WO2022245303A1 - Lithium-ion battery of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell - Google Patents

Lithium-ion battery of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell Download PDF

Info

Publication number
WO2022245303A1
WO2022245303A1 PCT/TH2022/000019 TH2022000019W WO2022245303A1 WO 2022245303 A1 WO2022245303 A1 WO 2022245303A1 TH 2022000019 W TH2022000019 W TH 2022000019W WO 2022245303 A1 WO2022245303 A1 WO 2022245303A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon
lithium
core
shell
nickel manganese
Prior art date
Application number
PCT/TH2022/000019
Other languages
French (fr)
Inventor
Montree SAWANGPHRUK
Atiweena KRITTAYAVATHANANON
Juthaporn WUTTHIPROM
Suchakree TUBTIMKUNA
Nattanon JORALEECHANCHAI
Komkrit SUTTIPONPARNIT
Original Assignee
Ptt Public Company Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ptt Public Company Limited filed Critical Ptt Public Company Limited
Publication of WO2022245303A1 publication Critical patent/WO2022245303A1/en

Links

Classifications

    • 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/13—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—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
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si 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
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • 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
    • H01M4/48—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
    • 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
    • H01M4/52—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
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/666—Composites in the form of mixed materials
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • 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

  • cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell
  • Batteries are power-storing devices capable of converting chemical energy into electrical power directly. Electrical power storage in various types of batteries is based on important criteria for determination of storage options, being capacity (kilowatt-hours) and storage density (kilowatt- hours per volume). In addition, battery selection has to take other factors into account, such as the efficiency of batteries because there is loss during charging, storage and discharging. This is because batteries are devices for storing electricity that can be recharged multiple times. Good batteries should have high energy and electricity power density, light weight, high safety for use, high reliability, and low manufacturing cost.
  • Lithium is a key element in the manufacture of batteries, and present in the form of an inorganic compound of cathode and an electrolyte solution as lithium salt in an organic solvent.
  • Lithium-ion secondary cell batteries (rechargeable battery) were first launched commercially in 1991 by Sony Corporation. Since then, lithium-ion batteries have been manufactured for use in several types of electronic devices and been a highly -popular group of batteries.
  • the use of lithium batteries can be divided into three main groups, namely:
  • Lithium battery cells used for portable devices or electrical appliances can be divided per their shapes into cylindrical, pouch, prismatic and button cells. While in various electrical motor vehicles, lithium batteries are in the form of battery packs; also divided into batteries in automobiles, buses, motorcycles and other mobile electrical motor vehicles; making the demand for battery in the group of electrical motor vehicles higher than that in the groups of portable devices and electrical appliances.
  • the structure of a lithium-ion battery cell consists of three major parts, namely electrodes (cathode and anode), a separator and an electrolyte solution.
  • the cathode is the most important part, usually made from lithium-containing inorganic compound materials, such as lithium cobalt oxide (LiCoC ), lithium iron phosphate (LiFePCL), lithium manganese oxide (LiMmCL) and so on.
  • lithium cobalt oxide LiCoC
  • LiFePCL lithium iron phosphate
  • LiMmCL lithium manganese oxide
  • common materials used are various types of carbon, namely graphite, hard carbon or graphene, where this anode is an element in determining the voltage of a prepared lithium battery cell.
  • the electrolyte solution it is a solution of lithium salt compound dissolved in an organic solvent, such as lithium hexafluorophosphate (LiPF 6) , lithium perchlorate (LiCICL), lithium hexafluoroarsenate (LiAsF 6) and so on.
  • an organic solvent such as lithium hexafluorophosphate (LiPF 6) , lithium perchlorate (LiCICL), lithium hexafluoroarsenate (LiAsF 6) and so on.
  • LiPF 6 lithium hexafluorophosphate
  • LiCICL lithium perchlorate
  • LiAsF 6 lithium hexafluoroarsenate
  • common material used for the making of separator in a battery is a thin polymer film that is strong, heat resistant and inert to the electrolyte solution.
  • nanostmctured materials incorporate or contain cavities, pores or nanosized components, such as nanostmctured powder, nanocomposites, nanodispersion, nanoporous materials, surface-structured nanomaterials and nanostmctured core-shell particles to increase energy and prolong battery life.
  • nanostmctured powder such as nanostmctured powder, nanocomposites, nanodispersion, nanoporous materials, surface-structured nanomaterials and nanostmctured core-shell particles to increase energy and prolong battery life.
