WO2022007582A1 - Batterie au lithium - Google Patents

Batterie au lithium Download PDF

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WO2022007582A1
WO2022007582A1 PCT/CN2021/099298 CN2021099298W WO2022007582A1 WO 2022007582 A1 WO2022007582 A1 WO 2022007582A1 CN 2021099298 W CN2021099298 W CN 2021099298W WO 2022007582 A1 WO2022007582 A1 WO 2022007582A1
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lithium
positive electrode
battery
active material
foil
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PCT/CN2021/099298
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English (en)
Chinese (zh)
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徐雄文
涂健
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湖南立方新能源科技有限责任公司
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    • H—ELECTRICITY
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
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    • 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
    • H—ELECTRICITY
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    • H01M4/06—Electrodes for primary cells
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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    • 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
    • H—ELECTRICITY
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    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
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    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
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    • 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
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    • 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
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    • 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
    • H01M4/582—Halogenides
    • H—ELECTRICITY
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    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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 invention belongs to the technical field of lithium ion batteries, and in particular relates to a lithium battery.
  • the theoretical specific capacity of metal lithium anode is 3860mAh/g, the voltage platform is -3.04V (vs standard hydrogen electrode), and it has excellent conductivity, which is very suitable as the anode of high energy density battery.
  • lithium metal is a very active metal, and it will have a violent combustion reaction with water, releasing flammable gas hydrogen, and at the same time releasing a lot of heat.
  • Lithium metal also easily reacts with nitrogen in the air to form tan lithium nitride on the surface. Lithium nitride cannot be removed after it is formed, which affects the performance of lithium metal, and sparks or even explodes when squeezed by high pressure. Lithium metal easily reacts with oxygen in the air to form white lithium oxide.
  • High-temperature (burning) lithium metal explodes when it comes into contact with concrete floors.
  • Lithium metal is soft and viscous, and debris is easy to adhere to fixtures and protective gear, increasing the danger. Therefore, the use of metallic lithium as the negative electrode of the battery is extremely demanding on the environment and has high safety risks.
  • the positive electrode uses a compound that can deintercalate lithium ions
  • the negative electrode uses conductive metal foil or conductive carbon paper, etc.
  • the lithium source of the entire battery comes from the positive electrode.
  • the cost of the battery can be reduced, the assembly safety and the safety performance of the battery itself can be improved.
  • the batteries of this technology have the disadvantages of rapid capacity loss during storage and poor cycle life when used in secondary batteries when used in primary batteries.
  • the technical problem to be solved by the present invention is to provide a lithium battery.
  • the lithium battery provided by the present invention has the characteristics of excellent storage performance when used in a primary battery, and also has a longer cycle life when used in a secondary battery.
  • the invention provides a lithium battery, comprising a positive electrode, a negative electrode, a diaphragm and an electrolyte;
  • the positive active material in the positive electrode includes positive active material 1 and positive active material 2;
  • the positive electrode active material 1 is selected from lithium cobalt oxide, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganate, lithium manganate, lithium nickel cobalt aluminate and lithium iron manganese phosphate and its doping modification. sexual substances;
  • the positive electrode active material 2 is selected from Li 2 NiO 2 , Li 5 FeO 4 , Li 3 N, Li 2 S/Co composite, LiF/Co composite, Li 2 O/Co composite, lithium azide, oxygen One or more of lithium carbide, lithium dicarboxylic acid salt, and hydrazide lithium salt;
  • the negative electrode is a conductive foil.
  • the lithium oxycarbide is selected from one or more of Li 2 C 3 O 3 , Li 2 C 4 O 4 , Li 2 C 5 O 5 and Li 2 C 6 O 6 ;
  • the lithium dicarboxylic acid salt is selected from one or more of Li 2 C 2 O 4 , Li 2 C 3 O 5 and Li 2 C 4 O 6 ;
  • the hydrazide-based lithium salt is selected from one or more of Li 2 C 2 N 4 O 2 and (Li 2 C 2 N 2 O 2 ) n , where n ranges from 2 to 100.
