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
  • H01M4/48—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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G53/00—Compounds of nickel
  • C01G53/40—Complex oxides containing nickel and at least one other metal element
  • C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
• • 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
  • H01M10/052—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
  • H01M4/04—Processes of manufacture in general
  • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
• • 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
  • H01M4/139—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
  • H01M4/36—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
  • H01M4/36—Selection of substances as active materials, active masses, active liquids
  • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
  • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
• • H—ELECTRICITY
  • 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
  • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/50—Solid solutions
  • C01P2002/52—Solid solutions containing elements as dopants
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
  • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
  • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2006/00—Physical properties of inorganic compounds
  • C01P2006/40—Electric properties
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M4/00—Electrodes
  • H01M4/02—Electrodes composed of, or comprising, active material
  • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
  • H01M2004/028—Positive electrodes
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• the present disclosure relates generally to energy storage devices, and specifically to cathode active materials for lithium-ion batteries and processes for forming the same.
• Electrochemical energy storage systems are widely used to provide power to electronic, electromechanical, electrochemical, and other useful devices.
• Lithium-ion bateries are one of the most common examples of electrochemical energy storage systems, and the prevalence of lithium-ion batteries is due to their higher energy density when compared to other electrochemical energy storage systems.
• a lithium-ion battery consists of four main components: a cathode electrode, anode electrode, electrolyte, and separator, and at least some of the success of lithium-ion batteries may be attributed to the development of high-energy density electrodes.
• cathode active materials which are known or have been investigated for use in cathode electrodes for lithium-ion batteries, for example in the automotive industry.
• cathode active materials include transition metal layered oxides belonging to the LiNiCh (LNO), LiNii-x-yCo x Al y ()2 (NCA) or LiNii- x - yCoxMhyOz (NCM or NMC) families.
• LNO LiNiCh
• NCA LiNii-x-yCo x Al y
• NCM or NMC LiNii- xMhyOz
• These nickel-rich cathode active materials can provide the high energy densities in part because of their high nickel content.
• these nickel- rich cathode active materials have shown significant promise they also have their drawbacks including a significant loss of charge capacity over repeated charge/discharge cycles. Accordingly, there is a need for the development of improved nickel-rich cathode active materials.
• a doped nickel-rich cathode active material includes the chemical formula LiNiaTnibMcCh, where Tm is a transition metal element, M is a dopant element, a is a value of at least 0.9, b is a value from 0,01 to 0.0995, and c is a value from 0.005 to 0.02.
• the dopant element is selected from the group consisting of Ca, Mg, Zr, and combinations thereof.
• the dopant element is Zr and another element selected from the group consisting of Ca, Mg, and combinations thereof
• the compound comprises an atomic amount of Zr of at least about 0.003.
• the transition metal element is selected from the group consisting of Al, Zr, Mn, Ti, Co, and combinations thereof
• the transition metal element includes Ah, where x is a value from 0.01 to 0.03.
• the transition metal element includes Mn y Coz, where y is a value from 0 to 0.05, where z is a value from 0 to 0.05.
• the transition metal element includes AlxMn y Coz, where x is a value from 0.01 to 0.03, where y is a value from 0.01 to 0.05, where z is a value from 0.01 to 0.05.
• the nickel-rich cathode active material further includes a coating material disposed over the nickel-rich cathode active material.
• the coating material is selected from the group consisting of a sulfur compound, a metal compound, and combinations thereof.
• an electrode film includes the doped nickel-rich cathode active material is provided. In some embodiments, the electrode film is disposed over a current collector forming a nickel-rich cathode electrode.
• an energystorage device includes the nickel-rich cathode electrode, a separator, an anode electrode, an electrolyte, and a housing, where the nickel-rich cathode electrode, the separator, and the anode electrode are positioned within the housing.
• the energy storage device is a battery.
• a coated nickel-rich cathode active material includes a nickel-rich cathode active material and a sulfur coating disposed over the nickel-rich cathode active material.
• the coated nickel-rich cathode active material further includes a metal coating.
