WO2020047228A1 - Matériaux actifs de batterie rechargeable au lithium-ion revêtus - Google Patents

Matériaux actifs de batterie rechargeable au lithium-ion revêtus Download PDF

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Publication number
WO2020047228A1
WO2020047228A1 PCT/US2019/048768 US2019048768W WO2020047228A1 WO 2020047228 A1 WO2020047228 A1 WO 2020047228A1 US 2019048768 W US2019048768 W US 2019048768W WO 2020047228 A1 WO2020047228 A1 WO 2020047228A1
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WIPO (PCT)
Prior art keywords
active material
battery
attritor
positive electrode
coating
Prior art date
Application number
PCT/US2019/048768
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English (en)
Inventor
Dongqiang LIU
Amélie FORAND
Abdelbast Guerfi
Karim Zaghib
Jan L. Allen
Samuel A. Delp III
T. Richard Jow
Original Assignee
HYDRO-QUéBEC
Government Of The United States Of America, As Represented By The Secretary Of The Army
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Application filed by HYDRO-QUéBEC, Government Of The United States Of America, As Represented By The Secretary Of The Army filed Critical HYDRO-QUéBEC
Priority to JP2021512278A priority Critical patent/JP7443340B2/ja
Priority to KR1020217009263A priority patent/KR20210062021A/ko
Priority to CN201980070904.2A priority patent/CN113169328A/zh
Priority to CA3109525A priority patent/CA3109525A1/fr
Priority to EP19856341.3A priority patent/EP3844831A4/fr
Publication of WO2020047228A1 publication Critical patent/WO2020047228A1/fr
Priority to US17/184,447 priority patent/US20210184209A1/en
Priority to JP2023183376A priority patent/JP2023181319A/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—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
    • 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
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • 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
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0468—Compression means for stacks of electrodes and separators
    • 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
    • H01M10/04—Construction or manufacture in general
    • H01M10/0481—Compression means other than compression means for stacks of electrodes and separators
    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0045—Room temperature molten salts comprising at least one organic ion
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the disclosure relates to a coated lithium ion rechargeable battery positive electrode active material, methods of manufacturing such materials, and lithium ion rechargeable batteries containing such materials.
  • Organic liquid electrolytes are able to operate over a variety of voltages and have other advantages.
  • organic liquid electrolytes can react with certain positive electrode active materials, generating gasses inside the battery. Gasses cause problems in batteries by interrupting the battery structure, often resulting in a decrease in battery capacity as the number of charge/discharge cycles increases (capacity fade) or failure of the battery to operate at all.
  • the present disclosure provides a coated positive electrode active material particle including an active material having the general chemical formula AxMyEz(X04)q and a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M includes cobalt (Co), E is located in the same structural location as A in the crystal structure and is a non-electrochemically active metal, a boron group element, or silicon (Si) or any alloys or combinations thereof, X is phosphorus (P), sulfur (S), or silicon (Si) or a combination thereof, 0 ⁇ x ⁇ l, y>0, z >0, q>0, and the relative values of x, y, z, and q are such that the general chemical formula is charge balanced.
  • A is an alkali metal or an alkaline earth metal
  • M includes cobalt (Co)
  • E is located in the same structural location as A in the crystal structure and is a non-electrochemically active metal, a boron group element, or
  • the coated positive electrode active material particle also includes a coating including AI2O3, Zrt , T1O2, ZnO, B2O3, Mg02, La202, LiF and any combinations thereof or LiM 1 P0 4 , where M 1 is Fe, Cr, Mn, Ni, V, or any alloys or combinations thereof.
  • the above coated positive electrode active material particle may be further characterized by one or more of the following additional features, which may be combined with one another or any other portion of the description in this specification, including specific examples, unless clearly mutually exclusive:
  • A may be lithium (Li);
  • M may further include cobalt (Co) in an alloy or combination with at least one other electrochemically active metal;
  • the at least one other electrochemically active material may include iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V), or titanium (Ti);
  • iii-b) M may be a combination of Co and Fe;
  • M may be a combination of Co and Cr;
  • M may be a combination of Co, Fe, and Cr;
  • iv) z may be greater than 0;
  • iv-a) E may be Si
  • iv-b) E may be a non-electrochemically active metal
  • the non-electrochemically active metal may be magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloys or combinations thereof.
  • iv-c) E may be a boron group element.
  • the boron group element may be aluminum (Al) or gallium (Ga) or a combination thereof;
  • LiM 1 P0 4 may include a carbon layer
  • the coated positive electrode active material may further include a carbon layer between the active material and the coating;
  • the carbon layer may be integrally formed with the active material
  • the coating may be between and including 0.1 wt% and 20 wt% of the coated particle;
  • the active material may be an attritor-mixed active material.
  • the present disclosure also provides a first method of coating an active material by applying a coating precursor solution to a particle of active material and heating the particle of active material with the coating precursor solution to between 300 °C and 600 °C to form a coating on the active material.
  • the active material may have the general chemical formula LixMyEz(X0 4 )q and a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located in the same structural location as A in the crystal structure and is a non- electrochemically active metal, a boron group element, or silicon (Si) or any alloys or combinations thereof, X is phosphorus (P), sulfur (S), or silicon (Si) or a combination thereof, 0 ⁇ x ⁇ l, y>0, z >0, q>0, and the relative values of x, y, z, and q are such that the general chemical formula is charge balanced and the coating precursor solution comprises a coating precursor operable to form AI2O
  • the above first method may be further characterized by one or more of the following additional features, which may be combined with one another or any other portion of the description in this specification, including specific examples, unless clearly mutually exclusive:
  • i) applying a coating precursor solution may include spray-drying the coating precursor and the particle of active material
  • i-a) spray-drying may include mixing the coating precursor solution and particles of the active material to form a spray-drying solution and spray-drying the spray-drying solution.
  • applying the coating precursor solution may include a hydrothermal method including adding particles of the active material to the coating precursor solution, maintaining the solution at a hydrothermal coating temperature between and including 70°C and 90 °C, and drying the solution.
  • the hydrothermal method may also include maintaining the solution at the hydrothermal coating temperature for between and including 10 hours and 30 hours.
  • the coating precursor solution may include an aqueous solvent
  • the coating precursor solution may include a non-aqueous solvent.
  • the coating precursor solution may include a solvent and a coating precursor solute in a solvent: solute ratio of between 99.9:0.1 and 90: 10; vi) the coating precursor may include a metal or boron salt;
  • the metal or boron salt may include an organic salt
  • heating may occur for a duration of 3-5 hours.
  • the present disclosure further provides a second method of coating an active material, the method including combining a coating precursor particle with a particle of active material to form a dry unprocessed mixture and subjecting the dry mixture to high-speed mixing at between and including 8,000 rpm and 15,000 rpm.
  • the active material may has the general chemical formula LixMyEz(X0 4 )q and a crystal structure, wherein A is an alkali metal or an alkaline earth metal, M comprises cobalt (Co), E is located in the same structural location as A in the crystal structure and is a non- electrochemically active metal, a boron group element, or silicon (Si) or any alloys or combinations thereof, X is phosphorus (P) or sulfur (S) or a combination thereof, 0 ⁇ x ⁇ l, y>0, z >0, q>0, and the relative values of x, y, z, and q are such that the general chemical formula is charge balanced and the coating precursor particle comprises LiM 1 P0 4 , where M 1 is Fe, Cr, Mn, Ni, V, or any alloys or combinations thereof.