  • electrode glazing with nanosized particles that increases the surface area of electrodes, enabling more currents to flow through electrodes and chemicals in batteries. This technique not only enhances the efficiency of batteries, but also reduces the weight of batteries while being capable of providing sufficient energy as required, as may be seen from description of inventions in various patents. For example:
  • the Thai patent application number 1601000853 discloses a lithium nickel manganese cobalt-type CR-2025 button cell that uses a nanocarbon sheet as a conductive material in its cathode, where the said button cell has an electricity power storage of 118 milliamp hours per gram.
  • the Thai patent application number 1801006035 discloses a preparation of battery electrode, comprising a nickel-cobalt hydroxide coating step.
  • the United States patent number US10741872B2 discloses a cathode of batteries that comprises nickel manganese cobalt oxide as its core and uses a lithium-transition metal composite as its shell, where the weight ratio of the core: the shell ranges from 20:80 to 80:20.
  • Deterioration issue of lithium-ion batteries comes from the main component; that is, the anode, where it expands and shrinks in alternation in each recharging cycle. Upon expansion and shrinkage in multiple recharging cycles, a crack occurs at the anode until it is too enlarged and dilated, disabling current flow.
  • Lithium-ion batteries of which anode is made from silicon have 10 times more capacity than those with anode made from graphite.
  • the anode made from silicon has much lower stability than that made from graphite. Therefore, in this invention, mesocarbon microbeads (MCMB) and/or graphite with silicon as its additive are used in making the anode, where MCMB is a hard carbon material, spherical, highly porous with a pore size of 2-50 nanometers, and has a particle size of approximately 1-40 microns.
  • MCMB mesocarbon microbeads
  • lithium-ion batteries of which the cathode comprises material with lithium nickel manganese cobalt oxide (Li-NMC or NMC) as its core, a carbon material as its shell and a polymer compound as a binder; and the anode comprises a carbon material-silicon composite, particularly nanosilicon powder; wherein the cathode uses a ratio of the material comprising the NMC as its core to the carbon material as its shell from 7:3 to 9.5:0.5 parts by weight, and the anode uses a ratio in weight percent of the nanosilicon between 2.5-30 parts by weight.
  • Li-NMC or NMC lithium nickel manganese cobalt oxide
  • this invention also involves preparation of lithium-ion batteries, wherein the approach comprises steps of:
  • cathode comprises materials with NMC as its core and carbon as its shell. It comprises the followings.
  • Cathode comprises a power-storing material in the form of core metal oxide and shell (core @ shell) with lithium nickel manganese cobalt oxide (NMC) forming the core metal oxide, and a carbon material as its shell.
  • a polymer compound is a binder, and a carbon material is a conductor.
  • a preferred weight ratio according to this invention can be selected from a range of 7:3 to 9.5:0.5 parts by weight, or 70-95 percent to 5-30 percent by weight, wherein a ratio of the power-storing materials comprising the NMC as the core and the carbon material as the shell to the conductive carbon material to the binder is 96:2:2 parts by weight, respectively.
  • Anode comprises a mesocarbon microbeads (MCMB)-silicon composite as a power-storing material, a polymer compound as a binder and a carbon material as a conductor.
  • MCMB mesocarbon microbeads
  • the MCMB-silicon composite is provided in that the silicon is nanosilicon powder with its particle size in a range of 5-100 nanometers.
  • the prepared composite for use in making the anode is smaller than 150 micrometers in size.
  • a battery case used in containing the anode, electrolyte in ion conduction, a separator and the cathode may be that with a general shape, such as button cell, panel, cylindrical cell or laminated material battery case. Then the assembled lithium-ion batteries are tested for their efficiency with battery tester under an electrochemical technique, wherein the preferred mixing of materials comprising the NMC as the core and the carbon material as the shell for making the cathode according to this invention is prepared by mechanofusion process.
  • a preferred duration of mixing the cathode-making materials according to this invention with mechanofusion process is in a range of 10-60 minutes.
  • a preferred weight ratio according to this invention for mixing the materials comprising the NMC as the core and the carbon material as the shell for making the cathode can be selected from a range of 7:3 to 9.5:0.5 parts by weight, or 70-95 percent to 5-30 percent by weight.
  • the most preferred weight ratio according to this invention for mixing the materials comprising the NMC as the core and the carbon material as the shell for making the cathode is 9:1 parts by weight, or 90 percent to 10 percent by weight.
  • the preferred mixing of silicon and carbon material for use in making the anode according to this invention uses high energy ball mill.
  • a preferred duration of mixing silicon and carbon material for use in making the anode with high energy ball mill according to this invention is 4 hours.
  • a preferred percentage for the mixing of silicon and carbon material for use in making the anode according to this invention can be selected between 2.5-30 percent by weight of silicon.