• the sulfur coating includes a compound selected from the group of dimethyl sulfone, dimethyl sulfoxide, sulfur nanoparticles, sodium dodecyl sulfate, sodium sulfate, lithium sulfate, and combinations thereof.
• the metal coating includes an element selected from the group consisting of Al, W, Mo, and combinations thereof.
• the coating includes a plurality of coating layers.
• the nickel-rich cathode active material further includes a dopant element.
• a method for preparing a doped nickel-rich cathode active material includes mixing a nickel-rich precursor with a dopant material, and a lithium source, to form a lithiated nickel-rich precursor mixture, and heating the lithiated nickel-rich precursor mixture to form a doped nickel-rich cathode active material.
• the method further includes disposing a sulfur coating material over the doped nickel-rich cathode active material.
• a method for preparing a coated nickel-rich cathode active material includes mixing a nickel-rich cathode active material with a sulfur coating material to form a nickel-rich cathode active material mixture, where the sulfur coating material is disposed over the nickel-rich cathode active material, and heating the nickel-rich cathode active material mixture to form a coated nickel-rich cathode active material.
• the nickel-rich cathode active material further includes a dopant element.
• FIG. 1 is a schematic depicting a process of forming a doped nickel-rich cathode active material, according to some embodiments.
• FIG. 2 is a schematic depicting a process for forming a coated nickel-rich cathode active material, according to some embodiments.
• FIG. 3 is an XRD pattern plot of a nickel-rich cathode active material, according to some embodiments.
• FIG. 4 is a plot showing the impact of doping a nickel-rich cathode active material with calcium on the normalized discharge capacity of a half cell, according to some embodiments.
• FIG. 5 is a plot showing the impact of doping a nickel-rich cathode active material with calcium on the normalized discharge energy of a full cell, according to some embodiments.
• FIG. 6 is a plot showing the impact of coating a nickel-rich cathode active material with sulfur on the normalized discharge capacity of a half cell, according to some embodiments.
• FIG. 7 is a plot showing the impact of coating a nickel-rich cathode active material with sulfur on the normalized cathode discharge energy of a full cell, according to some embodiments.
• FIG. 8A is a plot showing the impact of coating a nickel-rich cathode active materials with a metal on the normalized discharge capacity of a half cell, according to some embodiments.
• FIG. 8B is a plot showing the impact of coating a nickel-rich cathode active materials with a metal on the average charge voltage --- average discharge voltage of a half cell, according to some embodiments.
• FIG. 9 is a plot showing the impact of coating a calcium doped nickel-rich cathode active material with sulfur on the normalized discharge capacity of a half cell, according to some embodiments.
• FIG. 10 is a plot showing the impact of coating a calcium doped cathode active material with sulfur on the normalized cathode energy of a full cell, according to some embodiments.
• FIG. 11 A is a plot showing the impact of including various transition metals within the nickel-rich cathode active material on the normalized discharge capacity of a half cell, according to some embodiments.
• FIG. 1 IB is a plot showing the impact of including various transition metals within the nickel-rich cathode active material on the charge voltage - discharge voltage of a half cell, according to some embodiments.
• FIG. 12 is a plot showing the impact of including various transition metals within the nickel-rich cathode active material on the normalized cathode energy of a full cell, according to some embodiments.
• nickel-rich cathode active material with improved discharge capacity and capacity retention, and methods for preparing the nickel-rich cathode active materials.
• Such nickel-rich cathode active materials may be doped and/or coated to reduce 1) mixing of lithium and nickel atoms within the crystal lattice and 2) oxygen mobility or evolution at the cathode electrode surface during cycling.
• the improved nickel-rich cathode active materials described herein may be used to reduce electrical resistance and improve cycle lifetimes in energy storage devices.
• the nickel-rich cathode active materials are of the general formula LiNiaCh or LiNiaTmiXh, wherein “a” is at least, or is at least about, 0.8 and “Tm” is at least one transition metal element.
• nickel-rich cathode active materials include LiNii-x-yCoxAlyOz (“NCA”) and LiNii-x-yCoxMnyO? (“NCM”).
• the nickel-rich cathode active material may include a dopant material.