  • the positive electrode comprises a positive electrode current collector and a positive electrode membrane compounded on the surface of the positive electrode current collector;
  • the positive electrode membrane is prepared from a positive electrode active material 1, a positive electrode active material 2, a conductive agent and a binder, and the mass ratio of the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder is 75 ⁇ 97.5:1 ⁇ 15:0.5 ⁇ 5:1 ⁇ 5.
  • the conductive agent is selected from one or more of carbon black, acetylene black, Ketjen black, carbon nanotubes, and graphene;
  • the binder is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polypropylene, polyethylene, polyurethane and polyamide.
  • the conductive foil is selected from copper foil, nickel foil, stainless steel foil, alloy foil, conductive carbon paper, copper foil on the surface of plastic substrate, nickel foil on the surface of plastic substrate, stainless steel foil on the surface of plastic substrate,
  • the surface of the aluminum substrate is plated with copper foil, the surface of the aluminum substrate is plated with nickel foil, and the surface of the aluminum substrate is plated with stainless steel foil.
  • the separator comprises any one of polyethylene film, polypropylene film, polyethylene and polypropylene composite film, polyimide film and ceramic film.
  • the electrolyte is a non-aqueous organic electrolyte, including a lithium salt, a solvent and an additive, and the lithium salt includes one or more of LiPF 6 , LiClO 4 , LiBF 4 , LiBOB, LiFSI, and LiTFSI.
  • the solvent includes at least one of carboxylate-based solvents, carbonate-based solvents, ether-based solvents and fluorinated solvents.
  • a packaging film is also included, and the packaging film is selected from polymer soft packaging materials or metal shells.
  • the winding core structure of the lithium battery is a winding type and/or a lamination type.
  • the cell structure of the lithium battery is a square, cylindrical, button-shaped or special-shaped structure.
  • the lithium battery is a lithium primary battery or a lithium secondary battery.
  • the present invention provides a lithium battery, including a positive electrode, a negative electrode, a separator and an electrolyte;
  • the positive electrode active material in the positive electrode includes a positive electrode active material 1 and a positive electrode active material 2;
  • the positive electrode active material 1 is selected from lithium cobalt oxide, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganate, lithium nickel manganate, lithium nickel cobalt aluminate, lithium iron manganese phosphate and their doping modified derivatives;
  • the positive electrode active material 2 is selected from Li 2 NiO 2 , Li 5 FeO 4 , Li 3 N, Li 2 S/Co composite, LiF/Co composite, Li 2 O/Co composite, lithium azide, oxygen One or more of lithium carbide, lithium dicarboxylic acid salt, and hydrazide lithium salt;
  • the negative electrode is a conductive foil.
  • a positive electrode active material 2 with irreversible or partially reversible lithium release into the positive electrode, when charging for the first time, all the lithium ions of the material are extracted and deposited on the negative electrode, and when discharging for the first time, the material is only A small amount of lithium ions can be inserted or no lithium ions can be inserted, so that some lithium ions will remain on the surface of the negative electrode.
  • the primary battery since the primary battery will inevitably have capacity loss during storage, since the lithium ions of the negative electrode are excessive relative to the positive electrode, it can be ensured that the battery still has 100% capacity after a certain period of storage.
  • FIG. 1 is a schematic structural diagram of a lithium battery provided by the present invention.
  • FIG. 2 is a schematic structural diagram of a lithium battery provided by the present invention.
  • the invention provides a lithium battery, comprising a positive electrode, a negative electrode, a diaphragm and an electrolyte;
  • the positive active material in the positive electrode includes positive active material 1 and positive active material 2;
  • the positive electrode active material 1 is selected from lithium cobalt oxide, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganate, lithium manganate, lithium nickel cobalt aluminate, lithium iron manganese phosphate and its doping modification. Sexual derivatives;
  • the positive electrode active material 2 is selected from Li 2 NiO 2 , Li 5 FeO 4 , Li 3 N, Li 2 S/Co composite, LiF/Co composite, Li 2 O/Co composite, lithium azide, oxygen One or more of lithium carbide, lithium dicarboxylic acid salt, and hydrazide lithium salt;
  • the negative electrode is a conductive foil.