  • a preferred carbon material according to this invention as an ingredient for the electrode making can be selected from carbon black, carbon super P, graphite, carbon fiber, MCMB (pore size of 2-50 nanometers) or combination of two or more said carbon materials.
  • a preferred organic solvent according to this invention in the electrode assembly step can be selected from N-methyl-2-pyrrolidone or ethanol or water.
  • Binders for binding that are ingredients according to this invention in the assembly of the cathode and the anode prepared from steps A and B, and the assembly of lithium-ion batteries of which cathode is the material with the NMC as its core and the carbon as its shell can be selected from any one of polyvinylidene fluoride (PVDF) or carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose or butadiene rubber or styrene-butadiene rubber (SBR) or polyacrylic acid, or combination of two or more said glues.
  • PVDF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • SBR styrene-butadiene rubber
  • Material comprising NMC is mixed in mechanofusion process at a speed of 1,000 revolutions per minute for 10 minutes, and then carbon black is added, stirred and mixed further at a speed of 1,000 revolutions per minute for a duration of 10-60 minutes and with a weight ratio of the NMC to carbon black in a range from 7:3 to 9.5:0.5.
  • SEM scanning electron microscope
  • EDX energy dispersive x- ray spectrometer
  • Silicon and graphite-type carbon material are mixed with a ball mill, which is a device for size reduction of solid that consists of a closed container or a shell liner rotating slowly horizontally. Inside is a grinding media being a granite ball. Milling is caused by collision of the ball with material needed to be ground until the ground material is down to a proper size; that is, smaller than 150 micrometers.
  • a percentage for mixing of silicon and graphite-type carbon material for use in making the anode can be selected between 2.5-30.0 percent by weight of the silicon.
  • MCMB Silicon and mesoporous carbon microbeads
  • the material with the NMC as its core and the carbon as its shell (NMC@C) as obtained from sample A is mixed with conductive carbon black and fluorine polyvinylidene fluoride-type binder at a weight ratio of the material with the NMC as its core and the carbon as its shell to the conductive carbon to the binder of 7:2:1 for preparation of button cells and 96:2:2 for preparation of cylindrical cells, using N-methyl pyrrolidone-type solvent, and then coated on aluminum foil and dried in a vacuum dryer at 80 degrees Celsius for 24 hours.
  • the silicon-graphite carbon composite obtained from step B is mixed with conductive carbon black and polyvinylidene fluoride-type binder at a weight ratio of the silicon-graphite composite to the conductive carbon to the binder of 8:1:1, using N-methyl pyrrolidone-type solvent, and then coated on copper foil and dried in a vacuum dryer at 80 degrees Celsius for 24 hours.
  • Example F Anode Preparation for Cylindrical Cells
  • Anode preparation for cylindrical cells is performed in a vacuum mixer with cooling system to maintain a temperature at lower than 35 degrees Celsius, beginning with mixing of CMC- type binder, deionized water, conductive carbon and the silicon-MCMB composite obtained from C until homogeneous. Then SBR is added, stirred and mixed further for 12 hours with a weight ratio of the silicon-MCMB composite: the conductive carbon: the CMC-type binder: SBR of 96:1:1.5:1.5. After that, copper foil is coated, dried to remove the solvent at 120 degrees Celsius, and then compressed with a rolling press machine so that the coated copper foil is approximately 120- 150-micrometer thick.
  • Assembly of button cell batteries is performed in an argon-filled glove box, using the cathode prepared from step D and the anode prepared from step E, where this anode is soaked in electrolyte together with lithium foil (pre-lithiation) for 2 hours prior to the assembly of cells with a separator in the form of polyethylene polymer film functioning to prevent the cathode from contacting with the anode that would otherwise causes short circuit.
  • An electrolyte solution is used that contains 1 M lithium hexafluorophosphate in ethylene carbonate, ethylene tetylcarbonate and dimethyl carbonate at a volume ratio of ITT part.
  • This cylindrical cell 18650 has a diameter of approximately 18 millimeters and the height of 65 millimeters.
  • the entire assembly of cylindrical cells 18650 that use the cathode prepared from step D and the anode prepared from step F, using the silicon-mesoporous carbon microbeads (MCMB) composite, is performed in a dry room with dew points at -40 and -55 degrees Celsius for suitability in injecting and filling electrolyte, which is an organic solution also contained in the cylindrical cells.
  • MCMB silicon-mesoporous carbon microbeads
  • the assembly of cylindrical cells 18650 begins with rolling of the cathode prepared from step D and the anode prepared from step F in alternation and cutting with a roll to sheet cutting machine, and then welding with an ultrasonic welding machine.
  • a separator comprising polypropylene and polyethylene is put between the cathode and the anode to prevent short circuit between them, and let lithium ions move through pores of the material.
  • the rolled electrodes are put in battery case, and then the case containing the electrodes is passed through a case gouging process. After that, battery cover is welded together with the part of electrodes rolled in the battery case. Electrolyte-filling process then takes place, and batteries are crimped with an automatic crimping machine.