• the dopant material is selected from a metal (M), metal oxide (M y ()z), a metal hydroxide (M y (OH) z ), and combinations thereof, wherein “M” represents a metal and “y” and “z” are values which create a neutrally charged dopant material.
• the dopant material comprises a metal (“M”) selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof.
• the dopant material comprises Zr and a metal selected from calcium (Ca), magnesium (Mg), and combinations thereof.
• the nickel-rich cathode active material may include a coating material.
• the coating material includes a sulfur compound, a metal compound, or combinations thereof.
• the sulfur compound is selected from dimethyl sulfone (DMS), dimethyl sulfoxide (DMSO), and combinations thereof.
• the metal compound comprises a metal selected from tungsten (W), molybdenum (Mo), aluminum (Al), and combinations thereof.
• the nickel-rich cathode active material may include a dopant material and a coating material.
• a dopant material may include a dopant material and a coating material.
• Such doped and coated nickel-rich cathode active materials are described and may be prepared by the processes described herein.
• Cathode active materials with high nickel content may include a dopant to improve the performance of cathode electrodes.
• nickel-rich cathode active material comprises lithium (Li), nickel (Ni), a dopant element (M), and oxygen (O).
• the nickel-rich cathode active material further comprises a transition metal element (Tm).
• the nickel-rich cathode active material may include LiNiaZcCh, LiNiaTmbZcCh, or combinations thereof.
• the nickel-rich cathode active material may include LiNiaMcCh, LiNiaTmbMcCh, or combinations thereof.
• “a” is, is about, is at least, or is at least about, 0.7, 0.75, 0.8, 0.85, 0.9, 0.92, 0.95, 0.98 or 0.99, or any range of values therebetween.
• “a” is a numerical value between 0.7 and 0.99, between 0.85 and 0.95, or between 0.9 and 0.99.
• the transition metal element (“Tm”) is selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), zirconium (Zr), and combinations thereof.
• the transition metal element (“Tm”) is selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), and combinations thereof.
• the transition metal element comprises Mn y Coz, wherein y is a value from 0.01 to 0.05 or 0 to 0.05, and/or wherein z is a value from 0.01 to 0.05 or 0 to 0.05. In some embodiments, when y is 0 z is greater than 0 (e.g., 0.01). In some embodiments, when z is 0 y is greater than 0 (e.g., 0.01). In some embodiments, the transition metal element comprises AlxMnyCoz, wherein x is a value from 0.01 to 0.03, wherein y is a value from 0.01 to 0.05, wherein z is a value from 0.01 to 0.05.
• “b” is, or is about, 0, 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.0995, 0.1, or any range of values therebetween.
• “b” is a numerical value from 0.001 to 0.1, from 0.001 to 0.05, or from 0.001 to 0.03.
• each element of Tm is, or is about, 0, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, 0.08, 0.09, 0.0995 or 0.1 mol% of the nickel-rich cathode active material, or any range of values therebetween.
• the dopant element (“Z”) includes a metal (“M”).
• the metal (“M”) is selected from calcium (Ca), magnesium (Mg), zirconium (Zr) and combinations thereof.
• the dopant element (e.g., metal) comprises Zr and a metal selected from calcium (Ca), magnesium (Mg), and combinations thereof.
• “c” is, or is about, 0.005, 0.01, 0.015, 0.02, 0,025. 0.04, 0.06, 0.08, 0.1, or any range of values therebetween.
• “c” is a numerical value between 0.005 and 0.1, between 0.005 and 0.025, or between 0.005 and 0.01.
• the nickel-rich cathode active material may include an atomic amount of Zr of, of about, of at least, or at least about, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0,008, or any range of values therebetween.
• the nickel-rich cathode active material may have a formula of LiaNibAlcCadZreCh.
• “a” is, or is about, 0.97, 0.975, 0.98, 0.99, 0.995, 1 or any range of values therebetween.
• “a” is a numerical value of or between 0.97 to 1 , 0.98 to 1, or 0.99 to 1.