  • the present invention provides a lithium battery, comprising a positive electrode, wherein the positive electrode comprises a positive electrode current collector and a positive electrode membrane compounded on the surface of the positive electrode current collector;
  • the positive electrode membrane is prepared from a positive electrode active material 1, a positive electrode active material 2, a conductive agent and a binder.
  • the positive electrode active material 1 is selected from lithium cobalt oxide, lithium manganate, lithium nickelate, lithium iron phosphate, lithium nickel cobalt manganate, lithium manganate, lithium nickel cobalt aluminate, lithium iron manganese phosphate and its doped lithium Miscellaneous modified substances.
  • the positive electrode active material 1 is selected from lithium iron phosphate positive electrode active material and nickel cobalt lithium manganate positive electrode active material.
  • the positive electrode active material 2 is selected from one or more of lithium oxycarbide, lithium dicarboxylic acid salts, and hydrazide lithium salts;
  • the lithium oxycarbide is selected from one or more of Li 2 C 3 O 3 , Li 2 C 4 O 4 , Li 2 C 5 O 5 and Li 2 C 6 O 6 ;
  • the lithium dicarboxylic acid salt is selected from one or more of Li 2 C 2 O 4 , Li 2 C 3 O 5 and Li 2 C 4 O 6 ;
  • the hydrazide-based lithium salt is selected from one or more of Li 2 C 2 N 4 O 2 and (Li 2 C 2 N 2 O 2 ) n , where n ranges from 2 to 100.
  • the positive electrode active material 2 is selected from Li 2 NiO 2 or Li 5 FeO 4 .
  • the conductive agent is selected from one or more of carbon black, acetylene black, Ketjen black, carbon nanotube, and graphene;
  • the binder is selected from one or more of polyvinylidene fluoride, polytetrafluoroethylene, polyvinylpyrrolidone, polypropylene, polyethylene, polyurethane and polyamide.
  • the mass ratio of the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder is 75-97.5:1-15:0.5-5:1-5, preferably 80-95:3 ⁇ 12:1 ⁇ 3:2 ⁇ 4.
  • the proportion of the positive electrode active material 2 in the positive electrode is 1wt%-15wt%, preferably 3wt%-12wt%, more preferably 5wt%-10wt%.
  • the present invention does not specifically limit the preparation method of the positive electrode, and the preparation method known to those skilled in the art can be used. That is, the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder are mixed to prepare a positive electrode slurry, and then the positive electrode slurry is coated on the surface of the positive electrode current collector and dried to obtain a positive electrode.
  • the negative electrode of the lithium battery is a layer of conductive foil, and there is no active material on the foil.
  • the conductive foil is selected from copper foil, nickel foil, stainless steel foil, alloy foil, conductive carbon paper, copper foil on the surface of plastic substrate, nickel foil on the surface of plastic substrate, stainless steel foil on the surface of plastic substrate, aluminum substrate
  • the surface is plated with copper foil, the surface of the aluminum substrate is plated with nickel foil, and the surface of the aluminum substrate is plated with stainless steel foil.
  • the thickness of the conductive foil is between 5 microns and 100 microns.
  • the lithium battery further includes a separator and an electrolyte, wherein the present invention does not specifically limit the type of the separator, and the type of the separator known to those skilled in the art may be sufficient.
  • the separator is selected from any one of polyethylene film, polypropylene film, polyethylene and polypropylene composite film, polyimide film and ceramic film.
  • the electrolyte is a non-aqueous organic electrolyte, including a lithium salt, a solvent and an additive
  • the lithium salt includes one or more of LiPF 6 , LiClO 4 , LiBF 4 , LiBOB, LiFSI, and LiTFSI
  • the solvent includes at least one of carboxylate-based solvents, carbonate-based solvents, ether-based solvents and fluorinated solvents.