Abstract

A lithium-ion battery that comprises cathode consisting of metal oxide of lithium nickel manganese cobalt as its core and carbon material as its shell, anode consisting of mesocarbon microbeads-silicon composite, wherein the preparation method of the said lithium-ion battery comprises preparation of materials used in making the cathode by mixing lithium nickel manganese cobalt oxide as its core and carbon material as its shell with mechanofusion process, and then adding conductive carbon and a binder. Materials used in making the anode are then prepared by mixing mesocarbon microbeads and silicon as an energy-storing material with high energy bah mill, and then adding conductive carbon, a binder and an organic solvent. Then the lithium-ion battery is assembled using the prepared cathode and anode with polymer film as an electrode separator and an electrolyte solution as an ion conductor.

Description

LITHIUM ION BATTERY OF WHICH CATHODE COMPRISES MATERIAL WITH
LITHIUM NICKEL MANGANESE COBALT OXIDE AS ITS CORE AND CARBON AS
ITS SHELL
Field of the Invention
Chemical and electrochemical engineering involved with lithium-ion batteries of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell
Background of the Invention
Batteries are power-storing devices capable of converting chemical energy into electrical power directly. Electrical power storage in various types of batteries is based on important criteria for determination of storage options, being capacity (kilowatt-hours) and storage density (kilowatt- hours per volume). In addition, battery selection has to take other factors into account, such as the efficiency of batteries because there is loss during charging, storage and discharging. This is because batteries are devices for storing electricity that can be recharged multiple times. Good batteries should have high energy and electricity power density, light weight, high safety for use, high reliability, and low manufacturing cost.
Lithium is a key element in the manufacture of batteries, and present in the form of an inorganic compound of cathode and an electrolyte solution as lithium salt in an organic solvent.
Lithium-ion secondary cell batteries (rechargeable battery) were first launched commercially in 1991 by Sony Corporation. Since then, lithium-ion batteries have been manufactured for use in several types of electronic devices and been a highly -popular group of batteries. Nowadays, the use of lithium batteries can be divided into three main groups, namely:
1) Use in portable electronic devices
2) Use in road transport
3) Use as a power supply system
Among these, the first two groups are found to have large market share (source: https://waa.inter.nstda.or.th/stks/pub/2020/20200128-situation-recycling-lithium-battery.pdf).
Lithium battery cells used for portable devices or electrical appliances can be divided per their shapes into cylindrical, pouch, prismatic and button cells. While in various electrical motor vehicles, lithium batteries are in the form of battery packs; also divided into batteries in automobiles, buses, motorcycles and other mobile electrical motor vehicles; making the demand for battery in the group of electrical motor vehicles higher than that in the groups of portable devices and electrical appliances.
The structure of a lithium-ion battery cell consists of three major parts, namely electrodes (cathode and anode), a separator and an electrolyte solution. Typically, the cathode is the most important part, usually made from lithium-containing inorganic compound materials, such as lithium cobalt oxide (LiCoC ), lithium iron phosphate (LiFePCL), lithium manganese oxide (LiMmCL) and so on. While for the making of anode, common materials used are various types of carbon, namely graphite, hard carbon or graphene, where this anode is an element in determining the voltage of a prepared lithium battery cell. As for the electrolyte solution, it is a solution of lithium salt compound dissolved in an organic solvent, such as lithium hexafluorophosphate (LiPF6), lithium perchlorate (LiCICL), lithium hexafluoroarsenate (LiAsF6) and so on. Lastly, common material used for the making of separator in a battery is a thin polymer film that is strong, heat resistant and inert to the electrolyte solution.
Good batteries have to be light-weighted and efficient in transferring lithium ions to both electrodes. With highly efficient batteries, more lithium ions can enter both electrodes during each charging cycle. Search for proper materials for manufacture of lithium-ion batteries is an extremely important step because it will help enhance the efficiency in application of batteries. A report was prepared by the Industry Information Research, Thailand Automotive Institute, on types of main minerals used in the manufacture of battery cells, such as lithium, cobalt, manganese, nickel and graphite, with lithium, cobalt, manganese and nickel combined in proportions dependent on types of lithium-ion batteries as cathode. Prominent quality of each element is utilized; that is, nickel has a prominent point in its high specific energy but has low stability; manganese has quality of maintaining low resistance in cells; and combination of both metals helps strengthen each other.
This type of batteries would be fit for use with electrical vehicles because of very low intrinsic heating rate.
Nevertheless, development of batteries with higher efficiency is needed, particularly of lithium-ion batteries with light weight, high capacity and high surface-to-volume ratio, and nanostructured materials with high surface-to-volume ratio are thus applied. Although larger than nanomaterials on the outside, nanostmctured materials incorporate or contain cavities, pores or nanosized components, such as nanostmctured powder, nanocomposites, nanodispersion, nanoporous materials, surface-structured nanomaterials and nanostmctured core-shell particles to increase energy and prolong battery life. Examples include electrode glazing with nanosized particles that increases the surface area of electrodes, enabling more currents to flow through electrodes and chemicals in batteries. This technique not only enhances the efficiency of batteries, but also reduces the weight of batteries while being capable of providing sufficient energy as required, as may be seen from description of inventions in various patents. For example:
The Thai patent application number 1601000853 discloses a lithium nickel manganese cobalt-type CR-2025 button cell that uses a nanocarbon sheet as a conductive material in its cathode, where the said button cell has an electricity power storage of 118 milliamp hours per gram.
The Thai patent application number 1801006035 discloses a preparation of battery electrode, comprising a nickel-cobalt hydroxide coating step.
The United States patent number US10741872B2 discloses a cathode of batteries that comprises nickel manganese cobalt oxide as its core and uses a lithium-transition metal composite as its shell, where the weight ratio of the core: the shell ranges from 20:80 to 80:20.
The United States patent number US7892677B2 discloses an anode of batteries, comprising a carbon fiber-silicon composite.
Deterioration issue of lithium-ion batteries comes from the main component; that is, the anode, where it expands and shrinks in alternation in each recharging cycle. Upon expansion and shrinkage in multiple recharging cycles, a crack occurs at the anode until it is too enlarged and dilated, disabling current flow.