• “b” is, or is about, 0.95, 0.955, 0.96, 0.965, 0.97, 0.975, 0.98 or any range of values therebetween.
• “b” is a numerical value of or between 0.95 to 0.98, 0.96 to 0.97, or 0.96 to 0.98.
• “c” is, or is about, 0.001, 0.0015, 0.002, 0.0025, 0.003, or any range of values therebetween.
• “c” is a numerical value of or between 0.001 to 0.003, 0.0015 to 0.0025, or 0.0015 to 0.003.
• “d” is, or is about, 0.001, 0.0015, 0.002, 0.0025, 0.003, 0.0035, 0.004, or any range of values therebetween.
• “d” is a numerical value of or between 0.001 to 0.004, 0.0015 to 0.004, or 0.0015 to 0.0035.
• “e” is, is about, at least, or at least about 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, or any range of values therebetween.
• “e” is a numerical value of or between 0.002 to 0.008, 0.003 to 0.008, or 0.003 to 0.007.
• the nickel-rich cathode active material has a formula of LiaNibAlcCadZr eO2 ., wherein a is from about 0.99 to about 1, b is from about 0.96 to about 0.97, c is from about 0.015 to about 0.025, d is from about 0.0015 to about 0.0035, e is from about 0.003 to about 0.007. In some embodiments, the nickel-rich cathode active material has a formula of, or of about
• FIG. 1 is a flow chart 100 illustrating an example of the doped nickel-rich cathode active material formation process according to some of the embodiments.
• a nickel-rich precursor 102 and a dopant material 104 are provided and combined (e.g., mixed) in processing step 106 to form a nickel-rich precursor mixture 108,
• the nickel -rich precursor mixture 108 is combined (e.g., mixed) in processing step 112 with a lithium source 110 to form a lithiated nickel-rich precursor mixture 114.
• the lithiated nickel-rich precursor mixture 114 is heated (e.g., high temperature calcination) in processing step 116 to form the doped nickel-rich cathode active material 118.
• FIG, 1 depicts processing step 106 occurring prior to processing step 108, it. is understood that the processing steps may be carried out simultaneously, or processing step 106 may occur subsequent to processing step 108.
• the nickel-rich precursor is an oxide, hydroxide, or combinations thereof.
• the nickel-rich precursor comprises a transition metal element (“Tm”) selected from aluminum (Al), manganese (Mn), titanium (Ti), cobalt (Co), zirconium (Zr) and combinations thereof.
• Tm transition metal element
• the nickel-rich precursor is selected from NiAl(OH)2, NiMnAl(()H)2, NiMnCo(OH)2, NiCoAl(OH)2, NiZr(OH)2, and combinations thereof.
• the dopant material is selected from a metal (M), metal oxide (M y ()z), a metal hydroxide (My(OH)z), and combinations thereof, wherein “M” represents a metal and “y” and “z” are values which create a neutrally charged dopant material.
• the dopant material comprises a metal (“M”) selected from calcium (Ca), magnesium (Mg), zirconium (Zr), and combinations thereof.
• the dopant material is a metal hydroxide selected from Ca(OH)?., Mg(OH)2, and combinations thereof.
• the dopant material is a metal oxide such as ZrOa.
• the nickel-rich precursor mixture comprises, or comprises about, 0.1 mol.%, 0.125 mol.%, 0.25 mol.%, 0.5 mol.%, 0.75 mol.%, 1 mol.%, or 1.5 mol.% of a dopant material, or any range of values therebetween.
• the molar ratio of the nickekdopant material in the nickel-rich precursor mixture is, or is about, 1 :0.005, 1 :0.01, 1:0.015, 1:0.02, 1:0.025, 1 :0.03, 1 :0.035, 1:0.04, 1:0.045 or 1:0.05, or any range of values therebetween.
• a lithiated nickel-rich precursor mixture may comprise the nickel-rich precursor mixture and a lithium source.
• the lithium source includes a lithium salt.
• the lithium salt is selected from LiOH.HiO, LnCOy and combinations thereof.