  • the additives are selected from one or more of film-forming additives, low-temperature additives, high-temperature additives, and flame-retardant additives.
  • the positive electrode, the negative electrode, the separator and the electrolyte form the cell structure of the lithium battery, and the cell structure of the lithium battery is a square, cylindrical, button-shaped or special-shaped structure.
  • the lithium battery also includes a packaging film covering the surface of the cell structure, and the packaging film is selected from polymer soft packaging materials or metal shells.
  • the polymer soft packaging material is preferably an aluminum-plastic film or a steel-plastic film.
  • the lithium battery is a lithium primary battery or a lithium secondary battery.
  • FIG. 1 and FIG. 2 are schematic structural diagrams of the lithium battery provided by the present invention. Among them, the positive electrode (101), the negative electrode (102), and the separator (103).
  • the present invention does not specifically limit the preparation method of the lithium battery, and the preparation method of the lithium battery known to those skilled in the art may be sufficient.
  • a positive electrode active material 2 with irreversible or partially reversible lithium release into the positive electrode, when charging for the first time, all the lithium ions of the material are extracted and deposited on the negative electrode, and when discharging for the first time, the material is only A small amount of lithium ions can be inserted or no lithium ions can be inserted, so that some lithium ions will remain on the surface of the negative electrode.
  • the primary battery since the primary battery will inevitably have capacity loss during storage, since the lithium ions of the negative electrode are excessive compared to the positive electrode, it can ensure that the battery still has 100% capacity after a certain period of storage.
  • the lithium battery provided by the present invention is described below with reference to the examples, and the protection scope of the present invention is not limited by the following examples.
  • the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder with a mass ratio of 95:3:1:1 are mixed to prepare a positive electrode slurry, wherein the positive electrode active material 1 is nickel cobalt lithium manganate, the positive electrode active material Material 2 is Li 2 NiO 2 , the conductive agent is a mixture of CNT and carbon black, and the binder is PVDF.
  • the positive electrode slurry was coated on the surface of the positive electrode current collector Al foil, and after drying, the battery positive electrode was obtained.
  • the surface of the cell structure is covered with a packaging film aluminum-plastic film to obtain a lithium primary battery.
  • the battery still has a 100% capacity retention rate after being stored at 45°C for 1 month.
  • the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder with a mass ratio of 90:8:1:1 are mixed to prepare a positive electrode slurry, wherein the positive electrode active material 1 is nickel cobalt lithium manganate, and the positive electrode active material Material 2 is Li 2 NiO 2 , the conductive agent is a mixture of CNT and carbon black, and the binder is PVDF.
  • the positive electrode slurry was coated on the surface of the positive electrode current collector Al foil, and after drying, the battery positive electrode was obtained.
  • the surface of the cell structure is covered with a packaging film aluminum-plastic film to obtain a lithium secondary battery.
  • the battery was cycled at a rate of 0.2C/0.5C at RT, and the capacity retention rate was 88% after 100 cycles and 75% after 200 cycles.
  • a positive electrode slurry is prepared by mixing the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder with a mass ratio of 92:5:2:1, wherein the positive electrode active material 1 is lithium iron phosphate and the positive electrode active material 2. It is Li 5 FeO 4 , the conductive agent is a mixture of CNT+carbon black, and the binder is PVDF.
  • the positive electrode slurry was coated on the surface of the positive electrode current collector Al foil, and after drying, the battery positive electrode was obtained.
  • the surface of the cell structure is covered with a packaging film aluminum-plastic film to obtain a lithium primary or secondary battery.
  • the battery Used as a primary battery, the battery still has a 100% capacity retention rate after being stored at 45°C for 1 month. Used as a secondary battery, the battery was cycled 200 times at a rate of 0.2C/0.5C at RT, with a capacity retention rate of 80%.
  • the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder with a mass ratio of 90:6:2:2 are mixed to prepare a positive electrode slurry, wherein the positive electrode active material 1 is lithium cobalt oxide, and the positive electrode active material 2 is Li 2 O/Co composite, the conductive agent is a mixture of CNT and carbon black, and the binder is PVDF.