  • the above second method may be further characterized by one or more of the following additional features, which may be combined with one another or any other portion of the description in this specification, including specific examples, unless clearly mutually exclusive:
  • high-speed mixing may occur for between and including 5 minutes and 15 minutes.
  • first and second methods may both be further characterized by one or more of the following additional features, which may be combined with one another or any other portion of the description in this specification, including specific examples, unless clearly mutually exclusive:
  • A may be lithium (Li);
  • M may further include cobalt (Co) in an alloy or combination with at least one other electrochemically active metal;
  • the at least one other electrochemically active material may include iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V), or titanium (Ti);
  • ii-b) M may be a combination of Co and Fe;
  • ii-c) M may be a combination of Co and Cr;
  • M may be a combination of Co, Fe, and Cr;
  • iii) z may be 0.
  • iii-a) E may be Si
  • iii-b) E may be a non-electrochemically active metal
  • the non-electrochemically active metal may be magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloys or combinations thereof;
  • E may be a boron group element
  • the boron group element may be aluminum (Al) or gallium (Ga) or a combination thereof;
  • X may be P.
  • iii-e) X may be S.
  • iii-f) X may be Si.
  • LiM 1 P0 4 may include a carbon layer
  • the coated particle may have a carbon layer may between the active material and the coating;
  • the carbon layer may be integrally formed with the active material
  • the coating may be between and including 0.1 wt% and 20 wt% of the coated particle;
  • the method may further include an attritor-mixing method to form the active material, the attritor-mixing method including attritor-mixing precursors of the active material to form active material precursor particles having an average size and heating the stoichiometric amounts of the active material precursors to at least a temperature for at least a duration of time to form the active material.
  • the active material precursors may include at least one hydroxide, alkali metal phosphate, non-metal phosphate, metal oxide, acetate, oxalate, or carbonate; vii-a- 1) the hydroxide may include at least one of LiOH, Co(OH) 2 Al(OH) 3 ; vii-a-2) the alkali metal phosphate may include at least one of LiEbPCri or LriElPCri;
  • the non-metal phosphate may include at least one of NEEEbPCri or (NH 4 )2HP0 4 ;
  • the metal oxide may include at least one of CnCh, CaO, MgO, SrO, AI2O3, Ga2Cb, T1O2, ZnO, SC2O3, La203 or ZrCh;
  • the acetate may include Si(OOCCH 3 ) 4 ;
  • the oxalate may include FeC20 4, NiC20 4 or CoC20 4 ;
  • the carbonate may include L12CO3, MnC0 3 , C0CO3 or NiCCb;
  • Attritor-mixing may include placing balls and the active material precursors in an attritor in a set w:w ratio;
  • Attritor-mixing may include placing a total volume of balls and active material precursors in an attritor container that is no more than 75% of a total volume of the attritor container;
  • Attritor-mixing may occur until a particle size plateau is reached vii-e) attritor-mixing may occur for no more than 10% longer than the duration at which the particle size plateau is reached;
  • Attritor-mixing may occur for a duration of time sufficient to result in a yield in an active material yield plateau
  • Attritor-mixing may occur for no more than 10% longer than a duration of time sufficient to result in a yield in an active material yield plateau;
  • Attritor-mixing may occur for a duration of time sufficient to result in an active material capacity plateau
  • Attritor-mixing may occur for no more than 10% longer than a duration of time sufficient to result in an active material capacity plateau
  • Attritor-mixing may occur for a mixing duration of time between and including 10 hours and 12 hours.
  • the active material precursor particles may have an average particle size of between and including 1 pm and 700pm;
  • the attritor-mixing method may also include filtering the active material precursor particles to remove particles over a set size;
  • A is Li, M is Co or a Co alloy or combination, and X is P, and the temperature is between and including 600°C and 800 °C;
  • heating during attritor-mixing may occur for a heating duration of time between and including 6 hours and 24 hours; vii-o) the attritor-mixing method may have a yield of between least 95% and
  • the active material may have a purity of between 95% and 99.9%.
  • the disclosure further provides an alkali metal or alkaline earth metal rechargeable battery including an electrolyte including a liquid and an alkali metal salt or alkaline earth metal salt, a negative electrode including a surface that contacts the electrolyte, the negative electrode further including a negative electrode active material, a positive electrode including a surface that contacts the electrolyte, the positive electrode further including any positive electrode active material described above or elsewhere herein or prepared according to any of the above methods or methods described elsewhere herein, an electronically insulative separator between the positive electrode and the negative electrode, and a casing surrounding the electrolyte, electrodes, and separator.
  • the above battery may be further characterized by one or more of the following additional features, which may be combined with one another or any other portion of the description in this specification, including specific examples, unless clearly mutually exclusive:
  • the battery may further include a pressure application system that applies pressure to at least a portion of the electrode surfaces contacting the electrolyte;
  • the pressure application system may include a seal internal to the battery and a pressure application structure;
  • the pressure application structure may include plates and a clamp or screw
  • the pressure application structure may include a pressure bladder
  • the battery may further include a gas relocation area
  • the pressure application structure may apply pressure to at least 90% the surfaces of the electrodes contacting the electrolyte
  • i-f) pressure applied by the pressure application structure may not vary by more than 5% between any points where the pressure is applied; i-g) the pressure applied by the pressure application structure may be between 50 psi and 90 psi;
  • the pressure applied by the pressure application structure may be between 70 psi and 75 psi;
  • the electrolyte may include an organic liquid
  • the organic liquid may include an organic carbonate
  • the organic carbonate includes ethylene carbonate (EC) with dimethyl carbonate (DMC), propylene carbonate (PC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC), or any combinations thereof;
  • EC ethylene carbonate
  • DMC dimethyl carbonate
  • PC propylene carbonate
  • DEC diethyl carbonate
  • EMC ethyl methyl carbonate
  • the electrolyte may include a lithium salt
  • the lithium salt may include LiPF 6 , LiBF 4 , lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiDFOB), and lithium trifluorosulfonylimide (LiTFSI), lithium perchlorate (LiCl04), lithium bis(fluorosulfonyl)imide (LiFSI), or any combinations thereof;
  • the electrolyte may include an ionic liquid
  • the ionic liquid may include a nitrogen (N)-based ionic liquid
  • the N-based ionic liquid may include an ammonium ionic liquid;
  • i-j-l-A-*) the ammonium ionic liquid may include A( A'-di ethyl -A-methyl -L- (2-methoxyethyl) ammonium;
  • the N-based ionic liquid may include an imidazolium ionic liquid; i-j-l-B-*) the imidazolium ionic liquid may include ethyl methyl imidazolium (EMIm), methyl propyl imidazolium, (PMIm), butyl methyl imidazolium (BMIm), or 1 -ethyl-2,3 -dimethylimidazolium, or any combinations thereof;
  • EMIm ethyl methyl imidazolium
  • PMIm methyl propyl imidazolium
  • BMIm butyl methyl imidazolium
  • the N-based ionic liquids may include a piperidinium ionic liquid; i-j-l-C-*) the piperidinium ionic liquid may include ethyl methyl piperidinium (EMPip), methyl propyl piperidinium (PMPip), or butyl methyl piperidinium (BMPip), or any combinations thereof.
  • EMPip ethyl methyl piperidinium
  • PMPip methyl propyl piperidinium
  • BMPip butyl methyl piperidinium
  • the N-based ionic liquid may include a pyrrolidinium ionic liquid; i-j-l-D-*) the pyrrolidinium ionic liquid may include ethyl methyl pyrrolidinium (EMPyr), methyl propyl pyrrolidinium (PMPyr), or butyl methyl pyrrolidinium (BMPyr), or any combinations thereof;
  • EMPyr ethyl methyl pyrrolidinium
  • PMPyr methyl propyl pyrrolidinium
  • BMPyr butyl methyl pyrrolidinium
  • the ionic liquid may include a phosphorus (P)-based ionic liquid; i-j-2-A) the P-based ionic liquid may include a phosphonium ionic liquid; i-j-2-A-*) the phosphonium ionic liquid includes PR R’ phosphonium, wherein R is butyl, hexyl, or cyclohexyl, and R’ is methyl or (CFh ⁇ CFE, or tributyl(methyl)phosphonium tosylate, or any combinations thereof;
  • the alkali metal salt my include L1F2NO4S2, L1CF2SO3, LiNS02(F3)2, LiNS02(F2CF3)2, L1C2F6NO4S2, or any combinations thereof.
  • the negative electrode active material may include metal, carbon, a lithium or sodium titanate or niobate, or a lithium or sodium alloy.
  • FIG. 1A is a schematic cross-sectional drawing of a particle of coated lithium ion positive electrode active material.
  • FIG. IB is a schematic cross-sectional drawing of a particle of coated lithium ion positive electrode active material having a carbon layer.
  • FIG. 2 is an X-ray diffraction (XRD) profile of a multiple-substituted lithium cobalt phosphate ( LiCoo.82Feo.o976Cro.o488Sio.oo976P04) positive electrode active material.
  • Typical XRD patterns of the final product with trace of impurity are marked by *.
  • FIG. 3 is a representative energy-dispersive X-ray spectroscopy (EDX) analysis of an iron (Fe), silicon (Si) and chromium (Cr)-containing positive electrode active material showing trace Si and Cr agglomeration.
  • the scale bar in all images is 10 pm.
  • FIG. 4 is a representative cross-sectional energy-dispersive X-ray spectroscopy (EDX) analysis of a Fe, Cr and Si-containing positive electrode active material showing trace Cr impurities.
  • the scale bar in the leftmost image is 10 um.
  • the scale bars in all other images is 5 pm.
  • FIG. 5A and FIG. 5B are a pair of representative scanning electron microscope (SEM) image of particles of positive electrode active material.
  • the scale bar in FIG. 5A is 20 um.
  • the scale bar in FIG. 5B image is 5 gm.
  • FIG. 6 is a flow chart of a method of attritor-mixing precursors and heating to form an active material.
  • FIG. 7 is a schematic partially cross-sectional elevation drawing of an attritor suitable for use in the present disclosure.
  • FIG. 8 is a graph showing the effect of balfprecursor w:w ratio during attritor mixing on capacity of active material formed from the attritor-mixed precursors.
  • FIG. 9A is a graph showing particle size distribution after attritor-mixing for 6 hours with an 8: 1 balfprecursor w:w ratio.
  • FIG. 9B is a graph showing the particle size distribution of the same precursor mixture as in FIG. 9 A after attritor-mixing for 12 hours with an 8: 1 balfprecursor w:w ratio.
  • FIG. 10A is a flow chart of a coating method for forming a coated particle.
  • FIG. 10B is a flow chart of an alternative coating method for forming a coated particle.
  • FIG. 11 is a battery including a coated active material according to the present disclosure.
  • FIG. 12 is a schematic cross-sectional drawing of a battery according to the present disclosure.
  • FIG. 13 is a schematic drawing of a bottom portion of a battery according to the present disclosure.
  • FIG. 14 is a photograph of a side of a screw-pressure battery according to the present disclosure.
  • FIG. 15 is photograph of a side of an air-pressure battery according to the present disclosure.
  • FIG. 16 is a graph showing cycling stability of batteries containing coated positive electrode active materials according to the present disclosure and a comparative uncoated positive electrode active material.
  • FIG. 17 is a scanning electron microscope (SEM) image of a l0wt% c- LiFePCri-coated LiCoo.82Feo.o976Cro.o488Sio.oo976P04 positive electrode active material. LiFePCri and LiCoo.82Feo.o976Cro.o488Sio.oo976P04 particles are labeled.
  • FIG. 18 is a graph of discharge capacity for LiF-coated LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 at different wt% of LiF.
  • FIG. 19 is an XRD profile of a LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 active material after 6 hours or 12 hours of attritor-mixing with a 6: 1 ball precursor w:w ratio.
  • FIG. 20 is an XRD profile of a LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 active material after 12 hours of attritor-mixing with an 8: 1 ball precursor w:w ratio.
  • FIG. 21 is an XRD profile of a LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 active material after 12 hours of attritor-mixing a with a 10: 1 ball precursor w:w ratio.
  • FIG. 22 is an XRD profile of a LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 active material after 12 hours of attritor-mixing a with a 12: 1 ball precursor w:w ratio.
  • FIG. 23 is an XRD profile of a LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 active material after 12 hours of attritor-mixing a with a 14: 1 ball precursor w:w ratio.
  • the disclosure relates to a coated lithium ion rechargeable battery positive electrode active material, methods of manufacturing such a material, and lithium ion rechargeable batteries containing such a material.
  • the coating reduces exposure of the positive electrode active material to the electrolyte and thereby reduces generation of gasses in the battery.
  • a coated particle 2 of lithium ion rechargeable battery positive electrode active material 4 has a coating 6.
  • a carbon layer 8 is present between the active material 4 and the coating 6.
  • the active material 4 may have the general formula AxMyEzPCri and a crystal structure, where 0 ⁇ x ⁇ l, y>0, and z>0, A is an alkali metal or an alkaline earth metal, M is cobalt (Co) alone or in an alloy or combination with another electrochemically active metal and E, when z>0, is located in the same structural location as A in the crystal structure and is a non-electrochemically active metal or a boron group element (Group 13, Group III), or Si, or any combinations or alloys thereof.
  • the alkali metal (Group 1, Group I metal) in the active material may be lithium (Li) sodium (Na), or potassium (K).
  • the alkaline earth metal (Group 2, Group IIA metal) may be magnesium (Mg) or calcium (Ca).
  • the alkali metal or alkaline earth metal may be present as a mobile cation or able to form a mobile cation, such as lithium ion (Li + ), sodium ion (Na + ), potassium ion (K + ), magnesium ion (Mg 2+ ), or calcium ion (Ca 2+ ).
  • the electrochemically active metal is most commonly a transition metal, such as a Group 4-12 (also referred to as Groups IVB-VIII, IB and IIB) metal.
  • Particularly useful transition metals include those that readily exist in more than one valence state. Examples include iron (Fe), chromium (Cr), manganese (Mn), nickel (Ni), vanadium (V), and titanium (Ti).
  • non-electrochemically active metals may affect the electrical or electrochemical properties of the active material.
  • non-electrochemically active metals or boron group element or silicon (Si) may change the operating voltage of the active material, or increase the electronic conductivity of active material particles, or improve the cycle life or coulombic efficiency of an electrochemical cell containing the active material.
  • Suitable non-electrochemically active metals include alkaline earth metals (Group 2, Group II metals) such as magnesium (Mg), calcium (Ca) or strontium (Sr), or zinc (Zn), scandium (Sc), or lanthanum (La), or any alloys or combinations thereof.
  • Suitable boron group elements include aluminum (Al) or gallium (Ga) and combinations thereof.
  • the alkali metal or alkaline earth metal, Co and electrochemically active metal, non-electrochemically active metal or boron group element or Si, and phosphate are present in relative amounts so that the overall active material compound or mixture of compounds is charge balanced.
  • Example active materials include LiCoo.9Feo.1PO4, Lio.95Coo.85Feo.iCro.o5P0 4 , Lio.93Coo.84Feo.iCro.o5Sio.oiP04, and LiCo 0.82 Fe 0.0976 Cr0. 0488 Si 0.00976 PO4.
  • the active material compound or mixture of compounds are primarily present in a crystalline, as opposed to an amorphous form, which may be confirmed via XRD.
  • the active material may have an olivine crystal structure similar to that of lithium cobalt phosphate (L1C0PO4) regardless of whether other electrochemically active metals or non-electrochemically active metal or boron group element or Si are present.
  • An example of an XRD pattern sufficient to confirm crystal structure is presented in FIG. 2. If a carbon layer 8 is present, it may be observed via EDX or SEM. Such a carbon layer 8 may be integrally formed on at least a portion of the exterior surface of a particle of active material 4.
  • portions of the carbon layer that contact the exterior surface of the particle of active material 4 may be covalently bonded to the active material 4.
  • the carbon layer 8 may be at least 80% elemental carbon (C).
  • the carbon layer 8 may be between and including 0.01 wt% to 10 wt% of the total coated particle 2.
  • the active material 4 alone or with an carbon layer 8 will have a particle size of between and including 1 pm and 999 pm, 1 pm and 500 pm, 1 pm and 100 pm, 10 pm and 999 pm, 10 pm and 500 pm, or 10 pm and 100 pm.
  • the coating 6 may include an electrochemically inactive material, such as a metal or boron oxide, particularly AI2O3, ZrCh, T1O2, ZnO, B2O3, MgCh, La202, or a metal non-oxide, particularly a metal fluoride, such as LiF, and any combinations thereof.
  • the coating 6 may also include an electrochemically active material, such as a non-cobalt-containing lithium metal phosphate material, particularly LiM 1 P0 4 , where M 1 is Fe, Cr, Mn, Ni, V, or any alloys or combinations thereof, such as LiFePCri.
  • the electrochemically active coating material may have a carbon layer similar to the carbon layer 8 that may be present on the active material 4.
  • the relative amount of coating 6 to overall size of coated particle 2 may vary depending on the coating used. In addition, there is generally a trade-off between specific capacity of a battery containing coated particle 2 and the cycle life of such a battery. Non-electrochemically active coatings 6 tend to better cover the active material 4 and reduce its reaction with the electrolyte, increasing cycle life, but such coatings contribute non-electrochemically active weight to the particle decreasing specific capacity of the battery. Electrochemically active coatings 6 may also participate in an electrochemical reaction and increase the specific capacity of a battery containing coated particle 2, depending on the voltage range, leading to better performance such as high-rate properties of the battery. The electrochemically active coatings may reduce the side reaction between active material 4 and electrolyte as well, further increasing cycle life.
  • coating 6 may be between and including 0.1 wt% and 20 wt%, 0.1 wt% and 10 wt%, 0.1 wt% and 5 wt%, 0.5 wt% and 20 wt%, 0.5 wt% and 10 wt%, 0.5 wt% and 5 wt%; 1 wt% and 20 wt%, 1 wt% and 10 wt%, or 1 wt% and 5 wt% of the total coated particle 2.
  • active materials 4 as described above may be coated, active materials 4 produced using an attritor-mixing method may be particularly useful.
  • An attritor-mixing method may be usable to produce commercial-level quantities of active material with no or low levels of impurities.
  • Active materials produced using attritor-mixing methods may have a purity of at least 95%, at least 98%, at least 99%, or a purity in a range between and including any combinations of these values, as measured by XRD refinement, an example of which is provided in FIG. 2.
  • Impurities are typically in the form of unreacted precursors or precursors that have reacted to form compounds other than the active material and crystalline impurities in amounts of 1% or greater of a given crystalline impurity compound may be detected using XRD.
  • Non-crystalline impurities and impurities in amounts of less than 1% may be detected using EDX, examples of which are provided in FIG. 3 and FIG. 4.
  • Active materials formed by attritor-mixing when used in an electrochemical cell, may exhibit stable capacity, with a capacity fade of 50% or less, 40% or less, 20% or less, 10% or less, 5% or less, 1% or less, or a range between and including any combinations of these values over 110 cycles at C/2 as compared to the capacity at the tenth cycle at C/2.
  • Active materials 4 formed by attritor mixing herein may be in the form of particles that are, on average over the batch of particles, excluding agglomerates, no longer than 1 nm, 10 nm, 50 nm, 100 nm, 500 nm, or 999 nm, or any range between and including any combination of these values. Such particles are referred to as nanoparticles. Active materials formed using attritor-mixing methods may be in the form of particles that are, on average over the batch of particles excluding agglomerates, no longer than 1 pm, 10 pm, 50 pm, 100 pm, 500 pm, or 999 pm, or any range between and including any combination of these values. Such particles are referred to as microparticles.
  • Active materials particle may form agglomerates, in which case any agglomerate is excluded from the average particle size discussed above.
  • the agglomerate may itself be a nanoparticle or a microparticle.
  • the agglomerate may be a microparticle composed of nanoparticles of active material.
  • Particle and agglomerate size may be assessed using scanning electron microscopy (SEM), an example of which is shown in FIGs. 5A and 5B.
  • SEM scanning electron microscopy
  • Suitable precursors for use in manufacturing the active material will depend on the specific active material to be produced. Typically the precursors are in solid form, as the methods disclosed herein are solid state manufacturing methods. Wet precursors or those available as hydrates or containing substantial humidity may be dried prior to use in the methods of the present disclosure.
  • Common precursors include metal hydroxides, such as LiOH, Co(OH) 2 and Al(OH) 3 , alkali metal phosphates, such as L1H2PO4 or LriHPCri, alkaline earth metal phosphates, non-metal phosphates, such as NH4H2PO4, (ME ⁇ HPCri, metal oxides, such as CnCh, CaO, MgO, SrO, AI2O3, Ga 2 03, T1O2, ZnO, SC2O3, La 2 03 or ZrCk, acetates, such as Si(OOCCH3)4, and oxalates, such as FeCiCri, N1C2O4 or C0C2O4 (which are often stored as a hydrate, which may be dried before use in the present methods), or carbonates, such as L12CO3, MnCCh, C0CO3 or NiCCh.
  • metal hydroxides such as LiOH, Co(OH) 2 and Al(OH) 3
  • carbon layer precursors may also be included in the attritor-mixing methods described herein.
  • Suitable carbon layer precursors include elemental carbon or carbon-containing materials, such as polymers, that are broken down to form a carbon coating.
  • Active materials including those described above, may be manufactured from precursors, including those described above using solid-state attritor-mixing methods that generally include attritor-mixing of at least non-coating precursors, followed by heating the mixture.
  • Attritor-mixing methods may be used to form at least 1 kg, at least 2 kg, at least 3kg, at least 5 kg, at least 10 kg, at least 25 kg, at least 50 kg, at least 100 kg active material, or an amount between and including any two of these recited amounts (e.g . between and including 1 kg and 2 kg, between and including 1 kg and 3 kg, between and including 1 kg and 5 kg, between and including 1 kg and lOkg, between 1 kg and 50 kg, between and including 1 kg and 50 kg, between and including 1 kg and 100 kg, between 25 kg and 50 kg) per batch.
  • Attritor-mixing methods prior to particle size filtering, may have a yield of at least 80%, at least 85%, or at least 90%, at least 95%, or at least 99%, at least 99.9% or an amount between and including any two of these recited amounts per batch. Yield is measured prior to particle size filtering to exclude effects directly to the particle size selected, rather than the active-particle forming reaction and method.
  • the carbon layer precursor may be added prior to attritor-mixing, after attritor-mixing, but before heating, or after heating, depending largely on the carbon layer to be formed. Carbon layer precursors will typically be added prior to attritor-mixing.
  • One of ordinary skill in the art using the teachings of the present disclosure and, optionally, through conducting a series of simple experiments in which different carbon layer precursors are added at different stages of the methods, also optionally in different relative amounts, will be able to readily determine how to incorporate carbon layer formation steps into the methods disclosed herein.
  • the present disclosure provides an attritor-mixing method 110 for manufacturing an active material.
  • step 120 wet or hydrate precursors are dried.
  • step 130 precursors that are too large to fit in the attritor chamber or to be milled by the attritor are cut to a sufficiently small size. Steps 120 and 130 may be performed in any order.
  • step 140 stoichiometric amounts of precursors that will be attritor-mixed are placed in the chamber of the attritor and attritor-mixed to form precursor particles. Although, typically, all active material precursors will be attritor-mixed, some precursors may be added after attritor-mixing.
  • the attritor used in step 140 may be any suitable attritor.
  • An attritor is a mixing apparatus having a container, an arm extending from the exterior of the container through a lid of the container and into the interior of the container, and at least one and typically a plurality of paddles in the interior of the container coupled to the arm so that when the arm rotates in response to a rotational force applied outside of the container, the paddles rotate within the container. If a material is in the container, then it will be impacted by the paddles and its size will be reduced by a combination of friction and impact with the paddles or other materials in the container.
  • Attritor 200 includes a container 210, which has a lid 220. Attritor 200 also includes couple 230, which attaches to an external source of rotational force, such as a motor. Couple 230 is located at a first end of an arm 240, which is located exterior to the container 210. The arm 240 passes through a guide 250 mounted on the lid 220 and through the lid 220 into the interior of the container 210. At least one and, as depicted, typically a plurality of paddles 260 are located in the interior of the container 210 and are coupled to a portion of the arm 240 also in the interior of the container 210.
  • the attritor 200 also includes a plurality of balls 270 (depicted as only two balls for simplicity).
  • the balls are also impacted by the paddles and/or the material and help reduce the size of the precursors.
  • Balls used in step 140 may be of any size suitable to reduce the precursors to a set particle size within a set time. 19 mm diameter balls may work particularly well, and 12.7 mm diameter balls may also be suitable.
  • the balls may be made of any materials that do not react with the precursors to a degree that reduces yield below 80% or produces impurities in an amount of more than 5% total impurities. Suitable materials for the balls include steel, zirconium, or tungsten. The balls may have an interior made of a different material with an exterior coating of a suitable material.
  • the balls contribute to reduction of precursor size, they also occupy volume in the attritor chamber that might otherwise be occupied by precursors. Accordingly, the proportion of balls to total precursors (w:w) may be limited to the smallest ratio that still allows an active material having the selected particle size or other set property to result from the overall method 110.
  • FIG. 8 shows a comparison of capacity and ball Total precursors (w:w) such as might be used to select the proportion.
  • the particle size of precursors after attritor-mixing is typically 10 pm or less, 50 pm or less, 100 pm or less, 500 pm or less, 600 pm or less, or 750 pm or less and any ranges between and including and combinations of these values, (e.g. between and including 1 pm and 10 pm, between and including 1 gm and 50gm, between and including 10 gm and 50 gm, between and including 1 gm and 600 gm).
  • An appropriate w:w ratio may vary depending on the precursors used, the size of the precursors prior to attritor mixing, the size of the balls, and the attritor used, but one of ordinary skill in the art, using the teachings of this disclosure, may readily determine the appropriate balkprecursor ratio by simply varying these parameters until an acceptable precursor particle size or other set property such as capacity is obtained.
  • the total volume of balls and precursors in the attritor should not have a volume exceeding that specified by the attritor manufacturer. Typically, the total volume of balls and precursors is no more than 75% of the total volume of the attritor container, to allow sufficient room for the balls and precursors to move during mixing.
  • balkprecursor ratio for any given set of precursors (at a selected pre-attritor-mixing size), balkprecursor ratio, ball size, and attritor, there will be a reduction of average precursor particle size over time during attritor-mixing until a particle size plateau is reached. Once the particle size plateau is reached, any additional duration of attritor- mixing will not further reduce the average precursor particle size by more than 10%, as compared to the average precursor particle size at the duration of time when the particle size plateau is reached.
  • the plateau may also readily be determined by one of ordinary skill in the art, using the teachings of this disclosure.
  • step 140 may be continued after the particle size plateau is reached, typically step 140 will last only until the particle size plateau is reached, no more than 10% longer than the duration at which the particle size plateau is reached, or a duration between and including these two times. Common mixing times to reach plateau include 10-12 hours. Examples particle size distributions based on mixing duration that may be used to determine when plateau is reached are provided in FIG. 9A and FIG. 9B
  • Properties, such as yield or active material capacity, determined at least in part by particle size may also exhibit a plateau with respect to attritor-mixing duration and attritor-mixing duration may be set based on such an alternative plateau such that the attritor-mixing duration is only until the plateau is reached, no more than 10% longer than the duration at which the plateau is reached, or a duration between and including these two times.
  • the attritor may further contain a cooling system, such as an exterior cooling system or a cooling system located within the container, lid, arm, paddles, or any combinations of these.
  • the cooling system may keep the temperature below a set temperature during step 140.
  • the precursors may be cooled prior to attritor-mixing in step 140.
  • the attritor may include a thermometer to allow a ready determination of whether the precursors exceeded a set temperature during step 140, in which case they may be discarded or subjected to a quality control process.
  • step 140 After attritor-mixing in step 140, a stoichiometric amount of any precursors not subjected to attritor-mixing is added to the attritor-mixed precursor particles.
  • step 150 the attritor-mixed precursor particles are filtered to exclude particles above a set size, typically lOpm, 50 pm, or 100 pm.
  • the filtered precursors are then heated in step 160 for a duration of time to undergo a chemical reaction and form the active material.
  • the temperature to which the precursors are heated may vary depending on the precursors and active material.
  • the heating in step 50 may be a simple heating process, in which the precursors are heated to a set temperature and maintained at that temperature for the duration of time.
  • the heating in step 160 may also be a more complicated, stepped process, in which the precursors are heated to one or more temperatures for one or more times.
  • the rate at which heating in step 160 occurs may also be controlled to occur at a particular degrees per minute and step 160 may even include cooling followed by heating in the overall heating process.
  • the maximum temperature in heating step 50 may be at least 600 °C, particularly between and including 600 °C and 800 °C, and may be attained through temperature increases of between 1 °C/min and 10 °C/min.
  • the heating step may last for at least 6 hours, at least 8 hours, at least 10 hours, or at least 12 hours, at least 18 hours, least 24 hours and ranges between and including and combinations of these values particularly between and including 6 hours and 24 hours.
  • Heating may occur under a reducing or inert atmosphere, such as a nitrogen (N2) atmosphere. Heating may be preceded by a purge at room temperature (25 °C) under a reducing or inert atmosphere, such as a nitrogen atmosphere, for 1-4 hours, typically 3 hours.
  • step 170 the material is cooled. Cooling may be a simple, passive cooling process, an active cooling process, or a stepped process. The material may be maintained a particular temperatures for a duration of time. The rate at which cooling occurs may also be controlled to occur at a particular degrees per minute and step 170 may even include heating followed by cooling in the overall cooling process.
  • the active material is present by the end of the cooling process 170. Depending on the precursors and active material, the active material may often be present even at the end of heating in step 160. In some methods 110, the heating process 160 and the cooling process 170 may overlap to form one continuous heating/cooling process.
  • the active material is filtered to exclude particles above a set size. For example, 25 pm, 35 pm, 38 pm, 40 pm, 50pm, or 100 pm.
  • Attritor-mixing methods may practice only steps 140 and 160 (or step 160/170 in place of step 160 if heating and cooling form one continuous heating/cooling process).
  • the other steps described in connection with method 110 are each independently omittable.
  • All or part of the steps of method 110 may be carried out in conditions that limit humidity.
  • all or part of the steps of method 110 may be carried out in a dry room or in a water-exclusive atmosphere, such as an inert, hydrogen, or nitrogen atmosphere (although, for most active materials, this degree of precaution is not needed), or at ambient humidity of less than 25% or less than 10%.
  • any active material 4, whether formed by attritor-mixing method 110 or any other method, may have coating 6 applied using wet coating method l90a illustrated in FIG. 10A.
  • coating method l90a in step 191, a coating precursor solution is formed.
  • the solvent may be an aqueous solution or a non-aqueous solution.
  • an alcohol such as ethanol, may used as the solvent.
  • the solvent: solute ratio may vary from 99.9:0.1 to 90: 10.
  • the coating precursor may include particles of the coating material that are smaller than the particle of active material 4.
  • the coating precursor may include particles of LiFePCri having a carbon layer (c-LiFePCri). If the coating precursor particles may have a longest average dimension no more than 0.8% or 1% of the longest average dimension of the particles of active material 4 or particles of active material 4 with carbon layer 8.
  • the coating precursor may also include a compound that forms the coating 6 after heating.
  • the coating precursor may be a metal or boron salt that will form part of the coating 6.
  • the coating precursor may be an organic salt, such as C9H21O3AI, or an inorganic salt, such as Al(N03)3 if the coating 6 will include AI2O3. If an organic compound precursor is used, the carbon and hydrogen components burn away in the heating steps that follow.
  • step 192 the coating precursor solution is applied to particles of active material 4 or active material 4 with carbon layer 8.
  • the precursor may be applied by a spray-drying method in which particles of the active material are added to the coating precursor solution to form a spray drying solution.
  • the spray-drying solution may be mixed prior to spray-drying, for example at a temperature between and including 50 °C to 70 °C or 55 °C and 65 °C. Mixing may occur for between and including 2 and 6 hours or 3 and 4 hours.
  • the spray- drying solution may be stirred while mixing. After the spray-drying solution is mixed, it may be spray-dried, for example at a temperature of between and including 90 °C and 110 °C, or at least 100 °C for an aqueous solution, or another temperature based on the evaporation temperature of the solvent for a non-aqueous solution. Spray-drying may take place under a nitrogen (N2) atmosphere.
  • N2 nitrogen
  • the particles may simply be added to the precursor solution to form a hydrothermal coating solutions which may be maintained at a hydrothermal coating temperature prior to heating.
  • the hydrothermal coating temperature may be between and including 70°C and 90 °C or between 75 °C and 85 °C.
  • the hydrothermal coating solution may be maintained at the hydrothermal coating temperature for between and including 10 hours and 30 hours, 15 hours and 25 hours, or 18 hours and 22 hours.
  • the hydrothermal coating solution may be stirred during all or part of this time.
  • the hydrothermal coating solution may then be dried and the precipitate heated, or drying may occur during heating.
  • the particles with coating precursor are heated to a temperature of between and including 300 °C and 600 °C, 300 °C and 500 °C, 300 °C and 450 °C, 350 °C and 600 °C, 350 °C and 500 °C, 350 °C and 450 °C, 400 °C and 600 °C, 400 °C and 500 °C, or 400 °C and 450 °C, particularly 400 °C.
  • Heating lasts for between and including 3 and 5 hours, particularly 4 hours.
  • the process is generally not sensitive to the rate at which temperature is increased during heating, but the rate may typically be between 1 °C/min and 10 °C/min. Heating may occur under a reducing or inert atmosphere, such as a nitrogen (N2) atmosphere.
  • N2 nitrogen
  • coated particles 2 are cooled, typically through passive cooling.
  • any active material 4, whether formed by attritor-mixing method 110 or any other method, may also have coating 6 applied using dry coating method l90b illustrated in FIG. 10B.
  • the coating precursor includes particles of the coating material that are smaller than the particle of active material 4.
  • the coating precursor may include particles of LiFePCri having a carbon layer (c-LiFePCri). If the coating precursor particles may have a longest average dimension no more than 0.8% or 1% of the longest average dimension of the particles of active material 4 or particles of active material 4 with carbon layer 8.
  • step 195 dry particles of the active material and the coating precursor are combined to form an unprocessed mixture.
  • step 196 the unprocessed mixture is subjected to high-speed mixing to produce coated particle 2.
  • High-speed mixing is typically mixing at between and including 8,000 rpm and 15,000 rpm, or between and including 8,000 rpm and 10,000 rpm, such as mixing at 8,000 rpm, 9,000 rpm, or 10,000 rpm.
  • Typical mixing times are between and including 5 minutes and 15 minutes, 8 minutes and 12 minutes, and 9 minutes and 11 minutes, or 10 minutes.
  • All or part of the steps of methods l90a and l90b may be carried out in conditions that limit humidity.
  • all or part of the steps of methods l90a and l90b may be carried out in a dry room or in a water-exclusive atmosphere, such as an inert, hydrogen, or nitrogen atmosphere (although, for most active materials, this degree of precaution is not needed), or at ambient humidity of less than 25% or less than 10%.
  • Coated active materials produced using the above method may be used in the positive electrodes of batteries, such as battery illustrated in FIG. 11.
  • the battery 50 includes negative electrode (anode) 55, positive electrode (cathode) 60, and organic electrolyte 65 and a porous, electronically insulating separator (located in electrolyte 65) that permits ionic, but not electronic conductivity within the battery (not shown) disposed in the organic liquid electrolyte between the negative electrode 55 and the positive electrode 60.
  • the negative electrode 55 includes an active material. Suitable negative electrode active materials include lithium metal, carbon, such as graphite, lithium or sodium titanates or niobates, and lithium or sodium alloys.
  • the negative electrode may further include binders, conductive additives, and a current collector.
  • the positive electrode 60 includes a coated active material as disclosed herein.
  • the positive electrode may further include any of fluorinated carbonates, sulfolane based organic solvents, a binder, conductive additives, and a current collector.
  • the electrolyte 65 may include an organic liquid, such as an organic carbonate, particularly organic carbonates, in particular, ethylene carbonate (EC) with dimethyl carbonate (DMC), propylene carbonate (PC), diethyl carbonate (DEC), or ethyl methyl carbonate (EMC), and any combinations thereof.
  • organic carbonate particularly organic carbonates, in particular, ethylene carbonate (EC) with dimethyl carbonate (DMC), propylene carbonate (PC), diethyl carbonate (DEC), or ethyl methyl carbonate (EMC), and any combinations thereof.
  • the electrolyte 65 may include a lithium salt suitable for use with an organic liquid, such as LiPF 6 , LiBF 4 , lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiDFOB), and lithium trifluorosulfonylimide (LiTFSI), lithium perchlorate (LiClCM), lithium bis(fluorosulfonyl)imide (LiFSI) and any combinations thereof.
  • LiPF 6 LiBF 4
  • LiBOB lithium bisoxalato borate
  • LiDFOB lithium difluorooxalato borate
  • LiTFSI lithium trifluorosulfonylimide
  • LiClCM lithium perchlorate
  • LiFSI lithium bis(fluorosulfonyl)imide
  • Suitable ionic liquids include cationic components that may include nitrogen (N)-based ionic liquids.
  • N-based ionic liquids include ammonium ionic liquids, such as A( A-di ethyl -A'-methyl -AA(2-methoxyethyl ) ammonium.
  • N-based ionic liquids include imidazolium ionic liquids, such as ethyl methyl imidazolium (EMIm), methyl propyl imidazolium, (PMIm), butyl methyl imidazolium (BMIm), and 1 -ethyl-2,3 - dimethylimidazolium.
  • EMIm ethyl methyl imidazolium
  • PMIm methyl propyl imidazolium
  • BMIm butyl methyl imidazolium
  • N-based ionic liquids further include piperidinium ionic liquids, such as ethyl methyl piperidinium (EMPip), methyl propyl piperidinium (PMPip), and butyl methyl piperidinium (BMPip).
  • N-based ionic liquids additionally include pyrrolidinium ionic liquids, such as ethyl methyl pyrrolidinium (EMPyr), methyl propyl pyrrolidinium (PMPyr), butyl methyl pyrrolidinium (BMPyr).
  • Suitable cationic components of ionic liquids also include phosphorus (P)- based ionic liquids.
  • P-based ionic liquids include phosphonium ionic liquids, such as PR.3R’ phosphonium, where R is butyl, hexyl, or cyclohexyl, and R’ is methyl or (03 ⁇ 4) ⁇ 3 q3 ⁇ 4, or tributyl(methyl)phosphonium tosylate.
  • Any cationic components of ionic liquids in any of those described above, may be combined in any combinations in batteries of the present disclosure.
  • Ionic liquids may also include anionic components, in the form of other ionic liquids, such as bis(fluorsulfonyl)imide-based (FSI) ionic liquids including l-ethyl-3- methylimidazolium-bis(fluorsulfonyl)imide (EMI-FSI) and N-methyl-N- propylpyrrolidinium- bis(fluorsulfonyl)imide (Pyl3-FSI), bis(trifluoromethane)sulfonimide (TFSI), and (bis(pentafluoroethanesulfonyl)imide) (BETI).
  • Anionic components of the ionic liquids may also include BF 4 orPF 6.
  • Suitable lithium salts for use with ionic liquids include L1F2NO4S2, L1CF2SO3, LiNS02(F 3 )2, LiNS02(F2CF 3 )2, or L1C2F6NO4S2, or any combinations thereof.
  • many salts increase the viscosity of the ionic liquid such that the electrolyte effectively loses ionic conductivity and the battery does not function well. This effect may increase as salt concentration increases.
  • Some salts, such as the commonly used LiPF 6 simply will not function as an electrolyte in an ionic liquid.
  • the electrolyte may further include any of a number of co-solvents in any combinations.
  • Suitable co-solvents include fluorinated carbonates (FEMC), fluorinated ethers, such as CF3CH2OCF2CHF2, nitriles, such as succinonitrile or adiponitrile, or sulfolane.
  • the electrolyte may also include any of a number of additives in any combinations. Suitable additives include trimethyl silyl propanoic acid (TMSP), trimethyl silyl phosphite (TMSPi), trimethyl silyl boric acid (TMSB), trimethylboroxine, trimethoxyboroxine, or propane sultone.
  • TMSP trimethyl silyl propanoic acid
  • TMSPi trimethyl silyl phosphite
  • TMSB trimethyl silyl boric acid
  • the battery 55 may have particular structures to help control the formation of gasses or to minimize the effects of any gasses that do form.
  • the battery 55 may apply a pressure to at least a portion of the surfaces of the electrodes contacting the electrolyte. This pressure is applied over 100% of the surfaces of the electrodes contacting the electrolyte, or over at least 90%, at least 95%, or at least 98% of the surfaces of the electrodes contacting the electrolyte. The pressure is sufficient to prevent or decrease the formation of gas in the battery, or to cause gas that is formed to move to an area of the battery not between the surfaces of the electrodes contacting the electrolyte.
  • batteries according to the present disclosure may apply a pressure to the surfaces of the electrodes that is uniform and does not vary by more than 5% between any points where pressure is applied.
  • the pressure may be at least 50 psi, at least 60 psi, at least 70 psi, at least 75 psi at least 80 psi, at least 90 psi, and any range between and including any of the foregoing (e.g. between and including 70 psi and 75 psi).
  • an alkali metal or alkaline earth metal rechargeable battery 50 as described herein may further include a casing 70 sufficient to house and contain the electrodes 55, 60, the electrolyte 65 and the separator, and contacts 75 that, when connected via an electronically conductive connector, allow electric current to flow between the negative electrode 55 and the positive electrode 60.
  • the alkali metal or alkaline earth metal rechargeable battery 50 may further include a pressure application system that applies pressure to at least a portion of the surfaces of the electrodes 55 and 60 contacting the electrolyte 65.
  • Pressure application systems may include internal seals along with a pressure application structure, such as plates (often the casing 70) and clamps, screws, pressure bladders, or other such structures that apply pressure to the plates or to the battery casing to maintain pressure within the battery.
  • Pressure application systems may maintain pressure in a sealed portion of the battery, which likely inhibits the formation of gasses, but does not cause gasses to migrate once formed.
  • Some batteries 50 may include a gas relocation area, to which the pressure application system tends to direct gasses once formed.
  • Seals may be formed from any material that is not reactive with the electrolyte, negative electrode, positive electrode, or other battery components it contacts. Although the some seal materials may exhibit some minimal reactivity, the material may be considered not reactive if its reactivity is sufficiently low to avoid seal failure, in an average battery having a given design, over a set number of cycles, such as at least 100 cycles, at least 200 cycles, at least 500 cycles, at least 2000 cycles, at least 5000 cycles, at least 10,000 cycles, or a range between and including any combinations of these values, when cycled at C/2.
  • pressure application systems may apply pressure constantly once assembled.
  • Other pressure application systems may be adaptable to apply pressure on at set times, such as shortly prior to or during operation of the battery or both.
  • FIGs. 12-15 provide some specific pressure application systems, one of ordinary skill in the art, using the teachings of this disclosure, may design other pressure application systems.
  • FIGs. 12-15 illustrate pressure application systems in use on a single pouch-type cell, a pressure application system may be used to apply pressure to multiple cells and cells of any format.
  • FIGs. 12-15 illustrate pressure applications systems in use on flat cells, they may be used on curved, bent, or other non-planar cell formats.
  • the pressure application system includes ring seals 80 and screws 85.
  • This type of pressure application system seals a portion of the alkali metal or alkaline earth metal rechargeable battery 50 in which the electrodes 55 and 60 contact the electrolyte 65.
  • the screws 85 apply pressure to the casing 70, which is in the form of rigid plates.
  • the casing 40 transfers the pressure to the portion of the battery 50 inside the ring seals 80, which are located in a groove 90 such that there is pressure where the electrodes 55 and 60 contact the electrolyte 65 inside the ring seals 80.
  • the pressure application system includes air bladder 95, which may be inflated to a set pressure that is transferred to the casing 70.
  • this pressure application system does not contain any seals and will force and gasses that do form to gas relocation areas 100, particularly when pressure is newly applied to the casing 70. Accordingly, this pressure application system is particularly well-adapted to apply pressure shortly before or during battery use or both.
  • air bladder 95 may be inflated with any other fluid, such as another gas or a liquid.
  • the fluid in air bladder 95 may be selected, for example, to provide insulative or heat conduction properties.
  • batteries 50 of the present disclosure may attain a constant pressure on the electrodes 55 and 60 in contact with the electrolyte 65 simply by pressurizing the electrolyte 65 when it is added to the battery, then sealing the casing 70 in a manner that retains pressure.
  • Batteries containing coated active materials disclosed herein can be used in many applications. For example, they may be standard cell format batteries, such as coin cells, jelly rolls, or particularly prismatic cells. Batteries disclosed herein may be used in portable consumer electronics, such as laptops, phones, notebooks, handheld gaming systems, electronic toys, watches, and fitness trackers. Batteries disclosed herein may also be used in medical devices, such as defibrillators, heart monitors, fetal monitors, and medical carts. Batteries disclosed herein may be used in vehicles, such as cars, light trucks, heavy trucks, vans, motorcycles, mopeds, battery-assisted bicycles, scooters, boats and ships, piloted aircraft, drone aircraft, military land transports, and radio-controlled vehicles. Batteries disclosed herein may also be used in grid storage or large scale energy supply applications, such as large grid storage units or portable energy supply containers. Batteries disclosed herein may be used in tools, such as handheld power tools.
  • Batteries disclosed herein may be connected in series or in parallel and may be used in connection with control or monitoring equipment, such as voltage, charge, or temperature monitors, fire suppression equipment, and computers programmed to control battery usage or trigger alerts or safety measures if battery conditions may be unsafe.
  • control or monitoring equipment such as voltage, charge, or temperature monitors, fire suppression equipment, and computers programmed to control battery usage or trigger alerts or safety measures if battery conditions may be unsafe.
  • Example 1 lwt% AI2O3 coating on LiCoo.82Feo.o976Cro.o488Sio.oo976P04 by hydrothermal method
  • Example 2 lwt% A1203 coating on LiCoo.82Feo.o976Cro.o488Sio.oo976P04 by spray dray method
  • Coin-type half cells were prepared using 1 wt% positive electrode active material from Examples 1 and 2 or uncoated LiCoo.82Feo.o97 6 Cro.o488Sio.oo97 6 P04 as a comparison. Cycling stability results are presented in FIG. 16. All coated materials showed improved cycling stability as compared to the uncoated material.
  • Example 4 10wt% c-LiFeP04 coating on LiCoo.82Feo.o976Cro.o48sSio.oo976P04 by high speed dry mixing method
  • FIG. 17 is a representative SEM image of the 10 wt% c-LiFePCri-coated LiCoo.82Feo.o976Cro.o488Sio.oo976P04 obtained.
  • Example 5 4wt% LiF coating on LiCoo.82Feo.o976Cro.o488Sio.oo976P04 by hydrothermal method with continued stirring
  • LiF and 6.4311 g LiCoo.82Feo.o976Cro.o488Sio.oo976P04 were mixed in 267 ml deionized water for 1 hour before transferring into a 400 ml quartz autoclave and maintained at 200°C with continued stirring for 15 hours. After cooling, the precipitate was centrifuged and washed three times with 150 ml deionized water and then washed and centrifuged in 150 ml ethanol. The residual powders were air dried at 80°C in air. The same procedure was repeated with different percentages of LiF from lwt% to 4wt%. FIG. 18 shows that the discharge capacity increased with increasing LiF up to 4 wt%. Similar plateaus are expected with other coatings.
  • Attri tor-mixed precursors were transferred to an oven then heated to 700 °C for 12 hours under N2 and naturally cooled in the oven. After heat treatment, about 1.1 kg of final product was obtained and then filtered through a 38 pm sieve. XRD analysis of the resulting material is presented in FIG. 20. The XRD data confirm that active material having the same structure as LiCoPCri was produced.
  • Example 8 Attritor-Mixed LiCoo.82Feo.o976Cro.o488Sio.oo976P04 (10: 1 ratio)
  • Attritor-mixed precursors were transferred to an oven then heated to 700 °C for 12 hours under N2 and naturally cooled in the oven. After heat treatment, about 0.9 kg of final product was obtained and then filtered through a 38 pm sieve. XRD analysis of the resulting material is presented in FIG.
  • Attritor-mixed precursors were transferred to an oven then heated to 700 °C for 12 hours under N2 and naturally cooled in the oven. After heat treatment, about 0.73 kg of final product was obtained and then filtered through a 38 pm sieve. XRD analysis of the resulting material is presented in FIG.
  • Attri tor-mixed precursors were transferred to an oven then heated to 700 °C for 12 hours under N2 and naturally cooled in the oven. After heat treatment, about 0.62 kg of final product was obtained and then filtered through a 38 pm sieve. XRD analysis of the resulting material is presented in FIG. 23. The XRD data confirm that active material having the same structure of LiCoPCri was produced.

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Abstract

L'invention concerne une particule de matériau actif d'électrode positive revêtu comprenant un matériau actif ayant la formule chimique générale AxMyEz(X04)q, dans laquelle A est un métal alcalin ou un métal alcalino-terreux, M comprend du cobalt, E est un métal non-électrochimiquement actif, un élément du groupe du bore, ou du silicium ou n'importe quels alliages ou n'importe quelles combinaisons de ces derniers, x représente du phosphore ou du soufre ou une combinaison de ces derniers, 0 < x ≤ 1, y > 0, z ≥ 0, q > 0, et les valeurs relatives de x, y, z et q sont telles que la formule chimique générale soit équilibrée en charge. La particule de matériau actif d'électrode positive revêtu comprend également un revêtement comprenant de l'AI2O3, du ZriZE, du T1O2, du ZnO, du B2O3, du MgO2, du La202, du LiF et n'importe quelles combinaisons de ces derniers, ou du LiM1P04, où M1 est du Fe, du Cr, du Mn, du Ni, du V, ou n'importe quels alliages ou n'importe quelles combinaisons de ces derniers.
PCT/US2019/048768 2018-08-30 2019-08-29 Matériaux actifs de batterie rechargeable au lithium-ion revêtus WO2020047228A1 (fr)

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JP2021512278A JP7443340B2 (ja) 2018-08-30 2019-08-29 コーティングされたリチウムイオン再充電可能電池活物質
KR1020217009263A KR20210062021A (ko) 2018-08-30 2019-08-29 코팅된 리튬 이온 재충전 가능한 배터리 활물질
CN201980070904.2A CN113169328A (zh) 2018-08-30 2019-08-29 经涂覆的锂离子可充电电池活性材料
CA3109525A CA3109525A1 (fr) 2018-08-30 2019-08-29 Materiaux actifs de batterie rechargeable au lithium-ion revetus
EP19856341.3A EP3844831A4 (fr) 2018-08-30 2019-08-29 Matériaux actifs de batterie rechargeable au lithium-ion revêtus
US17/184,447 US20210184209A1 (en) 2018-08-30 2021-02-24 Coated lithium ion rechargeable battery active materials
JP2023183376A JP2023181319A (ja) 2018-08-30 2023-10-25 コーティングされたリチウムイオン再充電可能電池活物質

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EP3844831A4 (fr) 2022-06-29
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JP7443340B2 (ja) 2024-03-05
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