• the molar ratio of the lithium: nickel in the lithiated nickel-rich precursor mixture is, or is about, 0.9: 1, 0.95: 1, 0.99: 1, 1: 1, 1.01 :1, 1.05:1, or 1.1 : 1, or any range of values therebetween.
• the nickel-rich active material mixture comprises, or comprises about, 10 wt.%, 11 wt.%, 12 wt,%, 14 wt.%, 16 wt.%, 18 wt.%, 20 wt.%, 25 wt.%, 30 wt.%, 35 wt.% or 40 wt.% of a lithium source, or any range of values therebetween.
• the lithiated nickel-rich precursor mixture is heated after being formed. In some embodiments, heating is performed at a temperature of, of about, of at least, or at least about, 550°C, 600°C, 625°C, 650°C, 675°C, 700°C, 725°C, 750°C, 760°C, 780°C, 800°C, 820°C, 840°C, 850°C, 860°C, 880°C, 900°C, 950°C or 1000°C, or any range of values therebetween. In some embodiments, heating of the lithiated nickel-rich precursor mixture is performed in an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere.
• an oxidizing atmosphere is an atmosphere comprising oxygen, for example such as air or an oxygen rich atmosphere.
• an oxygen rich atmosphere comprises at least 21 vol% oxygen, at least 23.5 vol% oxygen or at least 25 vol% oxygen.
• an inert atmosphere is an atmosphere comprising helium, neon, argon, krypton, xenon, radon, nitrogen, or combinations thereof.
• a reducing atmosphere is an atmosphere comprising hydrogen, carbon monoxide, hydrogen sulfide, or combinations thereof.
• heating is performed for a duration of, of about, of at least, or at least about, 0, 1, 2, 3, 4, 5, 7, 10, 20 or 50 hours, or any range of values therebetween.
• the hthiated nickel-rich precursor mixture is calcinated when heated.
• the process further includes destructuring the doped nickel-rich cathode active material.
• destructuring comprises a step selected from crushing, milling, and combinations thereof.
• the process includes treating the doped nickel-rich cathode active material.
• treating comprises a step selected from sieving, washing, filtering, drying, coating, and combinations thereof.
• Nickel-rich cathode active materials may include a coating to improve the performance of cathode electrodes.
• the coating comprises a layer disposed over an outer surface of the cathode active material.
• the coating comprises a plurality 7 of coating elements disposed over an outer surface of the cathode active material.
• the coating e.g. layer and/or plurality' of coating elements
• the coating includes a plurality of coating layers, such as 1, 2, 3, 4, 5 coating layers, or any range of values therebetween.
• the coating includes a sulfur compound, a metal compound, or combinations thereof.
• the sulfur compound includes sulfur nanoparticles, a sulfur gel, a sulfur solution, or combinations thereof.
• the sulfur compound includes (CH3)2SO, (CHbjzSOz, NaCi2H2sSO4, or combinations thereof.
• the metal compound includes an element selected from W, Mo, Al and combinations thereof.
• the metal compound includes the compounds NH4W, NH4M0, NaAKh, or combinations thereof.
• the nickel-rich cathode active material is a doped nickel-rich cathode active material as described and prepared by the processes described herein.
• FIG. 2 is a flow chart 200 illustrating an example of the coated nickel-rich cathode active material formation process according to some of the embodiments.
• a nickel-rich cathode active material 202 and a coating material 204 are provided and combined (e.g., mixed) in processing step 206 to form a nickel-rich cathode active material mixture 208.
• the nickel-rich cathode active material mixture 208 is heated in processing step 210 to form the coated nickel-rich cathode active material 212.
• the coating material comprises a sulfur compound, a metal compound, or combinations thereof.
• the metal compound comprises a metal selected from tungsten (W), molybdenum (Mo), aluminum (Al), and combinations thereof.
• the aluminum coating material is selected from AhO3, NaAlCh, Al(OH)s, and combinations thereof.
• the tungsten coating material is selected from NHUW, (NH4)IOH2(W20?)6, Na2WO4, WOs, and combinations thereof.
• the molybdenum compound is NH4M0.
• the sulfur compound is selected from dimethyl sulfoxide (DMSO), dimethyl sulfone (DMS), sulfur nanoparticles, sodium dodecyl sulfate, sodium sulfate, lithium sulfate, and combinations thereof.
• the coating material is added to the nickel-rich cathode active material at 0.01, 0.02, 0.04, 0.08, 0.1, 0.15, 0.20, 0.25, 0.30, 0.35, 0.40, 0.45, 0.50 or 0.60 mol.%, or any range of values therebetween.
• the nickel-rich cathode active material is washed with water prior to mixing with the coating material. In some embodiments, a solid-liquid separation is performed on the washed nickel-rich cathode active material prior to mixing with the coating material. In some embodiments, the nickel-rich cathode active material comprises, or comprises about, 1 wt.%, 2 wt.%, 3 wt.%, 5 wt.%, 7 wt.%, 9 wt.% or 12 wt.% water, or any range of values therebetween.
• the nickel-rich cathode active material mixture is heated after being formed. In some embodiments, heating is performed at a temperature of, of about, of at least, or at least about, 100°C, 125°C, 150°C, 175°C, 200°C, 225°C, 250°C, 275°C, 300°C, 325°C, or 350°C, or any range of values therebetween. In some embodiments, heating of the nickel-rich cathode active material mixture is performed in an oxidizing atmosphere, an inert atmosphere, or a reducing atmosphere. In some embodiments, an oxidizing atmosphere is an atmosphere comprising oxygen, for example such as air or an oxygen rich atmosphere.
• an oxygen rich atmosphere comprises at least 21 vol% oxygen, at least 23.5 vol% oxygen or at least 25 vol% oxygen.
• an inert atmosphere is an atmosphere comprising helium, neon, argon, krypton, xenon, radon, nitrogen, or combinations thereof.
• a reducing atmosphere is an atmosphere comprising hydrogen, carbon monoxide, hydrogen sulfide, or combinations thereof.
• heating is performed for a duration of, of about, of at least, or at least about, 0, 1, 2, 4, 6, 8, 10, 20 or 30 hours, or any range of values therebetween.
• the doped and/or coated nickel-rich cathode active materials may be used in the preparation of an electrode for an energy storage device.
• an electrode film e.g., doped and/or coated nickel-rich electrode film
• an electrode comprises a current collector and the electrode film.
• the electrode is a cathode electrode.
• an energy storage device includes an electrode as described herein.
• the energy storage device comprises a separator, an anode electrode, a cathode electrode, and a housing, wherein the separator, anode electrode and cathode electrode are disposed within the housing and the separator is positioned between the anode and cathode electrodes.
• an energy storage device is formed by placing a separator, an anode electrode and the cathode electrode withm a housing, wherein the separator is placed between the anode electrode and the cathode electrode.
• the energy storage device is a battery.
• the energy storage device is a lithium-ion battery.
• Example embodiments of the present disclosure including processes, materials and/or resultant products, are described in the following examples.
• a calcium-doped and a doped-control nickel-rich cathode active material were prepared.
• a nickel-rich Nio.9gAlo.o2(OH)?. precursor material was mixed with 0.125-1.00 mol.% ZrCh and 0.25 mol.% Ca(OH)z dopant material to form a calcium-doped nickel-rich precursor mixture.
• a doped-control nickel-rich precursor mixture was prepared by mixing Nio.9sAlo.o2(OH)2 precursor material with 0.125-1.00 moL% ZrO? dopant material.
• the lithiated calcium-doped nickel-rich precursor mixture and the lithiated doped-control nickel-rich precursor mixture were heated at 670-700°C in oxygen for 3-8 hours.
• the heated lithiated calcium-doped nickel-rich precursor mixture and heated lithiated doped-control nickel-rich precursor were ground and sieved to produce a calcium- doped nickel-rich cathode active material and a doped-control nickel-rich cathode active material.
• the produced calcium-doped nickel-rich cathode active material had a formula of LiaNibAlcCadZreCh, wherein a is from about 0.99 to about 1, b is from about 0.96 to about 0.97, c is from about 0.015 to about 0.025, d is from about 0.0015 to about 0.0035, e is from about 0,003 to about 0.007.