  • the positive electrode slurry was coated on the positive electrode current collector Al foil, and dried to obtain a battery positive electrode.
  • the battery Used as a primary battery, the battery still has a 100% capacity retention rate after being stored at 45°C for 1 month. Used as a secondary battery, the battery was cycled 200 times at a rate of 0.2C/0.5C in an RT environment, and the capacity retention rate was 70%.
  • the positive electrode active material 1, the positive electrode active material 2, the conductive agent and the binder with a mass ratio of 90:6:2:2 are mixed to prepare a positive electrode slurry, wherein the positive electrode active material 1 is lithium nickel cobalt manganate, and the positive electrode active material is 2 is a dicarboxylic acid lithium salt Li 2 C 2 O 4 , the conductive agent is carbon black, and the binder is PVDF.
  • the positive electrode slurry was coated on the positive electrode current collector Al foil, and dried to obtain a battery positive electrode.
  • the battery Used as a primary battery, the battery still has a 100% capacity retention rate after being stored at 45°C for 1 month. Used as a secondary battery, the battery was cycled 200 times at a rate of 0.2C/0.5C in an RT environment with a capacity retention rate of 82%.
  • the positive electrode active material 1 with a mass ratio of 98:1:1, a conductive agent and a binder are mixed to prepare a positive electrode slurry, wherein the positive electrode active material 1 is nickel cobalt lithium manganate, and the conductive agent is a mixture of CNT and carbon black And the binder is PVDF.
  • the positive electrode slurry was coated on the surface of the positive electrode current collector Al foil, and after drying, the battery positive electrode was obtained.
  • the battery positive electrode, the battery negative electrode Cu foil, the separator PE+Al 2 O 3 coating, and the electrolyte non-aqueous organic electrolyte are assembled into a laminated cell structure.
  • the surface of the cell structure is covered with a packaging film and an aluminum-plastic film to obtain a lithium primary or secondary battery.
  • the capacity retention rate of the battery after being stored at 45°C for 1 month is only 90%.
  • the capacity retention rate was 81% after 50 cycles at a rate of 0.2C/0.5C in RT environment, and the capacity retention rate was 68% after 100 cycles.

Abstract

La présente invention concerne une batterie au lithium. Dans la présente invention, au moyen de l'ajout d'un matériau actif d'électrode positive, qui contient du lithium à désintercalation irréversible ou du lithium à désintercalation partiellement réversible, à une électrode positive, lors de la première charge, tous les ions lithium dans ladite substance sont séparés et déposés sur une électrode négative ; et lors de la première décharge, seule une petite quantité des ions lithium peut être intercalé dans ladite substance ou aucun des ions lithium ne peut être intercalé dans ladite substance. Ainsi, une partie des ions lithium reste sur la surface de l'électrode négative. Lorsqu'elle est utilisée en tant que batterie primaire, étant donné qu'une perte de capacité se produira inévitablement pour la batterie primaire pendant le stockage et que les ions lithium sur l'électrode négative sont en excédent par comparaison avec les ions lithium sur l'électrode positive, la batterie aura toujours une capacité de 100 % après avoir été stockée pendant une certaine période de temps. Ainsi, les performances de stockage de la batterie peuvent être améliorées. Lorsqu'elle est utilisée en tant que batterie secondaire, étant donné qu'une fine couche de lithium restera sur la surface d'une feuille d'électrode négative, dans un aspect, la morphologie subséquente de dépôt d'ions lithium peut être améliorée, et dans un autre aspect, un apport supplémentaire de source de lithium peut être fourni pour un cycle de charge/décharge subséquent, ce qui permet d'améliorer les performances de cycle de la batterie.
