrolactone, fluoroacet
  • the additive added to the electrolyte can form a stable solid electrolyte membrane on the surface of the anode current collector (metal foil), so that the metal foil is not destroyed when reacted as the anode active material, thereby improving the service life of the battery.
  • the additive has a mass fraction in the electrolyte of 0.1-20%, and further may be 2-5%.
  • the separator may be an insulating porous polymer film or an inorganic porous film, and specifically, one of a porous polypropylene film, a porous polyethylene film, a porous composite polymer film, a glass fiber paper, and a porous ceramic separator may be selected. Or a variety.
  • the positive electrode active material layer further includes a conductive agent and a binder, wherein the positive electrode active material has a mass content of 60-90%, the conductive agent has a mass content of 5-30%, and the binder has a mass content of 5-10%. Further, the positive electrode active material has a mass content of 70-85%.
  • the conductive agent and the binder are not particularly limited in the embodiment of the present invention, and it is generally used in the art.
  • the conductive agent may 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 may be polyvinylidene fluoride, polytetrafluoroethylene, polyvinyl alcohol, carboxymethyl One or more of a base cellulose, an SBR rubber, and a polyolefin.
  • an embodiment of the present invention further provides a method for preparing the above secondary battery, comprising the following steps:
  • Preparation of positive electrode providing a positive electrode current collector with a clean surface, weighing the positive electrode active material, the conductive agent and the binder in a certain ratio, adding a suitable solvent and thoroughly mixing to form a uniform slurry; then uniformly coating the slurry on the slurry Forming a positive electrode current collector surface, forming a positive electrode active material layer, pressing and cutting after being completely dried to obtain a battery positive electrode of a desired size;
  • a porous polymer film or an inorganic porous film is cut into a desired size, and after cleaning, a desired separator is obtained.
  • Battery assembly in the inert gas and waterless environment, the battery negative electrode, the separator and the positive electrode prepared in the above-mentioned manner are closely stacked in order, the electrolyte is added to completely infiltrate the separator, and then the stacked portion is packaged into the battery.
  • the housing is assembled to obtain a calcium ion-based secondary battery.
  • steps (1) to (4) describe the operation of the calcium ion-based secondary battery preparation method of the present invention in a specific order, it is not necessary to perform these operations in this specific order.
  • the operations of steps (1)-(4) can be performed simultaneously or in any order.
  • Battery assembly In the inert gas-protected glove box, the prepared negative electrode, separator, and positive electrode are sequentially closely stacked, and the electrolyte is dripped to completely infiltrate the separator, and then the stacked portion is packaged into the button battery case. The battery assembly is completed, and a secondary battery based on calcium ions is obtained.
  • Example 2 is a charge and discharge graph of a calcium ion-based secondary battery according to an embodiment of the present invention
  • FIG. 3 is a graph showing a rate performance of a calcium ion-based secondary battery according to an embodiment of the present invention
  • Cyclic performance map of a calcium ion secondary battery As can be seen from the figure, the calcium ion-based secondary battery of the present invention has a high discharge voltage, a high capacity, superior rate performance, and superior cycle performance.
  • the secondary battery of the first embodiment of the present invention has an operating average voltage of more than 4.2 V, a specific capacity of the battery of 85.8 mAh/g, an energy density of 168 Wh/kg, and a cycle number of 300 times when the capacity is attenuated to 90%.
  • the dual ion secondary battery using the calcium salt as the electrolyte in the embodiment 1 of the invention has high working voltage, high energy density, long cycle life, low raw material cost and process cost, environmental friendliness and high safety.
  • the preparation process of the secondary batteries of Examples 2-11 and Example 1 was the same except that the materials used in the preparation of the battery negative electrode were the same, and all the other steps and materials used were the same, while the secondary batteries of Examples 2-11 were subjected to the battery.
  • the electrochemical performance test was compared with the performance of Example 1 of the present invention.
  • the negative electrode materials used in Examples 2-11 and their electrochemical properties are shown in Table 1.
  • the preparation process of the secondary batteries of Examples 12-34 and Example 1 was the same except that the positive electrode active materials used in the preparation of the positive electrode of the battery were the same, and all the steps and materials used were the same, and Examples 12-34 were simultaneously applied.
  • the secondary battery was tested for electrochemical performance of the battery and compared with the performance of Example 1 of the present invention. See Table 2 for details.
  • the cathode active material is selected from a graphite-based carbon material
  • the specific capacity of the battery is higher, the energy density is higher, and the cycle performance is also better.
  • the preparation process of the secondary batteries of Examples 35-43 and Example 1 was the same except that the electrolyte materials used in the preparation of the electrolyte were the same, all the other steps and materials used were the same, and the batteries of the secondary batteries of Examples 35-43 were subjected to the battery.
  • the electrochemical performance test was compared with the performance of Example 1 of the present invention.
  • the electrolyte materials used in Examples 35-43 and the electrochemical performance of the battery are shown in Table 3.
  • the preparation process of the secondary batteries of Examples 44-48 and Example 1 was the same except that the electrolyte concentration used in the preparation of the electrolytic solution was different, all other steps and materials used were the same, and the secondary batteries of Examples 44 to 48 were subjected to the battery.
  • the electrochemical performance test was compared with the performance of Example 1 of the present invention.
  • the electrolyte concentration and electrochemical performance of the cells used in Examples 44-48 are detailed in Table 4.
  • the preparation process of the secondary batteries of Examples 49-61 and Example 1 was the same except that the solvent used in the preparation of the electrolytic solution was the same, all other steps and materials used were the same, and the secondary batteries of Examples 49-61 were subjected to the battery.
  • the electrochemical performance test was compared with the performance of Example 1 of the present invention.
  • the solvents used in Examples 49-61 and their electrochemical properties are detailed in Table 5.
  • the solvent is ethylene carbonate: propylene carbonate: dimethyl carbonate: ethyl methyl carbonate: (volume ratio 2:2:3:3) mixed solution,
  • the battery has higher specific capacity, higher energy density and better cycle performance.
  • the preparation process of the secondary batteries of Examples 62-70 and Example 1 was the same except that the types and amounts of the additives used in the preparation of the electrolytic solution were the same, and all the other steps and materials used were the same, and the secondary batteries of Examples 62-70 were simultaneously used.
  • the electrochemical performance test of the battery was carried out and compared with the performance of Example 1 of the present invention.
  • the solvent materials used in Examples 62-70 and their electrochemical properties are detailed in Table 6.
  • Example 7 The secondary battery preparation processes of Examples 71 to 74 and Example 1 were the same except that the separator materials used in the preparation of the separator were the same, and all the other steps and materials used were the same, while the secondary batteries of Examples 71 to 74 were subjected to the battery.
  • the electrochemical performance test was compared with the performance of Example 1 of the present invention.
  • the separator materials used in Examples 71-74 and their electrochemical properties are detailed in Table 7.
  • Example 75 The preparation process of the secondary batteries of Examples 75-81 and Example 1 was the same except that the conductive agent, the type of the binder, and the mass fraction used in the preparation of the positive electrode of the battery were the same, and all the other steps and materials used were the same, and Example 75 was The secondary battery of -81 was subjected to electrochemical performance test of the battery, and compared with the performance of Example 1 of the present invention, the conductive agent, the type of binder and the mass fraction used in Examples 75-81 were specifically See Table 8.
  • the form of the secondary battery according to the present invention is not limited to the button type battery, and may be designed in the form of a prismatic battery, a cylindrical battery, a soft pack battery or the like according to the core component.
  • the main active component of the secondary battery proposed by the present invention is a material having a layered crystal structure such as graphite, and the electrolyte is a calcium salt rich in resource reserves, environmentally friendly, low in cost, and high in battery capacity.
  • the metal foil serves as both the anode current collector and the anode active material, thereby significantly reducing the battery weight and cost, and improving the energy density of the battery.
  • the average operating voltage of the secondary battery proposed by the present invention is greater than 4.2V.