Lithium-ion batteries of which anode is made from silicon have 10 times more capacity than those with anode made from graphite. However, the anode made from silicon has much lower stability than that made from graphite. Therefore, in this invention, mesocarbon microbeads (MCMB) and/or graphite with silicon as its additive are used in making the anode, where MCMB is a hard carbon material, spherical, highly porous with a pore size of 2-50 nanometers, and has a particle size of approximately 1-40 microns. A study found that this carbon material had similar structure to graphite but more strength, could store lithium ions well and had a capacity based on the experiment of as much as 750 milliamp hours per gram (publication data in J Electrochem Soc, issue 142, 1995, pages 1041 1046).
Summary of the Invention
To provide batteries with higher efficiency, particularly lithium-ion batteries of which the cathode comprises material with lithium nickel manganese cobalt oxide (Li-NMC or NMC) as its core, a carbon material as its shell and a polymer compound as a binder; and the anode comprises a carbon material-silicon composite, particularly nanosilicon powder; wherein the cathode uses a ratio of the material comprising the NMC as its core to the carbon material as its shell from 7:3 to 9.5:0.5 parts by weight, and the anode uses a ratio in weight percent of the nanosilicon between 2.5-30 parts by weight.
In another embodiment, this invention also involves preparation of lithium-ion batteries, wherein the approach comprises steps of:
A. mixing of materials used in making the cathode,
B. preparation of a carbon-silicon composite for use in making the anode, and
C. assembly of lithium-ion batteries, using the cathode and the anode prepared from the materials in steps A and B.
Brief Description of the Drawings
Figure 1 Results of analysis with a scanning electron microscope (SEM) in combination with an energy dispersive x-ray spectrometer (EDX) of a cathode material that comprises nickel, manganese and cobalt as prepared according to this invention
Figure 2 Results of analysis with a scanning electron microscope (SEM) in combination with an energy dispersive x-ray spectrometer (EDX) of a cathode material that comprises nickel, manganese and cobalt as prepared according to this invention (black and white images)
Figure 3 Batteries’ capacity and Coulombic efficiency of button cells prepared according to this invention at a charge/discharge rate of 1 coulomb
Detailed Description of the Invention
This invention discloses lithium-ion battery of which cathode comprises materials with NMC as its core and carbon as its shell. It comprises the followings. Cathode comprises a power-storing material in the form of core metal oxide and shell (core @ shell) with lithium nickel manganese cobalt oxide (NMC) forming the core metal oxide, and a carbon material as its shell. A polymer compound is a binder, and a carbon material is a conductor.
For mixing of the materials comprising the NMC as the core and the carbon material as the shell for making the cathode, a preferred weight ratio according to this invention can be selected from a range of 7:3 to 9.5:0.5 parts by weight, or 70-95 percent to 5-30 percent by weight, wherein a ratio of the power-storing materials comprising the NMC as the core and the carbon material as the shell to the conductive carbon material to the binder is 96:2:2 parts by weight, respectively.
Anode comprises a mesocarbon microbeads (MCMB)-silicon composite as a power-storing material, a polymer compound as a binder and a carbon material as a conductor.
The MCMB-silicon composite is provided in that the silicon is nanosilicon powder with its particle size in a range of 5-100 nanometers.
Preparation of lithium-ion batteries of which cathode comprises materials with the NMC as its core and the carbon as its shell comprises the following procedure.
A. Mixing of the materials used in making the cathode, which comprises the NMC as its core and the carbon material as its shell according to this invention, is prepared by mechanofusion process. This method has small particles compressed and fused through energy input.
B. Preparation of the carbon material-silicon composite for use in making the anode to minimize volumetric expansion issue of the silicon. The prepared composite for use in making the anode is smaller than 150 micrometers in size.
C. Assembly of lithium-ion batteries using the cathode and anode materials prepared from steps A and B, using a carbon material as conductive carbon together with a binder. The said composite is then coated onto metal foil that is a current collectors. A battery case used in containing the anode, electrolyte in ion conduction, a separator and the cathode may be that with a general shape, such as button cell, panel, cylindrical cell or laminated material battery case. Then the assembled lithium-ion batteries are tested for their efficiency with battery tester under an electrochemical technique, wherein the preferred mixing of materials comprising the NMC as the core and the carbon material as the shell for making the cathode according to this invention is prepared by mechanofusion process.
A preferred duration of mixing the cathode-making materials according to this invention with mechanofusion process is in a range of 10-60 minutes.
A preferred weight ratio according to this invention for mixing the materials comprising the NMC as the core and the carbon material as the shell for making the cathode can be selected from a range of 7:3 to 9.5:0.5 parts by weight, or 70-95 percent to 5-30 percent by weight.
The most preferred weight ratio according to this invention for mixing the materials comprising the NMC as the core and the carbon material as the shell for making the cathode is 9:1 parts by weight, or 90 percent to 10 percent by weight.
The preferred mixing of silicon and carbon material for use in making the anode according to this invention uses high energy ball mill.
A preferred duration of mixing silicon and carbon material for use in making the anode with high energy ball mill according to this invention is 4 hours.
A preferred percentage for the mixing of silicon and carbon material for use in making the anode according to this invention can be selected between 2.5-30 percent by weight of silicon.
A preferred carbon material according to this invention as an ingredient for the electrode making can be selected from carbon black, carbon super P, graphite, carbon fiber, MCMB (pore size of 2-50 nanometers) or combination of two or more said carbon materials.
A preferred organic solvent according to this invention in the electrode assembly step can be selected from N-methyl-2-pyrrolidone or ethanol or water.
Binders for binding that are ingredients according to this invention in the assembly of the cathode and the anode prepared from steps A and B, and the assembly of lithium-ion batteries of which cathode is the material with the NMC as its core and the carbon as its shell, can be selected from any one of polyvinylidene fluoride (PVDF) or carboxymethyl cellulose (CMC) or sodium carboxymethyl cellulose or butadiene rubber or styrene-butadiene rubber (SBR) or polyacrylic acid, or combination of two or more said glues.