• a, b, c, d and e created a neutrally charged dopant material.
• Sulfur-coated and coated-control nickel-rich cathode active materials were prepared, A doped nickel-rich cathode active material was washed with water, then a solidliquid separation was performed on the washed nickel-rich cathode active material. The washed nickel-rich cathode active material was mixed with a NaAlCh solution, and subsequently mixed with an NITrW solution to form a metal coated nickel-rich cathode active material. A portion of the metal coated nickel-rich cathode active material was set aside and heated at 200-250°C in oxygen for 3-8 hours to form the coated-control nickel-rich cathode active material.
• the metal coated nickel-rich cathode active material was mixed with 0.1- 0.5 mol.% of a DMS dry powder and heated at 200-250°C in oxygen for 3-8 hours to form the sulfur-coated nickel-rich cathode active materials.
• FIG. 3 is an XRD pattern plot comparing the lattice structure of a calcium- doped nickel-rich cathode active material to the doped-control cathode active material.
• the data provided in FIG. 3 is further summarized in Table 1 below.
• Ca calcium-doped nickel-rich cathode active materials
• No Ca doped-control nickel-rich cathode active materials
• Half cells comprising calcium-doped and doped-control and/or sulfur- coated and coated- control nickel-rich cathode active materials were prepared and tested.
• Doped and/or coated cathode active materials were prepared utilizing similar processes to those described in Examples 1 and 2.
• Cathode electrodes were prepared by providing the doped and coated cathode active materials, and the materials were mixed with polyvinyl idene difluoride (PVDF) and Super-S carbon black at a ratio of 85: 10:5 w,% in N-methyl-2- pyrrolidone (NMP) to form a slurry'. The slurry was cast onto a piece of aluminum foil and then dried in an oven at 120°C for 3 hours.
• PVDF polyvinyl idene difluoride
• NMP N-methyl-2- pyrrolidone
• the dried mixture was then calendered at a pressure of 2000 atm to form a bulk electrode material with a loading of 10.51 mg/cm 2 .
• 1.2 cm coin cell electrodes were punched from the bulk electrode material and the com cell electrodes were dried under vacuum at 120°C for 14 hours.
• Coin cells were fabricated in an argon-filled glove box by stacking a coin cell electrode, a first separator, a second separator, and a lithium foil negative electrode.
• Full cells i.e., pouch cells
• Cathode electrodes for the full cells were prepared similarly to those prepared for the half cells.
• Full cells were prepared by stacking a cathode electrode, a separator, and an anode electrode together to form an electrode stack. The electrode stack was placed in a pouch which was filled with a lithium hexafluorophosphate electrolyte solution. As prepared, the full cells had an approximate capacity of 200 mAh.
• Galvanostatic charge and discharge cycling was performed using an Arbin battery testing system. The full cells were maintained at 40°C during testing. The full cells were initially charged to 4.2 V at a constant rate of C/20 and then discharged to 2.5 V at a rate of C/20. Then the full cells were then cycled between 2.85-4.20 V at a constant rate of C/3.
• Example 5 Electrochemical Cells including Calcium-Doped Nickel-Rich Cathode Active Materials
• FIGS. 4 and 5 are plots showing the performance of half cells and full cells, respectively, comprising a calcium-doped nickel-rich cathode active material, as compared to electrochemical cells comprising a doped-control nickel rich cathode active material.
• the normalized discharge capacity of electrochemical cells comprising a calcium-doped nickel-rich cathode active material demonstrated improved performances relative to cells comprising a doped-control nickel-rich cathode active material (labeled “Without Ca”).
• Example 6 Electrochemical Cells including Sulfur-Coated Nickel-Rich Cathode Active Materials
• FIGS. 6 and 7 are plots showing the performance of half cells and full cells, respectively, comprising a sulfur-coated nickel-rich cathode active material (labeled “Coated + Sulfur”), as compared with electrochemical cells comprising a coated-control nickel-rich cathode active material (“Coated”).
• Coated + Sulfur sulfur-coated nickel-rich cathode active material
• FIGS. 6 and 7 the normalized discharge capacity and normalized capacity retention, respectively, of electrochemical cells comprising a sulfur-coated nickel-rich cathode active material demonstrated improved performance relative to cells comprising a coated-control nickel-rich cathode active material.
• Example 7 Electrochemical Cells including either Tungsten-Coated or Molybdenum-Coated Nickel-Rich Cathode Active Materials
• FIGS. 8 A and 8B are plots showing the performance of half cells comprising a tungsten-coated nickel-rich cathode active material (labeled “W treatment”) and a molybdenum-coated nickel-rich cathode active material (labeled “Mo treatment”), as compared with cells comprising an unwashed non-coated nickel-rich cathode active material (labeled “Unwashed”), a washed non-coated nickel-rich cathode active material (labeled “Washed”), and a washed and reheated non-coated nickel-rich cathode active material (labeled “Washed + reheat”).
• W treatment tungsten-coated nickel-rich cathode active material
• Mo treatment molybdenum-coated nickel-rich cathode active material
• the discharge capacity and dV growth, respectively, of electrochemical cells comprising a tungsten-coated or molybdenum- coated nickel-rich cathode active material demonstrated improved performance relative to electrochemical cells comprising an unwashed non-coated nickel-rich cathode active material, a washed non-coated nickel-rich cathode active material, and a washed and reheated noncoated nickel-rich cathode active material.
• Example 8 Electrochemical Cells including Sulfur-Coated and/or Calcium-Doped Active Materials
• FIGS, 9 and 10 are plots showing the performance of half cells and full cells, respectively, comprising a DMS-coated (i.e. sulfur-coated) and calcium -doped nickel- rich cathode active material (labeled “Ca + Sulfur”), as compared to electrochemical cells comprising a DMS-coated nickel-rich cathode active material (labeled “Sulfur-only”) and calci um-doped nickel-rich cathode active material (“Ca-only”).
• a DMS-coated i.e. sulfur-coated
• Ca + Sulfur calcium -doped nickel- rich cathode active material
• Example 9 Electrochemical Cells including Cathode Active Materials with either Aluminum or Zirconium Transition Metals
• FIGS. 11A and 11B are plots showing the performance of half cells comprising cathode active materials comprising 2 mol.%, 1 mol.%, or 0.5 mol.% aluminum transition metal within the active material (labeled “2% Al”, “1%A1”, “0.5%Al” respectively), or alternatively 0.5 mol.% or 0.25 mol.% zirconium transition metal (labeled “0.5%Zr”, “0.25%Zr” respectively).
• the normalized discharge capacity and average charge voltage - average discharge voltage growth, respectively, of electrochemical cells comprising nickel-rich cathode active material including an aluminum transition metal showed improved performances as transition metal mol.% were increased.
• FIG. 12 is a plot showing the performance of full cells comprising cathode active materials comprising 2 mol.%, 1 mol.%, or 0.5 mol.% aluminum transition metal within the active material (labeled “2%A1”, “1%A1”, “0.5%Al” respectively), or alternatively 0.5 mol.% or 0.25 mol.% zirconium transition metal within the active material (labeled “0.5%Zr”, “0.2.5%Zr” respectively), as compared with electrochemical cells having a LiNio 8Coo.jMno.1O2 (labeled “NMC 811”) cathode active material or a LiNiCh (labeled ‘‘LiNiCh”) cathode active material.
• electrochemical cells having a nickel-rich cathode active material with a zirconium transition metal included demonstrated improved lifetimes relative to electrochemical cells with NMC811 and LNO cathode active materials.
• Conditional language such as “can,” “could,” “might,” or “may,” unless specifically stated otherwise, or otherwise understood within the context as used, is generally intended to convey that certain embodiments include, while other embodiments do not include, certain features, elements, and/or steps. Thus, such conditional language is not generally intended to imply that features, elements, and/or steps are in any way required for one or more embodiments or that one or more embodiments necessarily include logic for deciding, with or without user input or prompting, whether these features, elements, and/or steps are included or are to be performed in any particular embodiment.

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