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Abstract

L'invention concerne une pile rechargeable au calcium-ion et son procédé de fabrication. La pile comprend une électrode positive, une solution électrolytique (30), une électrode négative (50) et une membrane séparatrice (40). L'électrode positive comprend un collecteur de courant d'électrode positive (10) et une couche de matériau actif d'électrode positive (20) disposée sur le collecteur de courant d'électrode positive (10). La couche de matériau actif d'électrode positive (20) comprend un matériau actif d'électrode positive, et le matériau actif d'électrode positive comprend un ou plusieurs éléments parmi un matériau carboné, un sulfure, un nitrure, un oxyde, un carbure, et un composite des matériaux susmentionnés. La solution électrolytique (30) comprend un sel de calcium et un solvant non aqueux. L'électrode négative (50) comprend une feuille métallique servant de collecteur de courant d'électrode négative et un matériau actif d'électrode négative. La pile rechargeable utilise un sel de calcium en tant qu'électrolyte pour réduire les coûts et fournir une tension de fonctionnement élevée, une capacité élevée et une performance de cycle élevée.
PCT/CN2017/078203 2017-03-24 2017-03-24 Pile rechargeable au calcium-ion et son procédé de fabrication Ceased WO2018170925A1 (fr)

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Cited By (7)

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Publication number Priority date Publication date Assignee Title
CN109174125A (zh) * 2018-10-15 2019-01-11 中国科学院城市环境研究所 一种硫化钒钛催化剂及其制备方法和用途
CN109638249A (zh) * 2018-12-10 2019-04-16 桂林理工大学 用于锂离子电池的矿物/碳/热解碳负极材料的制备方法
CN109659524A (zh) * 2018-12-10 2019-04-19 桂林理工大学 用于锂离子电池的矿物/碳复合负极材料的制备方法
CN110270362A (zh) * 2019-07-02 2019-09-24 华东理工大学 一种锰氮共掺杂碳化钼纳米棒及其制备方法和应用
CN112010291A (zh) * 2020-09-03 2020-12-01 郑州工程技术学院 一种镍掺杂二硫化钼/石墨烯三维复合材料的制备方法及应用
CN113540446A (zh) * 2021-07-05 2021-10-22 武汉钜能科技有限责任公司 一种锂离子电池负极材料及其制备方法
EP4053937A1 (fr) * 2021-03-05 2022-09-07 Consejo Superior de Investigaciones Científicas (CSIC) Électrode d'un oxyde mixte de batteries au calcium et son procédé de fabrication

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