Hereinafter, this invention is described in detail with reference to examples. This invention is, however, not limited to these examples. Examples
Example A: Mixing of Materials Used in Cathode Making
Material comprising NMC is mixed in mechanofusion process at a speed of 1,000 revolutions per minute for 10 minutes, and then carbon black is added, stirred and mixed further at a speed of 1,000 revolutions per minute for a duration of 10-60 minutes and with a weight ratio of the NMC to carbon black in a range from 7:3 to 9.5:0.5. Upon the obtained mixture being analyzed with a scanning electron microscope (SEM) in combination with an energy dispersive x- ray spectrometer (EDX) that is a device for use in distinguishing characteristic x-rays of different elements by energy spectrum coupled with the use of a computer program to process obtained signals, elements that are ingredients in the prepared material can be identified. Based on the analytical results as shown in Figures 1 and 2, the NMC material as the core and the carbon material as the shell (or so called NMC@C) may be seen clearly.
Example B. Mixing of Materials Used for Anode Making for Button Cell Batteries
Silicon and graphite-type carbon material are mixed with a ball mill, which is a device for size reduction of solid that consists of a closed container or a shell liner rotating slowly horizontally. Inside is a grinding media being a granite ball. Milling is caused by collision of the ball with material needed to be ground until the ground material is down to a proper size; that is, smaller than 150 micrometers. A percentage for mixing of silicon and graphite-type carbon material for use in making the anode can be selected between 2.5-30.0 percent by weight of the silicon. Example C. Mixing of Materials Used in Anode Making for Cylindrical Cells
Silicon and mesoporous carbon microbeads (MCMB) with pore size of 2-50 nanometers were mixed with a high energy ball mill at a weight ratio of 2.5 percent silicon for 4 hours until the mixture is smaller than 150 micrometers in size.
Example D Cathode Preparation
The material with the NMC as its core and the carbon as its shell (NMC@C) as obtained from sample A is mixed with conductive carbon black and fluorine polyvinylidene fluoride-type binder at a weight ratio of the material with the NMC as its core and the carbon as its shell to the conductive carbon to the binder of 7:2:1 for preparation of button cells and 96:2:2 for preparation of cylindrical cells, using N-methyl pyrrolidone-type solvent, and then coated on aluminum foil and dried in a vacuum dryer at 80 degrees Celsius for 24 hours.
Example E. Anode Preparation for Button Cell Batteries
The silicon-graphite carbon composite obtained from step B is mixed with conductive carbon black and polyvinylidene fluoride-type binder at a weight ratio of the silicon-graphite composite to the conductive carbon to the binder of 8:1:1, using N-methyl pyrrolidone-type solvent, and then coated on copper foil and dried in a vacuum dryer at 80 degrees Celsius for 24 hours. Example F: Anode Preparation for Cylindrical Cells
Anode preparation for cylindrical cells is performed in a vacuum mixer with cooling system to maintain a temperature at lower than 35 degrees Celsius, beginning with mixing of CMC- type binder, deionized water, conductive carbon and the silicon-MCMB composite obtained from C until homogeneous. Then SBR is added, stirred and mixed further for 12 hours with a weight ratio of the silicon-MCMB composite: the conductive carbon: the CMC-type binder: SBR of 96:1:1.5:1.5. After that, copper foil is coated, dried to remove the solvent at 120 degrees Celsius, and then compressed with a rolling press machine so that the coated copper foil is approximately 120- 150-micrometer thick.
Example G: Assembly of Button Cell Batteries
Assembly of button cell batteries is performed in an argon-filled glove box, using the cathode prepared from step D and the anode prepared from step E, where this anode is soaked in electrolyte together with lithium foil (pre-lithiation) for 2 hours prior to the assembly of cells with a separator in the form of polyethylene polymer film functioning to prevent the cathode from contacting with the anode that would otherwise causes short circuit. An electrolyte solution is used that contains 1 M lithium hexafluorophosphate in ethylene carbonate, ethylene tetylcarbonate and dimethyl carbonate at a volume ratio of ITT part.
Example H.- Electrochemical Efficiency Test of Button Cell Batteries
An electrochemical efficiency test of the cells prepared per example G, when cells of which anode contained 10 percent by weight silicon were selected for the test, could be performed using galvanostatic charge discharge (GCD). Results were obtained as in Table 1.
Table 1 Capacity of the prepared batteries
Figure imgf000010_0001
In addition, a Coulombic efficiency test of the batteries prepared per example G at 1 coulomb charge and 0-500 cycles as shown in Figure 3 demonstrated that the Coulombic efficiency of the batteries prepared per example G could be up to 100% from the 20th cycle onward, but the capacity of the prepared batteries was decreased as the number of cycles increased.
Example 1 Assembly of Cylindrical Cells 18650
This cylindrical cell 18650 has a diameter of approximately 18 millimeters and the height of 65 millimeters. The entire assembly of cylindrical cells 18650 that use the cathode prepared from step D and the anode prepared from step F, using the silicon-mesoporous carbon microbeads (MCMB) composite, is performed in a dry room with dew points at -40 and -55 degrees Celsius for suitability in injecting and filling electrolyte, which is an organic solution also contained in the cylindrical cells.
The assembly of cylindrical cells 18650 according to this description begins with rolling of the cathode prepared from step D and the anode prepared from step F in alternation and cutting with a roll to sheet cutting machine, and then welding with an ultrasonic welding machine. A separator comprising polypropylene and polyethylene is put between the cathode and the anode to prevent short circuit between them, and let lithium ions move through pores of the material. After that, the rolled electrodes are put in battery case, and then the case containing the electrodes is passed through a case gouging process. After that, battery cover is welded together with the part of electrodes rolled in the battery case. Electrolyte-filling process then takes place, and batteries are crimped with an automatic crimping machine. Example J Electrochemical Efficiency Test of Cylindrical Cells
An electrochemical efficiency test of the cylindrical cells prepared from step I, which used the cathode prepared from step D and the anode prepared from step F using the silicon-MCMB composite compared with the anode prepared from graphite, used galvanostatic charge discharge (GCD) at 0.1 coulomb charge and the voltage of 3-4.2 volts. Results were obtained as in Table 2.
Table 2 Electrochemical efficiency of the cylindrical cells using the cathode prepared from step D
Figure imgf000011_0001
Based on Table 2, it can be seen that the cylindrical cell using the cathode prepared from step D and the anode prepared from step F using the silicon-MCMB composite had higher capacity and energy density than those using the anode prepared from graphite. Best Mode of the Invention
As described in Detailed Description of the Invention