PCT/CN2021/099298 2020-07-09 2021-06-10 Batterie au lithium WO2022007582A1 (fr)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114566393A (zh) * 2022-03-23 2022-05-31 上海奥威科技开发有限公司 一种用于锂离子电容器的复合正极材料及其应用
CN114784223A (zh) * 2022-04-28 2022-07-22 广东马车动力科技有限公司 一种正极片及其制备方法与应用
CN114899551A (zh) * 2022-05-30 2022-08-12 安普瑞斯（无锡）有限公司 一种复合膜及含有该膜的锂离子电池

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111628159A (zh) * 2020-07-09 2020-09-04 湖南立方新能源科技有限责任公司 一种锂电池
CN112635770A (zh) * 2020-12-17 2021-04-09 惠州亿纬锂能股份有限公司 一种锂离子电池预锂化正极极片及锂离子电池的制备方法
CN113871725A (zh) * 2021-09-28 2021-12-31 洛阳储变电系统有限公司 一种无负极锂二次电池
CN114551785A (zh) * 2021-12-28 2022-05-27 惠州虎电科技发展有限公司 一种低成本的一次性锂离子电池
CN117650246A (zh) * 2024-01-30 2024-03-05 深圳海辰储能科技有限公司 补锂材料及其制备方法和应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015126932A1 (fr) * 2014-02-18 2015-08-27 Brookhaven Science Associates, Llc Additifs de cathode multifonctionnels pour des technologies de batterie
CN109659495A (zh) * 2018-11-20 2019-04-19 湖南立方新能源科技有限责任公司 一种锂金属电池正极片及锂金属电池
CN110476279A (zh) * 2017-06-21 2019-11-19 株式会社Lg化学 锂二次电池
CN110651389A (zh) * 2017-12-27 2020-01-03 株式会社Lg化学 锂二次电池
WO2020091428A1 (fr) * 2018-10-30 2020-05-07 주식회사 엘지화학 Accumulateur au lithium
CN111628159A (zh) * 2020-07-09 2020-09-04 湖南立方新能源科技有限责任公司 一种锂电池

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4401737A (en) * 1980-09-24 1983-08-30 Rayovac Corporation Protective active nitrides as additives to nonaqueous cathode materials
US20050130042A1 (en) * 2003-12-11 2005-06-16 Byd America Corporation Materials for positive electrodes of lithium ion batteries and their methods of fabrication
CN104781961A (zh) * 2013-09-05 2015-07-15 株式会社Lg化学 用于具有高容量的锂二次电池的正极添加剂
CN103441236B (zh) * 2013-09-11 2017-10-13 东莞新能源科技有限公司 锂离子电池阴极片、锂离子电池及其制备方法
JP2018014398A (ja) * 2016-07-20 2018-01-25 旭化成株式会社 非水系リチウム蓄電素子
CN110311149A (zh) * 2019-06-27 2019-10-08 湖南立方新能源科技有限责任公司 一种锂一次电池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015126932A1 (fr) * 2014-02-18 2015-08-27 Brookhaven Science Associates, Llc Additifs de cathode multifonctionnels pour des technologies de batterie
CN110476279A (zh) * 2017-06-21 2019-11-19 株式会社Lg化学 锂二次电池
CN110651389A (zh) * 2017-12-27 2020-01-03 株式会社Lg化学 锂二次电池
WO2020091428A1 (fr) * 2018-10-30 2020-05-07 주식회사 엘지화학 Accumulateur au lithium
CN109659495A (zh) * 2018-11-20 2019-04-19 湖南立方新能源科技有限责任公司 一种锂金属电池正极片及锂金属电池
CN111628159A (zh) * 2020-07-09 2020-09-04 湖南立方新能源科技有限责任公司 一种锂电池

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114566393A (zh) * 2022-03-23 2022-05-31 上海奥威科技开发有限公司 一种用于锂离子电容器的复合正极材料及其应用
CN114784223A (zh) * 2022-04-28 2022-07-22 广东马车动力科技有限公司 一种正极片及其制备方法与应用
CN114899551A (zh) * 2022-05-30 2022-08-12 安普瑞斯（无锡）有限公司 一种复合膜及含有该膜的锂离子电池

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