Claims

Claims
1. A lithium-ion battery, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell, comprising: a cathode that comprises an energy-storing material in the form of core metal oxide with a shell (core @ shell) with lithium nickel manganese cobalt oxide (NMC) combined as the core metal oxide and a carbon material as the shell as well as a binder to facilitate binding and a carbon material as a conductor, an anode that comprises mesocarbon microbeads (MCMB) and silicon as an energy-storing material as well as a binder to facilitate binding and a carbon material as a conductor, wherein the energy-storing material in the form of core @ shell of the cathode has a ratio of the lithium nickel manganese cobalt oxide (Li-NMC or NMC) as its core to the carbon material as its shell between 7:3 to 9.5:0.5 parts by weight.
2. The lithium-ion battery, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell according to claim 1, wherein a ratio of the energy-storing material comprising the lithium nickel manganese cobalt oxide as its core and the carbon material as its shell to the conductive carbon to the binder is 96:2:2 by weight, respectively.
3. The lithium-ion battery, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell according to claim 1, wherein the MCMB -silicon composite is provided with silicon as nanosilicon powder with particle size between 5-100 nanometers in the amount of 2.5-30.0 percent by weight of the MCMB-silicon composite.
4. The lithium-ion battery, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell according to claim 1, wherein the binder can be selected from any one or more of polyvinylidene fluoride (PVDF), sodium carboxymethyl cellulose, butadiene rubber or polyacrylic acid in combination thereof.
5. The lithium-ion battery, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell according to claim 1, wherein the carbon material can be selected from any one or more of carbon black, carbon super P, graphite, carbon fiber or MCMB (pore size of 2-50 nanometers) in combination thereof.
6. A preparation method of lithium-ion batteries, of which cathode comprises metal oxide of lithium nickel manganese cobalt as its core and carbon as its shell, comprising:
A. Materials used in making the cathode are prepared by mixing lithium nickel manganese cobalt oxide as its core and a carbon material as its shell with mechanofusion process and then adding conductive carbon and a binder.
B. Materials used in making the anode are prepared by mixing MCMB and silicon as an energy-storing material with high energy ball mill and then adding conductive carbon, a binder and an organic solvent.
C. Lithium-ion batteries are assembled using the cathode prepared from step A and the anode prepared from step B with polymer film as a separator, and using an electrolyte solution as an ion conductor.
7. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein the preferred mixing of the lithium nickel manganese cobalt oxide as the core and the carbon material as the shell for making the cathode according to this invention is prepared by mechanofusion process.
8. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein the mixing between MCMB and silicon to yield the material for making the anode is prepared using high energy ball mill.
9. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein the energy-storing material in the form of core @ shell of the cathode has a ratio of the lithium nickel manganese cobalt oxide (Li-NMC or NMC) as its core to the carbon material as its shell between 7:3 to 9.5:0.5 parts by weight.
10. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein a ratio of the energy-storing material comprising the lithium nickel manganese cobalt oxide as its core and the carbon material as its shell to the conductive carbon to the binder is 96:2:2 parts by weight, respectively.
11. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, where the binder can be selected from any one or more of polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), sodium carboxymethyl cellulose, butadiene rubber, styrene-butadiene rubber (SBR)or polyacrylic acid in combination thereof.
12. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein the carbon material can be selected from any one or more of carbon black, carbon super P, graphite, carbon fiber or MCMB (pore size of 2-50 nanometers) in combination thereof.
13. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein the organic solvent in the electrode assembly can be selected from any one or more of N- methyl-2-pyrrolidone, ethanol or water in combination thereof.
14. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein it further comprises a step of coating the material used in making the cathode as obtained from step A onto a current collector that is aluminum with a thickness between 140-250 micrometers, and then drying
15. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein a ratio between the silicon-MCMB composite to the conductive carbon to the CMC -type binder to SBR is 96:1:1.5:1.5 parts by weight, respectively.
16. The preparation method of lithium-ion batteries, of which cathode comprises the metal oxide of lithium nickel manganese cobalt as its core and the carbon as its shell according to claim 6, wherein it further comprises a step of coating the material used in making the anode as obtained from step B onto a current collector that is copper with a thickness between 100-250 micrometers, and then drying.
PCT/TH2022/000019 2021-05-21 2022-05-11 Lithium-ion battery of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell WO2022245303A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
TH2101002939 2021-05-21
TH2101002939 2021-05-21

Publications (1)

Publication Number Publication Date
WO2022245303A1 true WO2022245303A1 (en) 2022-11-24

Family

ID=84141555

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/TH2022/000019 WO2022245303A1 (en) 2021-05-21 2022-05-11 Lithium-ion battery of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell

Country Status (1)

Country Link
WO (1) WO2022245303A1 (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1653534A1 (en) * 2004-10-28 2006-05-03 Samsung SDI Co., Ltd. Conductive agent - positive active material composite for lithium secondary battery, method of preparing the same, and positive electrode and lithium secondary battery comprising the same
JP2015503185A (en) * 2011-11-10 2015-01-29 ジェネラル リサーチ インスティテュート フォア ノンフェラス メタルス Nanosilicon carbon composite material and method for preparing the same
US20150349333A1 (en) * 2014-05-30 2015-12-03 Samsung Electronics Co., Ltd. Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials
KR20180035752A (en) * 2018-03-23 2018-04-06 주식회사 엘지화학 Surface coated porous silicon based anode active material and preparation method thereof
US20200354222A1 (en) * 2019-05-08 2020-11-12 Eocell Limited Silicon Carbon Nanocomposite (SCN) Material, Fabrication Process Therefor, and Use Thereof in an Anode Electrode of a Lithium Ion Battery
KR20210041684A (en) * 2019-10-07 2021-04-16 현대자동차주식회사 Lithium secondary battery and manufacturing method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1653534A1 (en) * 2004-10-28 2006-05-03 Samsung SDI Co., Ltd. Conductive agent - positive active material composite for lithium secondary battery, method of preparing the same, and positive electrode and lithium secondary battery comprising the same
JP2015503185A (en) * 2011-11-10 2015-01-29 ジェネラル リサーチ インスティテュート フォア ノンフェラス メタルス Nanosilicon carbon composite material and method for preparing the same
US20150349333A1 (en) * 2014-05-30 2015-12-03 Samsung Electronics Co., Ltd. Composite cathode active materials, preparation methods thereof, and lithium batteries including the composite cathode active materials
KR20180035752A (en) * 2018-03-23 2018-04-06 주식회사 엘지화학 Surface coated porous silicon based anode active material and preparation method thereof
US20200354222A1 (en) * 2019-05-08 2020-11-12 Eocell Limited Silicon Carbon Nanocomposite (SCN) Material, Fabrication Process Therefor, and Use Thereof in an Anode Electrode of a Lithium Ion Battery
KR20210041684A (en) * 2019-10-07 2021-04-16 현대자동차주식회사 Lithium secondary battery and manufacturing method thereof

Similar Documents

Publication Publication Date Title
EP2260527B1 (en) Method for manufacturing lithium secondary battery, lithium secondary battery, and lithium secondary battery system
CN100565984C (en) Positive electrode and lithium secondary battery
US9172091B2 (en) Core-shell type anode active material for lithium secondary batteries, method for preparing the same and lithium secondary batteries comprising the same
EP2654108B1 (en) Positive electrode for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery and battery module
US10014524B2 (en) Nonaqueous secondary battery
JP5133020B2 (en) Method for producing positive electrode plate for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery using the positive electrode plate
US9219278B2 (en) Non-aqueous electrolyte secondary battery and use thereof
WO2020111201A1 (en) Lithium ion secondary battery positive electrode composition, lithium ion secondary battery positive electrode, and lithium ion secondary battery
JP2008108649A (en) Manufacturing method of vehicular lithium secondary cell cathode
US20230108289A1 (en) Positive-electrode material, positive electrode plate, lithium secondary battery, battery module, battery pack, and apparatus
JPH11102729A (en) Manufacture of nonaqueous solvent type secondary battery
WO2022245303A1 (en) Lithium-ion battery of which cathode comprises material with lithium nickel manganese cobalt oxide as its core and carbon as its shell
JP7223999B2 (en) Positive electrode composition for lithium ion secondary battery, positive electrode for lithium ion secondary battery, and lithium ion secondary battery
KR20220132947A (en) Black phosphorus-carbon nanotube composite synthesized using surfactant and method of manufacturing the same and lithium secondary battery including the same
JP2011134535A (en) Positive electrode for lithium secondary battery, and method for manufacturing the same
CA2674783C (en) Core-shell anode material comprising positive temperature co-effecient medium for lithium secondary battery
Cao et al. Strategies to optimize performance of lithium-ion supercapacitors: Screening of cathode configuration, anode pre-lithiation loading and separator type
EP4239712A1 (en) Positive electrode sheet, secondary battery, battery module, battery pack, and electrical device
JP7358790B2 (en) Electrodes for energy storage devices
Guillaume Development of high power hybrid cathodes for lithium ion batteries
Adepoju A Study of LiFePO 4 Cathode Material with Carbon Nanomaterial Additives for Li-Ion Batteries
Chiluwal Three-Dimensional Electrode Architectures for Beyond Lithium-Ion Batteries
GB2620391A (en) Lithium battery
KR20240040623A (en) Electrodes comprising blended active material
WO2023249567A1 (en) Lithium-ion battery with positive electrode containing nmc material as the core and carbon black as the shell

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22805104

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE