WO2022016179A1 - Mixed metal manganese oxide material - Google Patents

Mixed metal manganese oxide material Download PDF

Info

Publication number
WO2022016179A1
WO2022016179A1 PCT/US2021/070860 US2021070860W WO2022016179A1 WO 2022016179 A1 WO2022016179 A1 WO 2022016179A1 US 2021070860 W US2021070860 W US 2021070860W WO 2022016179 A1 WO2022016179 A1 WO 2022016179A1
Authority
WO
WIPO (PCT)
Prior art keywords
chemical formula
multiplied
composition
average valence
mixture
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US2021/070860
Other languages
French (fr)
Other versions
WO2022016179A9 (en
Inventor
Stuart Miller
Susan C. Koster
Natalie L. NICHOLLS
Elmira GHANBARI
John P. S. MOWAT
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Honeywell UOP LLC
Original Assignee
UOP LLC
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by UOP LLC filed Critical UOP LLC
Publication of WO2022016179A1 publication Critical patent/WO2022016179A1/en
Publication of WO2022016179A9 publication Critical patent/WO2022016179A9/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0821—Oxynitrides of metals, boron or silicon
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Complex oxides containing manganese and at least one other metal element
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/20—Compounds containing manganese, with or without oxygen or hydrogen, and containing one or more other elements
    • C01G45/22—Compounds containing manganese, with or without oxygen or hydrogen, and containing two or more other elements
    • 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
    • C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/02—Amorphous compounds
    • 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
    • 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
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/74—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by peak-intensities or a ratio thereof only
    • 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

  • This invention relates generally to the storage of electrical energy, and more particularly to batteries, and even more specifically to a material for a cathode in a battery.
  • Zinc provides the benefit of high energy densities as well as being chemically compatible with aqueous electrolytes. Due to this, the electrochemical properties of zinc have been a long-standing curiosity for over 200 years, with one of the first documented occurrences starting with Alessandro Volta, who, in 1798, is credited with the invention of the first true battery, consisting of a stacks of alternating copper and zinc disks separated by a layer of cloth or cardboard soaked in brine.
  • the Leclanche cell comprises of a zinc anode and a manganese dioxide (and carbon) cathode wrapped in a porous material and dipped in a vessel containing ammonium chloride, providing a voltage -1.4V.
  • the Leclanche cell was further modified by German physicist Carl Gassner by mixing ammonium chloride and a small volume of zinc chloride, in plaster of Paris, immobilizing the electrolyte.
  • the manganese dioxide cathode was dipped in the plaster of Paris paste and then encased inside a zinc cell, providing a potential of ⁇ 1.5V.
  • the system was referred to as the dry cell as there was no liquid electrolyte, which enabled the use of the dry cell in any orientation.
  • the dry cell was mass produced until the late 1950s when it was replaced by Union Carbide’s innovation, the modern Zn
  • Mn0 2 alkaline batteries are considered as primary batteries, i.e. non-rechargeable, as there is an irreversible transformation to the cell upon discharge.
  • the manganese oxide cathode material used in the production of zinc batteries is electrolytic manganese dioxide (EMD) and can also be described as the g-Mhq2 phase.
  • EMD electrolytic manganese dioxide
  • the manganese oxide mineral Nsutite was used as the cathode material in zinc-carbon dry cell batteries, however in recent years production EMD has enabled a more reliable Mn0 2 source as well as enhanced performance and stability. Nsutite and EMD are both ingrown pyrolusite / Ramsdellite materials.
  • Rechargeable alkaline manganese (RAM) batteries were developed from primary alkaline battery technology and are capable of being recharged for a limited number of cycles at limited depth of discharge.
  • RAM Rechargeable alkaline manganese
  • Several companies and academic institutions pursued different routes to establishing rechargeable alkaline manganese oxide technologies however research interest in the area subsided with the commercialization of lithium-ion technology in 1991, a collaborative effort between Sony and Asahi Kasei. Since then lithium-ion batteries (LIBs) have established themselves as technology leaders assuming the dominant market share for rechargeable energy solutions.
  • LIBs lithium-ion batteries
  • the present invention provides a novel, poorly crystalline manganese-based mixed metal oxides that are suitable for use as a cathode material for rechargeable batteries.
  • the mixed metal oxides exhibit a poorly crystalline diffraction pattern.
  • Mn0 2 battery may be economically produced which is economically competitive to current rechargeable battery alternatives, such as lithium-ion batteries.
  • the present invention may be characterized, in at least one aspect, as providing a unique mixed metal manganese oxide material which may be processed to facilitate the storage of electrical energy— specifically to form a cathode in a battery.
  • the mixed metal manganese oxide material may be characterized by the formula:
  • A represents a group I or group II metal or ammonium (NH4 + ) or an alkyl ammonium ion or a quaternary organic cation equivalent and may be selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, NR 4 + , and combinations of the foregoing, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof; ‘B’ represents Bi, Pb, and mixtures thereof; ‘C’ represents Cu, Au, Ag, and combinations thereof; ‘M’ represents Ni, Co, Al, Sc, V, Cr, Ce, Zn, and mixtures thereof; wherein D represents a charge balancing anionic species that may include, for example, C1-, F-, OH-, S 2 -, HS-, Br-, and combinations thereof.
  • Chemical Formula 1 a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’.
  • ‘a’ in Chemical Formula may vary between 0 to 0.4
  • ‘b’ may vary between 0 to 0.3
  • ‘c’ may vary between 0 to 5
  • ‘x’ may vary between 0 to 0.5.
  • the composition includes at least two of: A, B, C, and M.
  • the present invention may be characterized as providing a process for producing the mixed metal manganese oxide material of Chemical Formula 1 by forming a slurry reaction mixture containing sources of protic solvent and sources of Mn, A, B, C and M; reacting the mixture together at elevated temperature with an autogenous pressure and then recovering the poorly crystalline manganese-based mixed metal oxide material.
  • the reaction may be conducted at a temperature of from 10°C to 150°C for a period of time from 30 minutes to 14 days.
  • the present invention may be generally characterized as providing a rechargeable battery comprising a housing, an anode material inside the housing, a cathode material inside the housing and electrically separated from the anode material and an electrolyte in the housing, wherein the cathode material comprises Chemical Formula 1.
  • the present invention may be broadly characterized as providing a composition comprising: manganese oxide; copper, silver, gold, or combinations thereof; a first additional cation selected from the group consisting of: bismuth, lead, and mixtures thereof; and a second additional cation selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR 4 + , with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • the present invention may be characterized, generally, as providing an amorphous composition comprising: a mixed metal manganese dioxide, wherein the amorphous composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 592Q.
  • the present invention may be generally characterized as providing a rechargeable battery comprising: a housing; an anode material inside the housing; a cathode material inside the housing and electrically separated from the anode material; and, an electrolyte in the housing, wherein the cathode material comprises: a mixed metal manganese dioxide an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
  • Figure l is a representation of the phase transformation which occurs upon cell discharge of a conventional alkaline Zn
  • Figure 2 is a cross sectional view of an embodiment of the battery in a prismatic arrangement.
  • Figure 3 is an X-ray diffraction pattern of various Examples according to the present invention.
  • Figure 4 is an X-ray diffraction pattern comparing Examples according to the present invention to electrolytic manganese dioxide (EMD) and Bimessite (delta-MnO?).
  • EMD electrolytic manganese dioxide
  • Bimessite delta-MnO?
  • the novel, poorly crystalline manganese-based mixed metal oxides are best prepared by the dissolution and heat treatment of a soluble manganese salt, such as KMnCri with other metal components such as the nitrates or oxides of bismuth or copper.
  • Metal precursors are selected either as metal salts (such as the nitrate or chloride), the oxides or hydroxides (such as B1 2 O 3 or Ni(OH) 2 ).
  • a battery 10 may include a housing 12, a cathode current collector 14, a cathode material 16, a separator 18, an anode current collector 20, and an anode material 22. While the battery 10 of FIG. 2 is shown as a prismatic battery arrangement, it is possible that the battery 10 may also be a cylindrical battery.
  • the electrolyte may be an alkaline electrolyte (e.g. an alkaline hydroxide, such as NaOH, KOH, LiOH, Mg(OH)2, Ca(OH)2 or mixtures thereof).
  • alkaline hydroxide such as NaOH, KOH, LiOH, Mg(OH)2, Ca(OH)2 or mixtures thereof.
  • the cathode current collector 14 and the anode current collector 20 may be a conductive material, for example, nickel, nickel-coated steel, tin-coated steel, silver coated copper, copper plated nickel, nickel plated copper or similar material.
  • the cathode current collector 14, the anode current collector 20, or both may be formed into an expanded mesh, perforated mesh, foil or a wrapped assembly.
  • the separator 3 may be a polymeric separator (e.g. cellophane, sintered polymer film, or a polyolefin material).
  • the cathode material 16 of the battery 10 comprises a mixed metal manganese dioxide (MnO?).
  • MnO? mixed metal manganese dioxide
  • the cathode material 16 includes: manganese oxide; copper, silver, gold, or combinations thereof; a first additional cation selected from the group consisting of: bismuth, lead, and mixtures thereof; and a second additional cation selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ⁇ , with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • the cathode material 16 may also include a third additional cation selected from the group consisting of: nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof.
  • a composition of the cathode material 16 has a chemical formula of:
  • a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d ⁇
  • ‘a’ may be in the range of 0 to 0.4
  • ‘b’ may be in the range of 0 to 0.3
  • ‘c’ may be in the range of 0 to 5
  • ‘x’ may be in the range of 0 to 0.5.
  • the values for these variables are inclusive of the end points of the ranges. As will be appreciated, these values are in relation to the “1” of Mn in Chemical Formula 1.
  • ‘c’ is in the range of 0 to 0.8.
  • the composition includes at least two of A, B, C, and M from Chemical Formula 1.
  • ‘A’ is representative of a group I or group II metal or ammonium (NFL ⁇ ) or an alkyl ammonium ion or a quaternary organic cation equivalent and may be selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, or NR 4 + , with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • ‘A’ may be ammonium (NFL + ) or an alkyl ammonium ion.
  • ‘B’ in Chemical Formula 1 represents bismuth or lead or combinations thereof.
  • ‘C’ in Chemical Formula 1 represents gold, silver, copper, or combinations thereof.
  • ‘M’ in Chemical Formula 1 represents nickel, cobalt, magnesium, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof.
  • ‘D’ in Chemical Formula 1 represents a charge balancing anionic species, for example, fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (HS ), or combinations thereof.
  • Lithium, sodium, potassium, cesium, rubidium, beryllium magnesium, calcium, strontium, barium can be added as salts.
  • Examples include LiMnCL, NaMnO and KMnCL .
  • Bismuth may be incorporated into the cathode material 16 as an inorganic or organic salt of bismuth (oxidation states 5, 4, 3, 2, or 1), as a bismuth oxide, or as elemental bismuth (bismuth metal).
  • exemplary inorganic bismuth compounds are thought to include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth s
  • the lead may be incorporated into the cathode material 16 as an inorganic or organic salt of lead (oxidation states 2 or 4), as a lead oxide, or as elemental lead (lead metal).
  • exemplary inorganic lead compounds are thought to include lead chloride, lead bromide, lead fluoride, lead iodide, lead sulfate, lead nitrate, lead trichloride, lead citrate, lead carbonate, lead acetate, lead trifluoromethanesulfonate, lead nitrate oxide, lead phosphate, lead oxychloride.
  • the copper may be incorporated into the cathode material 16 as an organic or inorganic salt of copper (oxidation states 1, 2, 3 or 4), as a copper oxide, or as copper metal (i.e. elemental copper).
  • Exemplary copper compounds are thought to be copper and copper salts such as copper aluminum oxide, copper (I) oxide, copper (II) oxide, and copper salts in a +1, +2, +3, or +4 oxidation state such as, copper nitrate, copper sulfate, and copper chloride.
  • Gold may be incorporated into the cathode material 16 as an inorganic or organic salt of gold (oxidation states 1, 2 or 3), as a gold oxide, or as elemental gold (gold metal).
  • exemplary inorganic gold compounds are thought to include gold chloride, gold bromide, gold fluoride, gold iodide, gold sulfate, gold nitrate and gold trichloride.
  • Silver may be incorporated into the cathode material 16 as an inorganic or organic salt of silver (oxidation states 1, 2 or 3), as a silver oxide, or as elemental silver (silver metal).
  • exemplary inorganic silver compounds are thought to include silver chloride, silver bromide, silver fluoride, silver iodide, silver sulfate, silver nitrate and silver trichloride.
  • a binder is used to form the cathode material 16 into a cathode.
  • the binder may be present in a concentration of 0-50 wt %.
  • the binder comprises water-soluble cellulose-based hydrogels, which were used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers.
  • the binder may also be a cellulose film sold as cellophane.
  • the binders may be formed by physically cross-linking the water-soluble cellulose-based hydrogels with a polymer through repeated cooling and thawing cycles. For example, 0-50 wt. % carboxymethyl cellulose (CMC) solution may be cross-linked with 0-50 wt.
  • CMC carboxymethyl cellulose
  • % polyvinyl alcohol (PVA) on an equal volume basis The binder, compared to the traditionally-used TEFLON®, is thought to have superior performance. TEFLON® is a very resistive material, but its use in the industry has been widespread due to its good Tollable properties. This, however, does not rule out using TEFLON® as a binder. Mixtures of TEFLON® with the aqueous binder and some conductive carbon may be used to create Tollable binders.
  • the binder may be water-based, is thought to have superior water retention capabilities, adhesion properties, and helps to maintain the conductivity relative to identical cathode using a TEFLON® binder instead.
  • hydrogels include methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroypropyl cellulose (HPH), hydroypropylmethyl cellulose (HPMC), hydroxethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (ELEC).
  • crosslinking polymers include polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole.
  • a 0-50 wt % solution of water-cased cellulose hydrogen may be cross linked with a 0-50% wt solution of crosslinking polymers by repeated freeze/thaw cycles, radiation treatment or chemical agents (e.g. epichlorohydrin).
  • Charge balancing anionic species can be incorporated into the cathode material 16 through its addition as part of a salt, with the cation of the salt forming one of the metals in Chemical Formula 1.
  • the manganese compound may be incorporated into the cathode material 16 as an organic or inorganic salt of manganese (oxidation states 2, 3, 4, 6, or 7+), as a manganese oxide, or as manganese salts in a such as, manganese nitrate, manganese sulfate, manganese chloride, potassium permanganate, sodium permanganate or lithium permanganate.
  • Hydroxide anions may be incorporated into the cathode material 16 through the incorporation of a base, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide or organic alternatives such as quaternary ammonium hydroxides.
  • a base such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide or organic alternatives such as quaternary ammonium hydroxides.
  • the present mixed metal manganese dioxide material is poorly crystalline.
  • the present mixed metal manganese dioxide is “amorphous.”
  • amorphous it is meant that an x-ray powder diffraction pattern showing no very strong Bragg reflections and in particular only vw-w Bragg reflections in the range 54 to 592Q (1.697-1.564 d-spacing) less than 0.1.
  • Patterns presented in the following examples were obtained using standard x- ray powder diffraction techniques, by mixing 20wt.% alpha-alumina (corundum structure: AI2O3) powder as an internal intensity reference point.
  • 20wt.% alpha-alumina (corundum structure: AI2O3) powder as an internal intensity reference point.
  • AI2O3 alpha-alumina
  • alumina source must be used.
  • One such choice is the NIST certified Standard Reference Material 676a.
  • purity and particle morphology as alumina grains should be sub -micrometer in size and equi axial in shape to prevent preferred orientation effects when preparing a sample.
  • the radiation source was a high-intensity, x-ray tube operated at 40 kV and 40 mA.
  • the diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer-based techniques. Powder samples were pressed flat into a plate and continuously scanned between 5 degrees and 70 degrees (2Q). Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as theta, where theta is the Bragg angle as observed from digitized data. Intensities were determined from the diffraction peak height after subtracting background, “Io” being the peak height of the strongest peak of the added internal reference alpha-alumina (corundum structure: AI2O3) powder, namely the (113) reflection at 43.35 degrees 2Q (using Cu Kalpha radiation), and “I” being the peak height for each of the other peaks.
  • the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination can impose an uncertainty of +/-0.4 degrees on each reported value of 2Q. This uncertainty is also translated to the reported values of the d-spacings, which are calculated from the 2Q values.
  • a solution was prepared in a 1 liter TeflonTM bottle by dissolving N ⁇ (Nq 3 ) 2 *6H 2 q (0.02 moles, 5.81g) in DI water (0.55 moles, 10 grams), followed by the addition of KMnCE (0.1 moles, 15.80g) and (NEL ⁇ CCh (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko .22 Nio .22 Mn.
  • the x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
  • a solution was prepared in a 1 liter TeflonTM bottle by dissolving NH 4 VO 3 (0.02 moles, 2.34g) in DI water (0.55 moles, 10 grams) and concentrated NH 4 OH (2.8g, 0.024 moles) followed by the addition of KMnCE (1 moles, 15.80g) and ( EL ⁇ CCh (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 75 °C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 .
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving Bi(N0 3 ) 3 *5H 2 0 (O.Olmoles, 4.85 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, KMnCE (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE ⁇ CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 70°C for 8 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C.
  • Elemental analysis of the final product determined the composition to be K0 . 17Bi0 . 1MnC0 . 23N0 . 28.
  • the x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving Bi(N0 3 ) 3 *5H 2 0 (0.005moles, 2.42 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 65°C for 10 minutes until there were no precipitates, after which, KMnCE (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE ⁇ CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C.
  • Elemental analysis of the final product determined the composition to be K0.22Bi0.05MnC0.26N0.07.
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
  • Example 5 A solution was prepared in a 1-L TeflonTM bottle by dissolving Pb(N0 3 ) 3 *5H 2 0 (O.Olmoles, 3.31 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 75°C for 10 minutes until there were no precipitates, after which, KMn0 4 (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE ⁇ CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 . 21Pb0 . 11MnC0 . 21N0 . 02.
  • the x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving Bi (N0 3 ) 3 *5H 2 0 (O.Olmoles, 4.75 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, N ⁇ (Nq3)2*6H2q (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL ⁇ CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko . 14Bio . 11Nio . 2MnCo .i 8No . 17.
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving Bi(CH 3 COO) 3 (O.Olmoles, 3.86 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, N ⁇ (Nq3)2*6H2q (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL ⁇ CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 .1 Bi0 .1 Ni0 .21 MnC0 .36 N0 .12 .
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving Pb(N0 3 ) 3 *5H 2 0 (0.005moles, 1.17 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, Co(N0 3 ) 2 *6H 2 0 (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL ⁇ CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 .i8 Pb0 .04 Co0 .2 MnC0 .11 N0 .05 .
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared by dissolving Bi(N0 3 ) 3 *5H 2 0 (0.6moles, 29.1 grams) in (0.315 moles, 30g) of HNO3 and DI water (7.2 moles, 130g) The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, N ⁇ (Nq3)2*6H2q (0.12 moles, 34.9g) was added to the solution followed by KMnCE (0.6 mole, 94.82g) and (NFL ⁇ CCE (0.47 moles, 45g). The solution was mixed for 1 hour before being transferred to a two liter stirred reactor and digested at 90°C for 16 hours at 150rpm.
  • the obtained slurry was then filtered and washed with DI water (3 x 300ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko . 15Bio . 13Nio .i 6MnNo . 14.
  • the x- ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared in a 1-L TeflonTM bottle by dissolving CU(N0 3 ) 3 *2.5H 2 0 (0.02moles, 4.65g) in DI water (0.55 moles, 10 grams). KMnCfi (0.1 mole, 15.80g) and (NFL ⁇ CCE (0.078 moles, 7.5 g) were added. All reactants were mixed before the bottle was heated at 65 °C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko . 22Cuo . 22Mn. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
  • a solution was prepared by dissolving Ag(NC> 3 ) (O.Olmoles, 1.69 grams) in DI H20 (0.55 moles, 10 grams). KMnCfi (0.1 mole, 15.80g) and ( FL ⁇ CCE (0.078 moles, 7.5 g) were added. All reactants were mixed for lhr before being transferred to a two liter stirred reactor and digested at 90°C for 16hrs at 150rpm. The obtained slurry was then filtered and washed with DI H2O (3 x 300ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 . 24Ag0 . 05MnC0 . 4N0 . 07.
  • the x- ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
  • a solution was prepared in a one liter TeflonTM bottle by dissolving Ni(N0 3 ) 2 *6H 2 0 (0.02 moles, 5.81g) and Cu(N0 3 ) 3 *2.5H 2 0 (O.Olmoles, 2.33g) in DI water (0.55 moles, 10 grams followed by the addition of KMnCfi (0.1 moles, 15.80g) and ( FL ⁇ CCE (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 75°C for 24 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C.
  • Elemental analysis of the final product determined the composition to be Ko . 17Cuo . 11Nio . 24MnCo . 26No . 11.
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
  • a solution was prepared in a one liter TeflonTM bottle by dissolving Bi(N0 3 ) 3 *5H 2 0 (O.Olmoles, 4.85 grams) in (0.042 moles, 4g) of HNO3.
  • CU(N0 3 ) 3 *2.5H 2 0 (0.02moles, 4.65g) was added followed by the addition of KMnCE (0.1 moles, 15.80g) and (NFL ⁇ CCE (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 55°C for 48 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C.
  • Elemental analysis of the final product determined the composition to be K0 .13 Bi0 .1 Cu0 .21 MnC0 .i6 N0 .07 .
  • the x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
  • a solution was prepared in a one liter TeflonTM bottle by dissolving Bi(N0 3 ) 3 *5H 2 0 (0.005 moles, 2.42 grams) in (0.042 moles, 4g) of HNO3.
  • KOH 0.05 moles, 2.8g
  • DI H20 0.167, 3g
  • Cu(N0 3 ) 3 *2.5H 2 0 0.4moles, 9.3g
  • KMnCE 0.08 moles, 12.64g
  • (NFL ⁇ CCE 0.1 moles, 9.6g
  • Example 15 The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 . 03Bi0 . 07Cu0 . 49Mn. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q. [00085]
  • Example 15 Example 15
  • a solution was prepared in a one liter TeflonTM bottle by dissolving Bi(N03)3*5H20 (0.01 moles, 4.85 grams) in (0.042 moles, 4g) of HNO and DI water (0.28 moles, 5g). Next N ⁇ (Nq3)2*6H2q (0.02 moles, 5.81g) and Cu(N03)3*2.5H20 (0.005moles, 1.16g) was added followed by the addition of KMnCE (0. 1 moles, 15.8g) and (NFL ⁇ CCb (0.078 moles, 7.5g). All reactants were mixed together before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Bio .i Cuo . osNio .i Mn.
  • the x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0. 1 in a range of 54 to 592Q, as shown in FIG. 3.
  • a solution was prepared in a one liter TeflonTM bottle by dissolving Bi(N03)3*5H20 (0.01 moles, 4.85 grams) in (0.042 moles, 4g) of HNO and DI water (0.28 moles, 5g). Next N ⁇ (Nq3)2*6H2q (0.02 moles, 5.81g) and Cu(N03)3*2.5H20 (0.0042moles, 2.36g) was added followed by the addition of KMn04 (0.1 moles, 15.8g) and (NH4)2C03 (0.078 moles, 7.5g). All reactants were mixed together before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion.
  • the obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0 . 02Bi0 . 1Cu0 . 1Ni0 . 2Mn.
  • the x- ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
  • a solution was prepared in a one liter TeflonTM bottle by dissolving B ⁇ (Nq3)3.5H2q (O.Olmoles, 4.85 grams) in a solution of HNO3 (0.042 moles, 4g) and DI water (5g, 0.277 moles). The mixture was heated to 65°C for 10 minutes until there were no precipitates, after which, N ⁇ (Nq3)2*6H2q (0.02 moles, 5.81g) in DI H2O (lOg, 0.555 moles) was added to the solution followed by KMnCE (0.1 mole, 15.80g) in concentrated NFEOH (0.15 moles, 16g).
  • Examples 3 and 15 of the present application were compared against EMD and delta-MnCh.
  • the EMD was purchased as a commercially available material.
  • the delta-MnCh was prepared according to the method described in The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese, McKenzie, R. M., Mineralogical Magazine, vol. 38, pp. 493-502 (Dec. 1971).
  • the present invention is believed to provide a material that is suitable as a cathode material in a rechargeable battery.
  • a first embodiment of the invention is a composition comprising a chemical formula of A a B b C c M x Mni. x O y OH z D d , [Chemical Formula 1], wherein A in Chemical Formula 1 is a group I metal, group II metal, ammonium (NFL ⁇ ), an alkyl ammonium ion, or a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein A in Chemical Formula 1 is selected from the group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR 4 + , and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • An embodiment 0 f the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the charge balancing anionic species is selected from the group consisting of fluorine (F ), chlorine (O ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (FIS ), and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein C is copper.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein c is between 0 and 0.8.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein B is bismuth.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein M is nickel.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the composition is amorphous.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the composition has an x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 59 2Q.
  • a second embodiment of the invention is a composition comprising manganese oxide; copper, silver, gold, or a combination thereof; a first additional cation selected from a group consisting of bismuth, lead, and mixtures thereof; and a second additional cation selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4 + , and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a third additional cation selected from a group consisting of nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a hydroxyl group.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 592Q.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a charge balancing anionic species.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the charge balancing anionic species is selected from a group consisting of: fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (FIS ), and mixtures thereof.
  • An amorphous composition comprising a mixed metal manganese dioxide, wherein the amorphous composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 592Q.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the mixed metal manganese dioxide has a chemical formula of A a B b C c M x Mni. x O y OH z D d , [Chemical Formula 1], wherein A in Chemical Formula l is a group I metal, group II metal, ammonium (NH 4 + ), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein A in Chemical Formula 1 is selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ⁇ , and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (CF), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (FIS ), and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein C is copper.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein c is between 0 and 0.8.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein B is bismuth.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein M is nickel.
  • a third embodiment of the invention is a rechargeable battery comprising a housing; an anode material inside the housing; a cathode material inside the housing and electrically separated from the anode material; and, an electrolyte in the housing, wherein the cathode material comprises a mixed metal manganese dioxide an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 59 2Q.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese dioxide has a chemical formula of A a B b C c M x Mni.
  • a in Chemical Formula 1 is a group I metal, group II metal, ammonium (NH 4 + ), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof
  • B in Chemical Formula 1 is bismuth, lead, or a mixture thereof
  • C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof
  • M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof
  • D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x)
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein A in Chemical Formula 1 is selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR.4 + , and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (O ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (HS ), and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein C is copper.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein c is between 0 and 0.8.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein B is bismuth.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein M is nickel.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide comprises manganese oxide; copper, silver, gold, or a combination thereof; a first additional cation selected from a group consisting of bismuth, lead, and mixtures thereof; and a second additional cation selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ⁇ , and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a third additional cation selected from a group consisting of nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a hydroxyl group.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a charge balancing anionic species.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (HS ), and mixtures thereof.
  • the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2 ), nitrate (NO3 1 ), sulfide (S 2 ), bisulfide (HS ), and mixtures thereof.
  • a fourth embodiment of the invention is a method for forming a composition having a chemical formula of A a B b C c M x Mni. x O y OH z D d , [Chemical Formula 1], wherein A in Chemical Formula 1 is a group I metal, group II metal, ammonium (NH 4 + ), alkyl ammonium ion, a quaternary organic cation, or a mixture thereof, wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the fourth embodiment in this paragraph, wherein the elevated temperature is from 10°C to 150°C.
  • An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the fourth embodiment in this paragraph, wherein the slurry mixture is held at a temperature in a range from 10°C to 150°C for a period of time in a range from 30 minutes to 14 days.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A poorly crystalline mixed metal manganese oxide material. The mixed metal manganese oxide material may be used for making a cathode for a rechargeable battery. Generally, the mixed metal manganese oxide includes: manganese oxide; copper, silver, gold, or a combination thereof; a first additional cation selected from the group consisting of: bismuth, lead, and mixtures thereof; and a second additional cation selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4 +, or a combination thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. The amorphous composition has an essentially amorphous x-ray powder diffraction pattern.

Description

MIXED METAL MANGANESE OXIDE MATERIAL
STATEMENT OF PRIORITY
[0001] This application claims priority to U.S. Provisional Patent Application Ser. No.
63/053,302 filed on July 17, 2020, the entirety of which is incorporated herein by reference. FIELD OF THE INVENTION
[0002] This invention relates generally to the storage of electrical energy, and more particularly to batteries, and even more specifically to a material for a cathode in a battery.
BACKGROUND OF THE INVENTION [0003] The efficient and cost-effective capture and storage of energy is critically important, in particular, the storage and use of electrical energy has become a cornerstone to our modern lives. From cellular phones and electric vehicles to the continual development, refinement and deployment of energy from renewable sources, electrochemical energy storage plays a pivotal role in our developing world and provides significant market opportunity.
[0004] Owing to its relative abundance, low cost, toxicity equilibrium potential, zinc rapidly became a key component in the fabrication of electrochemical cells. Zinc provides the benefit of high energy densities as well as being chemically compatible with aqueous electrolytes. Due to this, the electrochemical properties of zinc have been a long-standing fascination for over 200 years, with one of the first documented occurrences starting with Alessandro Volta, who, in 1798, is credited with the invention of the first true battery, consisting of a stacks of alternating copper and zinc disks separated by a layer of cloth or cardboard soaked in brine. [0005] Since Volta’s invention of the Voltaic pile, zinc has been a key component of several different battery technologies, however it was not until 1866 that French electrical engineer Georges Leclanche paired the electrochemical properties of zinc and manganese inventing the Leclanche cell. The Leclanche cell comprises of a zinc anode and a manganese dioxide (and carbon) cathode wrapped in a porous material and dipped in a vessel containing ammonium chloride, providing a voltage -1.4V. The Leclanche cell was further modified by German physicist Carl Gassner by mixing ammonium chloride and a small volume of zinc chloride, in plaster of Paris, immobilizing the electrolyte. The manganese dioxide cathode was dipped in the plaster of Paris paste and then encased inside a zinc cell, providing a potential of ~1.5V. The system was referred to as the dry cell as there was no liquid electrolyte, which enabled the use of the dry cell in any orientation. Taking advantage of low material costs, the dry cell was mass produced until the late 1950s when it was replaced by Union Carbide’s innovation, the modern Zn|Mn02 alkaline battery. Zn|Mn02 alkaline batteries are considered as primary batteries, i.e. non-rechargeable, as there is an irreversible transformation to the cell upon discharge.
[0006] The simplified electrochemical reactions which take place at the anode and the cathode are shown below:
[0007] Anode (oxidation) Zn + 20H ZnO + ThO +2e
[0008] Cathode (reduction) 2Mn02 + ThO + 2e M112O3 + 20H
[0009] Overall reaction Zn + 2Mn02 ZnO + M112O3
[00010] The manganese oxide cathode material used in the production of zinc batteries is electrolytic manganese dioxide (EMD) and can also be described as the g-Mhq2 phase. Historically, the manganese oxide mineral Nsutite, was used as the cathode material in zinc-carbon dry cell batteries, however in recent years production EMD has enabled a more reliable Mn02 source as well as enhanced performance and stability. Nsutite and EMD are both ingrown pyrolusite / Ramsdellite materials. It has been well demonstrated, the current Zn|Mn02 batteries are limited in their ability to recharge owing to an irreversible transformation of the MnCh phase upon discharge to the dense phases of MmCh and MmCri, a cartoon representation of which is shown in Figure 1. However, prior to the formation of these phases, it is understood that EMD undergoes as dissolution / recrystallization procedure involving the in-situ crystallization of d-MnCh. [00011] Since the invention of the Zn|Mn02 alkaline battery, there has been considerable efforts to provide a rechargeable solution to enable the recharge and reuse the of cell after the primary discharge. Rechargeable alkaline manganese (RAM) batteries were developed from primary alkaline battery technology and are capable of being recharged for a limited number of cycles at limited depth of discharge. In the 1970s, a collaborative effort between Union Carbide and Mallory resulted in the introduction of the first-generation of rechargeable alkaline batteries. Several companies and academic institutions pursued different routes to establishing rechargeable alkaline manganese oxide technologies however research interest in the area subsided with the commercialization of lithium-ion technology in 1991, a collaborative effort between Sony and Asahi Kasei. Since then lithium-ion batteries (LIBs) have established themselves as technology leaders assuming the dominant market share for rechargeable energy solutions. [00012] For over 25 years, LIBs have cemented themselves as the rechargeable battery of choice, finding applications in technologies as diverse as portable electronics and electric vehicles to large scale energy storage complexes such as the 100-megawatt battery built by Tesla in South Australia. [00013] Today, LIBs remain the rechargeable battery of choice, however there are several factors which bring into question its continued market dominance, including cost, durability and potential safety hazards. Over the last 60 years, Zn|Mn02 alkaline cells have established themselves as a principle battery technology with an estimated $7.73B in global sales for consumer single use batteries by 2021. Modern Zn|Mn02 alkaline batteries use cheap, abundant materials (Mn ~ $0.45-0.9kg) (Zn ~ $0.45$kg) (K ~ $0.1kg) to provide safe batteries cells which are EPA certified for disposal.
[00014] The low material price enables the manufacture of primary Zn|Mn02 alkaline batteries for $18-25kWh, which makes them attractive for a variety of potential energy storage solutions if their chemistry could be altered to make them rechargeable. [00015] Therefore, there remains a need for providing a rechargeable battery that utilizes the Zn|MnC>2 chemistry.
SUMMARY OF THE INVENTION
[00016] The present invention provides a novel, poorly crystalline manganese-based mixed metal oxides that are suitable for use as a cathode material for rechargeable batteries. The mixed metal oxides exhibit a poorly crystalline diffraction pattern. By using material that is relatively abundant, has a low toxicity, and which has established manufacturing infrastructure, a rechargeable Zn|Mn02 battery may be economically produced which is economically competitive to current rechargeable battery alternatives, such as lithium-ion batteries.
[00017] Therefore, the present invention may be characterized, in at least one aspect, as providing a unique mixed metal manganese oxide material which may be processed to facilitate the storage of electrical energy— specifically to form a cathode in a battery. The mixed metal manganese oxide material may be characterized by the formula:
AaBbCcMxMn 1-xOy OHzDd,
[Chemical Formula 1] wherein ‘A’ represents a group I or group II metal or ammonium (NH4+) or an alkyl ammonium ion or a quaternary organic cation equivalent and may be selected from Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba, NR4 +, and combinations of the foregoing, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof; ‘B’ represents Bi, Pb, and mixtures thereof; ‘C’ represents Cu, Au, Ag, and combinations thereof; ‘M’ represents Ni, Co, Al, Sc, V, Cr, Ce, Zn, and mixtures thereof; wherein D represents a charge balancing anionic species that may include, for example, C1-, F-, OH-, S2-, HS-, Br-, and combinations thereof.
[00018] In Chemical Formula 1, a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’. Additionally, ‘a’ in Chemical Formula may vary between 0 to 0.4, ‘b’ may vary between 0 to 0.3; ‘c’ may vary between 0 to 5, and ‘x’ may vary between 0 to 0.5. The composition includes at least two of: A, B, C, and M.
[00019] In another aspect, the present invention may be characterized as providing a process for producing the mixed metal manganese oxide material of Chemical Formula 1 by forming a slurry reaction mixture containing sources of protic solvent and sources of Mn, A, B, C and M; reacting the mixture together at elevated temperature with an autogenous pressure and then recovering the poorly crystalline manganese-based mixed metal oxide material. The reaction may be conducted at a temperature of from 10°C to 150°C for a period of time from 30 minutes to 14 days.
[00020] In another aspect, the present invention may be generally characterized as providing a rechargeable battery comprising a housing, an anode material inside the housing, a cathode material inside the housing and electrically separated from the anode material and an electrolyte in the housing, wherein the cathode material comprises Chemical Formula 1.
[00021] In still a further aspect, the present invention may be broadly characterized as providing a composition comprising: manganese oxide; copper, silver, gold, or combinations thereof; a first additional cation selected from the group consisting of: bismuth, lead, and mixtures thereof; and a second additional cation selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4 +, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
[00022] In yet another aspect, the present invention may be characterized, generally, as providing an amorphous composition comprising: a mixed metal manganese dioxide, wherein the amorphous composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 592Q. [00023] In a further aspect, the present invention may be generally characterized as providing a rechargeable battery comprising: a housing; an anode material inside the housing; a cathode material inside the housing and electrically separated from the anode material; and, an electrolyte in the housing, wherein the cathode material comprises: a mixed metal manganese dioxide an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
[00024] Additional aspects, embodiments, and details of the invention, all of which may be combinable in any manner, are set forth in the following detailed description of the invention.
DESCRIPTION OF THE DRAWINGS
[00025] One or more exemplary embodiments of the present invention will be described below in conjunction with the following drawing figures, in which:
[00026] Figure l is a representation of the phase transformation which occurs upon cell discharge of a conventional alkaline Zn|Mn02 battery;
[00027] Figure 2 is a cross sectional view of an embodiment of the battery in a prismatic arrangement; and,
[00028] Figure 3 is an X-ray diffraction pattern of various Examples according to the present invention; and,
[00029] Figure 4 is an X-ray diffraction pattern comparing Examples according to the present invention to electrolytic manganese dioxide (EMD) and Bimessite (delta-MnO?).
DETAILED DESCRIPTION OF THE INVENTION [00030] As mentioned above, a novel, poorly crystalline manganese-based mixed material metal oxide has been invented which is believed to provide a superior material for making a cathode for a rechargeable battery. Rechargeable Zn-Mn batteries fabricated using composite cathodes containing the novel, poorly crystalline manganese-based mixed material metal oxide are believed to be capable of thousands of charge-discharge cycles, enabling a safe and economically affordable energy storage system.
[00031] Generally, the novel, poorly crystalline manganese-based mixed metal oxides are best prepared by the dissolution and heat treatment of a soluble manganese salt, such as KMnCri with other metal components such as the nitrates or oxides of bismuth or copper. Metal precursors are selected either as metal salts (such as the nitrate or chloride), the oxides or hydroxides (such as B12O3 or Ni(OH)2).
[00032] With these general principles in mind, one or more embodiments of the present invention will be described with the understanding that the following description is not intended to be limiting.
[00033] As shown in FIG. 2, a battery 10 according to the present invention may include a housing 12, a cathode current collector 14, a cathode material 16, a separator 18, an anode current collector 20, and an anode material 22. While the battery 10 of FIG. 2 is shown as a prismatic battery arrangement, it is possible that the battery 10 may also be a cylindrical battery.
[00034] As is known, dispersed within the housing 12 of the battery 10 is an electrolyte. The electrolyte may be an alkaline electrolyte (e.g. an alkaline hydroxide, such as NaOH, KOH, LiOH, Mg(OH)2, Ca(OH)2 or mixtures thereof).
[00035] The cathode current collector 14 and the anode current collector 20 may be a conductive material, for example, nickel, nickel-coated steel, tin-coated steel, silver coated copper, copper plated nickel, nickel plated copper or similar material. The cathode current collector 14, the anode current collector 20, or both may be formed into an expanded mesh, perforated mesh, foil or a wrapped assembly. [00036] The separator 3 may be a polymeric separator (e.g. cellophane, sintered polymer film, or a polyolefin material).
[00037] As discussed above, the cathode material 16 of the battery 10 according to the present invention comprises a mixed metal manganese dioxide (MnO?). Various metals and metal combinations have been discovered which may be used as the cathode material 16 with the manganese dioxide. Generally, the cathode material 16 includes: manganese oxide; copper, silver, gold, or combinations thereof; a first additional cation selected from the group consisting of: bismuth, lead, and mixtures thereof; and a second additional cation selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ^, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. The cathode material 16 may also include a third additional cation selected from the group consisting of: nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof.
[00038] Generally, a composition of the cathode material 16 has a chemical formula of:
AaBbCcMxMni-xOyOHzDd
[Chemical Formula 1]
[00039] In Chemical Formula 1, a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d\ Additionally, ‘a’ may be in the range of 0 to 0.4, ‘b’ may be in the range of 0 to 0.3, ‘c’ may be in the range of 0 to 5, and ‘x’ may be in the range of 0 to 0.5. The values for these variables are inclusive of the end points of the ranges. As will be appreciated, these values are in relation to the “1” of Mn in Chemical Formula 1. In a preferred embodiment, ‘c’ is in the range of 0 to 0.8.
[00040] The composition includes at least two of A, B, C, and M from Chemical Formula 1. [00041] In Chemical Formula 1 ‘A’ is representative of a group I or group II metal or ammonium (NFL^) or an alkyl ammonium ion or a quaternary organic cation equivalent and may be selected from lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, or NR4 +, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. For example, ‘A’ may be ammonium (NFL+) or an alkyl ammonium ion. ‘B’ in Chemical Formula 1 represents bismuth or lead or combinations thereof. Additionally, ‘C’ in Chemical Formula 1 represents gold, silver, copper, or combinations thereof. ‘M’ in Chemical Formula 1 represents nickel, cobalt, magnesium, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof. Finally, ‘D’ in Chemical Formula 1 represents a charge balancing anionic species, for example, fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (HS ), or combinations thereof.
[00042] Lithium, sodium, potassium, cesium, rubidium, beryllium magnesium, calcium, strontium, barium can be added as salts. Examples include LiMnCL, NaMnO and KMnCL.
[00043] Bismuth may be incorporated into the cathode material 16 as an inorganic or organic salt of bismuth (oxidation states 5, 4, 3, 2, or 1), as a bismuth oxide, or as elemental bismuth (bismuth metal). Exemplary inorganic bismuth compounds are thought to include bismuth chloride, bismuth bromide, bismuth fluoride, bismuth iodide, bismuth sulfate, bismuth nitrate, bismuth trichloride, bismuth citrate, bismuth telluride, bismuth selenide, bismuth subsalicylate, bismuth neodecanoate, bismuth carbonate, bismuth subgallate, bismuth strontium calcium copper oxide, bismuth acetate, bismuth trifluoromethanesulfonate, bismuth nitrate oxide, bismuth gallate hydrate, bismuth phosphate, bismuth cobalt zinc oxide, bismuth sulphite agar, bismuth oxychloride, bismuth aluminate hydrate, bismuth tungsten oxide, bismuth lead strontium calcium copper oxide, bismuth antimonide, bismuth antimony telluride, bismuth oxide yittia stabilized, bismuth-lead alloy, ammonium bismuth citrate, 2-napthol bismuth salt, duchloritri(o-tolyl)bismuth, dichlordiphenyl(p-tolyl)bismuth, triphenylbismuth.
[00044] The lead may be incorporated into the cathode material 16 as an inorganic or organic salt of lead (oxidation states 2 or 4), as a lead oxide, or as elemental lead (lead metal). Exemplary inorganic lead compounds are thought to include lead chloride, lead bromide, lead fluoride, lead iodide, lead sulfate, lead nitrate, lead trichloride, lead citrate, lead carbonate, lead acetate, lead trifluoromethanesulfonate, lead nitrate oxide, lead phosphate, lead oxychloride.
[00045] The copper may be incorporated into the cathode material 16 as an organic or inorganic salt of copper (oxidation states 1, 2, 3 or 4), as a copper oxide, or as copper metal (i.e. elemental copper). Exemplary copper compounds are thought to be copper and copper salts such as copper aluminum oxide, copper (I) oxide, copper (II) oxide, and copper salts in a +1, +2, +3, or +4 oxidation state such as, copper nitrate, copper sulfate, and copper chloride.
[00046] Gold may be incorporated into the cathode material 16 as an inorganic or organic salt of gold (oxidation states 1, 2 or 3), as a gold oxide, or as elemental gold (gold metal). Exemplary inorganic gold compounds are thought to include gold chloride, gold bromide, gold fluoride, gold iodide, gold sulfate, gold nitrate and gold trichloride.
[00047] Silver may be incorporated into the cathode material 16 as an inorganic or organic salt of silver (oxidation states 1, 2 or 3), as a silver oxide, or as elemental silver (silver metal). Exemplary inorganic silver compounds are thought to include silver chloride, silver bromide, silver fluoride, silver iodide, silver sulfate, silver nitrate and silver trichloride.
[00048] In some embodiments a binder is used to form the cathode material 16 into a cathode. The binder may be present in a concentration of 0-50 wt %. In one embodiment, the binder comprises water-soluble cellulose-based hydrogels, which were used as thickeners and strong binders, and have been cross-linked with good mechanical strength and with conductive polymers. The binder may also be a cellulose film sold as cellophane. The binders may be formed by physically cross-linking the water-soluble cellulose-based hydrogels with a polymer through repeated cooling and thawing cycles. For example, 0-50 wt. % carboxymethyl cellulose (CMC) solution may be cross-linked with 0-50 wt. % polyvinyl alcohol (PVA) on an equal volume basis. The binder, compared to the traditionally-used TEFLON®, is thought to have superior performance. TEFLON® is a very resistive material, but its use in the industry has been widespread due to its good Tollable properties. This, however, does not rule out using TEFLON® as a binder. Mixtures of TEFLON® with the aqueous binder and some conductive carbon may be used to create Tollable binders. The binder may be water-based, is thought to have superior water retention capabilities, adhesion properties, and helps to maintain the conductivity relative to identical cathode using a TEFLON® binder instead. Examples of hydrogels include methyl cellulose (MC), carboxymethyl cellulose (CMC), hydroypropyl cellulose (HPH), hydroypropylmethyl cellulose (HPMC), hydroxethylmethyl cellulose (HEMC), carboxymethylhydroxyethyl cellulose and hydroxyethyl cellulose (ELEC). Examples of crosslinking polymers include polyvinyl alcohol, polyvinylacetate, polyaniline, polyvinylpyrrolidone, polyvinylidene fluoride and polypyrrole. For example, a 0-50 wt % solution of water-cased cellulose hydrogen may be cross linked with a 0-50% wt solution of crosslinking polymers by repeated freeze/thaw cycles, radiation treatment or chemical agents (e.g. epichlorohydrin).
[00049] Charge balancing anionic species can be incorporated into the cathode material 16 through its addition as part of a salt, with the cation of the salt forming one of the metals in Chemical Formula 1.
[00050] The manganese compound may be incorporated into the cathode material 16 as an organic or inorganic salt of manganese (oxidation states 2, 3, 4, 6, or 7+), as a manganese oxide, or as manganese salts in a such as, manganese nitrate, manganese sulfate, manganese chloride, potassium permanganate, sodium permanganate or lithium permanganate.
[00051] Hydroxide anions may be incorporated into the cathode material 16 through the incorporation of a base, such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, rubidium hydroxide, beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide or organic alternatives such as quaternary ammonium hydroxides.
[00052] As noted above, the present mixed metal manganese dioxide material is poorly crystalline. Thus, in contrast to other manganese dioxide materials which can be described as crystalline, the present mixed metal manganese dioxide is “amorphous.” By “amorphous” it is meant that an x-ray powder diffraction pattern showing no very strong Bragg reflections and in particular only vw-w Bragg reflections in the range 54 to 592Q (1.697-1.564 d-spacing) less than 0.1.
[00053] Patterns presented in the following examples were obtained using standard x- ray powder diffraction techniques, by mixing 20wt.% alpha-alumina (corundum structure: AI2O3) powder as an internal intensity reference point. To ensure the consistency in the measurement, only a high purity and suitably prepared alumina source must be used. One such choice is the NIST certified Standard Reference Material 676a. Of particular importance is both purity and particle morphology as alumina grains should be sub -micrometer in size and equi axial in shape to prevent preferred orientation effects when preparing a sample. The radiation source was a high-intensity, x-ray tube operated at 40 kV and 40 mA. The diffraction pattern from the copper K-alpha radiation was obtained by appropriate computer-based techniques. Powder samples were pressed flat into a plate and continuously scanned between 5 degrees and 70 degrees (2Q). Interplanar spacings (d) in Angstrom units were obtained from the position of the diffraction peaks expressed as theta, where theta is the Bragg angle as observed from digitized data. Intensities were determined from the diffraction peak height after subtracting background, “Io" being the peak height of the strongest peak of the added internal reference alpha-alumina (corundum structure: AI2O3) powder, namely the (113) reflection at 43.35 degrees 2Q (using Cu Kalpha radiation), and “I” being the peak height for each of the other peaks. As will be understood by those skilled in the art the determination of the parameter 2 theta is subject to both human and mechanical error, which in combination can impose an uncertainty of +/-0.4 degrees on each reported value of 2Q. This uncertainty is also translated to the reported values of the d-spacings, which are calculated from the 2Q values.
[00054] It should be noted and will be understood by those skilled in the art, that when running the scan mixed with corundum as specified above, the Bragg reflections arising from the internal reference are for intensity comparisons only and are not part of the present invention. The expected reflections for the corundum are as follows: Reflection Indices (hkl) and Peak Position (2Q, degrees using Cu Kalpha radiation) (012) 25.574, (104) 35.149, (110) 37.773, (113) 43.351, (024) 52.548, (116) 57.497 (214) 66.513 (300) 68.203. Of note here is an expected hkl index (116) strong reflection arising from the internal reference in the specified range of 54 to 592Q that should be excluded from the comparisons listed in the claims.
[00055] In some of the x-ray patterns reported, the relative intensities of the d-spacings are indicated by the notations s, m, w and vw which represent strong, medium, weak and very weak, respectively. In terms of 100(I/Io), the above designations are defined as: vw=0.01-5, w=5-10, m=10-50, s=50-100, vs= >100 .
[00056] In the examples which follow elemental analyses were conducted on air dried samples. Analysis was carried out for all elements except oxygen.
EXAMPLES
[00057] Example 1
[00058] A solution was prepared in a 1 liter Teflon™ bottle by dissolving Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) in DI water (0.55 moles, 10 grams), followed by the addition of KMnCE (0.1 moles, 15.80g) and (NEL^CCh (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko.22Nio.22Mn. The x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
[00059] Example 2
[00060] A solution was prepared in a 1 liter Teflon™ bottle by dissolving NH4VO3 (0.02 moles, 2.34g) in DI water (0.55 moles, 10 grams) and concentrated NH4OH (2.8g, 0.024 moles) followed by the addition of KMnCE (1 moles, 15.80g) and ( EL^CCh (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 75 °C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.31V0.i8MnN0.i6. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q.
[00061] Example 3
[00062] A solution was prepared in a 1-L Teflon™ bottle by dissolving Bi(N03)3*5H20 (O.Olmoles, 4.85 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, KMnCE (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE^CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 70°C for 8 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.17Bi0.1MnC0.23N0.28. The x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
[00063] Example 4
[00064] A solution was prepared in a 1-L Teflon™ bottle by dissolving Bi(N03)3*5H20 (0.005moles, 2.42 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 65°C for 10 minutes until there were no precipitates, after which, KMnCE (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE^CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.22Bi0.05MnC0.26N0.07. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00065] Example 5 [00066] A solution was prepared in a 1-L Teflon™ bottle by dissolving Pb(N03)3*5H20 (O.Olmoles, 3.31 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 75°C for 10 minutes until there were no precipitates, after which, KMn04 (0.1 mole, 15.80g) followed by the addition of DI water (0.275 moles, 5g) and (NFE^CCE (0.078 moles, 7.5 g). All reactants were mixed before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.21Pb0.11MnC0.21N0.02. The x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
[00067] Example 6
[00068] A solution was prepared in a 1-L Teflon™ bottle by dissolving Bi (N03)3*5H20 (O.Olmoles, 4.75 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL^CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko.14Bio.11Nio.2MnCo.i8No.17. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00069] Example 7
[00070] A solution was prepared in a 1-L Teflon™ bottle by dissolving Bi(CH3COO)3 (O.Olmoles, 3.86 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL^CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.1Bi0.1Ni0.21MnC0.36N0.12. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00071] Example 8
[00072] A solution was prepared in a 1-L Teflon™ bottle by dissolving Pb(N03)3*5H20 (0.005moles, 1.17 grams) in (0.042 moles, 4g) of HNO3. The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, Co(N03)2*6H20 (0.02 moles, 5.81g) was added to the solution followed by a solution of KMnCE (0.1 mole, 15.80g) in DI water (0.825 moles, 15g). (NFL^CCE (0.078 moles, 7.5 g) was added to the solution with all reactants were mixed before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.i8Pb0.04Co0.2MnC0.11N0.05. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00073] Example 9
[00074] A solution was prepared by dissolving Bi(N03)3*5H20 (0.6moles, 29.1 grams) in (0.315 moles, 30g) of HNO3 and DI water (7.2 moles, 130g) The mixture was heated at 70°C for 10 minutes until there were no precipitates, after which, Nΐ(Nq3)2*6H2q (0.12 moles, 34.9g) was added to the solution followed by KMnCE (0.6 mole, 94.82g) and (NFL^CCE (0.47 moles, 45g). The solution was mixed for 1 hour before being transferred to a two liter stirred reactor and digested at 90°C for 16 hours at 150rpm. The obtained slurry was then filtered and washed with DI water (3 x 300ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko.15Bio.13Nio.i6MnNo.14. The x- ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 59 2Q.
[00075] Example 10
[00076] A solution was prepared in a 1-L Teflon™ bottle by dissolving CU(N03)3*2.5H20 (0.02moles, 4.65g) in DI water (0.55 moles, 10 grams). KMnCfi (0.1 mole, 15.80g) and (NFL^CCE (0.078 moles, 7.5 g) were added. All reactants were mixed before the bottle was heated at 65 °C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko.22Cuo.22Mn. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00077] Example 11
[00078] A solution was prepared by dissolving Ag(NC>3) (O.Olmoles, 1.69 grams) in DI H20 (0.55 moles, 10 grams). KMnCfi (0.1 mole, 15.80g) and ( FL^CCE (0.078 moles, 7.5 g) were added. All reactants were mixed for lhr before being transferred to a two liter stirred reactor and digested at 90°C for 16hrs at 150rpm. The obtained slurry was then filtered and washed with DI H2O (3 x 300ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.24Ag0.05MnC0.4N0.07. The x- ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q, as shown in FIG. 3.
[00079] Example 12
[00080] A solution was prepared in a one liter Teflon™ bottle by dissolving Ni(N03)2*6H20 (0.02 moles, 5.81g) and Cu(N03)3*2.5H20 (O.Olmoles, 2.33g) in DI water (0.55 moles, 10 grams followed by the addition of KMnCfi (0.1 moles, 15.80g) and ( FL^CCE (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 75°C for 24 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Ko.17Cuo.11Nio.24MnCo.26No.11. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
[00081] Example 13
[00082] A solution was prepared in a one liter Teflon™ bottle by dissolving Bi(N03)3*5H20 (O.Olmoles, 4.85 grams) in (0.042 moles, 4g) of HNO3. Next CU(N03)3*2.5H20 (0.02moles, 4.65g) was added followed by the addition of KMnCE (0.1 moles, 15.80g) and (NFL^CCE (0.078 moles, 7.5 g). All reactants were mixed together before the bottle was heated at 55°C for 48 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.13Bi0.1Cu0.21MnC0.i6N0.07. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
[00083] Example 14
[00084] A solution was prepared in a one liter Teflon™ bottle by dissolving Bi(N03)3*5H20 (0.005 moles, 2.42 grams) in (0.042 moles, 4g) of HNO3. Next, KOH (0.05 moles, 2.8g) was dissolved in DI H20 (0.167, 3g) after which Cu(N03)3*2.5H20 (0.04moles, 9.3g) was added followed by the addition of KMnCE (0.08 moles, 12.64g) and (NFL^CCE (0.1 moles, 9.6g). All reactants were mixed together before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.03Bi0.07Cu0.49Mn. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q. [00085] Example 15
[00086] A solution was prepared in a one liter Teflon™ bottle by dissolving Bi(N03)3*5H20 (0.01 moles, 4.85 grams) in (0.042 moles, 4g) of HNO and DI water (0.28 moles, 5g). Next Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) and Cu(N03)3*2.5H20 (0.005moles, 1.16g) was added followed by the addition of KMnCE (0. 1 moles, 15.8g) and (NFL^CCb (0.078 moles, 7.5g). All reactants were mixed together before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be Bio.iCuo.osNio.iMn. The x-ray powder diffraction pattern of the product is an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0. 1 in a range of 54 to 592Q, as shown in FIG. 3.
[00087] Example 16
[00088] A solution was prepared in a one liter Teflon™ bottle by dissolving Bi(N03)3*5H20 (0.01 moles, 4.85 grams) in (0.042 moles, 4g) of HNO and DI water (0.28 moles, 5g). Next Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) and Cu(N03)3*2.5H20 (0.0042moles, 2.36g) was added followed by the addition of KMn04 (0.1 moles, 15.8g) and (NH4)2C03 (0.078 moles, 7.5g). All reactants were mixed together before the bottle was heated at 70°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.02Bi0.1Cu0.1Ni0.2Mn. The x- ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 592Q.
[00089] Example 17
[00090] A solution was prepared in a one liter Teflon™ bottle by dissolving Bΐ(Nq3)3.5H2q (O.Olmoles, 4.85 grams) in a solution of HNO3 (0.042 moles, 4g) and DI water (5g, 0.277 moles). The mixture was heated to 65°C for 10 minutes until there were no precipitates, after which, Nΐ(Nq3)2*6H2q (0.02 moles, 5.81g) in DI H2O (lOg, 0.555 moles) was added to the solution followed by KMnCE (0.1 mole, 15.80g) in concentrated NFEOH (0.15 moles, 16g). All reactants were mixed before the bottle was heated at 65°C for 16 hours with intermittent venting during the digestion. The obtained slurry was then filtered and washed with DI water (3 x 100ml) after which the material was dried at 100°C. Elemental analysis of the final product determined the composition to be K0.1Bi0.1Ni0.19MnC0.29N0.15. The x-ray powder diffraction pattern of the phase matches the pattern shown in Figure 3, showing no Bragg reflections with an EIo >1, and only peaks with an EIo less than 0.1 in a range of 54 to 59 2Q.
[00091] As shown in FIG. 4, Examples 3 and 15 of the present application were compared against EMD and delta-MnCh. The EMD was purchased as a commercially available material. The delta-MnCh was prepared according to the method described in The synthesis of birnessite, cryptomelane, and some other oxides and hydroxides of manganese, McKenzie, R. M., Mineralogical Magazine, vol. 38, pp. 493-502 (Dec. 1971).
[00092] Thus, the present invention is believed to provide a material that is suitable as a cathode material in a rechargeable battery.
SPECIFIC EMBODIMENTS
[00093] While the following is described in conjunction with specific embodiments, it will be understood that this description is intended to illustrate and not limit the scope of the preceding description and the appended claims.
[00094] A first embodiment of the invention is a composition comprising a chemical formula of AaBbCcMxMni.xOyOHzDd, [Chemical Formula 1], wherein A in Chemical Formula 1 is a group I metal, group II metal, ammonium (NFL^), an alkyl ammonium ion, or a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3, ‘c’ is between 0 to 5, and ‘x’ is between 0 to 0.5, and, wherein the composition includes at least two of A, B, C, and M. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein A in Chemical Formula 1 is selected from the group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4 +, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. An embodiment 0f the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph wherein the charge balancing anionic species is selected from the group consisting of fluorine (F ), chlorine (O ), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (FIS ), and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein C is copper. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein c is between 0 and 0.8. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein B is bismuth. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein M is nickel. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the composition is amorphous. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the first embodiment in this paragraph, wherein the composition has an x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 59 2Q.
[00095] A second embodiment of the invention is a composition comprising manganese oxide; copper, silver, gold, or a combination thereof; a first additional cation selected from a group consisting of bismuth, lead, and mixtures thereof; and a second additional cation selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4+, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a third additional cation selected from a group consisting of nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a hydroxyl group. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 592Q. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph further comprising a charge balancing anionic species. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the charge balancing anionic species is selected from a group consisting of: fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (FIS ), and mixtures thereof. An amorphous composition comprising a mixed metal manganese dioxide, wherein the amorphous composition has an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 592Q. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein the mixed metal manganese dioxide has a chemical formula of AaBbCcMxMni.xOyOHzDd, [Chemical Formula 1], wherein A in Chemical Formula l is a group I metal, group II metal, ammonium (NH4 +), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3; ‘c’ is between 0 to 5, and ‘x’ is between 0 to 0.5; and, wherein the amorphous composition comprises at least two of A, B, C, and M. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein A in Chemical Formula 1 is selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ^, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (CF), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (FIS ), and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein C is copper. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein c is between 0 and 0.8. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein B is bismuth. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the second embodiment in this paragraph, wherein M is nickel.
[00096] A third embodiment of the invention is a rechargeable battery comprising a housing; an anode material inside the housing; a cathode material inside the housing and electrically separated from the anode material; and, an electrolyte in the housing, wherein the cathode material comprises a mixed metal manganese dioxide an essentially amorphous x-ray powder diffraction pattern, showing no Bragg reflections with an Flo >1, and only peaks with an Flo less than 0.1 in a range of 54 to 59 2Q. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese dioxide has a chemical formula of AaBbCcMxMni. xOyOHzDd, [Chemical Formula 1], wherein A in Chemical Formula 1 is a group I metal, group II metal, ammonium (NH4 +), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3; ‘c’ is between 0 to 5, and ‘x’ is between 0 to 0.5, and, wherein the mixed metal manganese dioxide comprises at least two of A, B, C, and M. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein A in Chemical Formula 1 is selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR.4+, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (O ), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (HS ), and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein C is copper. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein c is between 0 and 0.8. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein B is bismuth. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein M is nickel. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide comprises manganese oxide; copper, silver, gold, or a combination thereof; a first additional cation selected from a group consisting of bismuth, lead, and mixtures thereof; and a second additional cation selected from a group consisting of lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, N ^, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a third additional cation selected from a group consisting of nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, and mixtures thereof. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a hydroxyl group. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the mixed metal manganese oxide further comprises a charge balancing anionic species. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the third embodiment in this paragraph, wherein the charge balancing anionic species is selected from a group consisting of fluorine (F ), chlorine (Cl ), bromine (Br ), carbonate (CO3 2), nitrate (NO3 1), sulfide (S2 ), bisulfide (HS ), and mixtures thereof.
[00097] A fourth embodiment of the invention is a method for forming a composition having a chemical formula of AaBbCcMxMni.xOyOHzDd, [Chemical Formula 1], wherein A in Chemical Formula 1 is a group I metal, group II metal, ammonium (NH4 +), alkyl ammonium ion, a quaternary organic cation, or a mixture thereof, wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3; ‘c’ is between 0 to 5 and ‘x’ is between 0 to 0.5, and wherein the composition comprises at least two of A, B, C, and M, and the method comprising forming a slurry mixture comprising protic solvent and a source for each of Mn, A, B, C, and M; reacting the slurry mixture at elevated temperature with an autogenous pressure; and, then recovering a material comprising the composition from the slurry mixture. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the fourth embodiment in this paragraph, wherein the elevated temperature is from 10°C to 150°C. An embodiment of the invention is one, any or all of prior embodiments in this paragraph up through the fourth embodiment in this paragraph, wherein the slurry mixture is held at a temperature in a range from 10°C to 150°C for a period of time in a range from 30 minutes to 14 days.
[00098] Without further elaboration, it is believed that using the preceding description that one skilled in the art can utilize the present invention to its fullest extent and easily ascertain the essential characteristics of this invention, without departing from the spirit and scope thereof, to make various changes and modifications of the invention and to adapt it to various usages and conditions. The preceding preferred specific embodiments are, therefore, to be construed as merely illustrative, and not limiting the remainder of the disclosure in any way whatsoever, and that it is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.
[00099] In the foregoing, all temperatures are set forth in degrees Celsius and, all parts and percentages are by weight, unless otherwise indicated.
[000100] While at least one exemplary embodiment has been presented in the foregoing detailed description of the invention, it should be appreciated that a vast number of variations exist. It should also be appreciated that the exemplary embodiment or exemplary embodiments are only examples, and are not intended to limit the scope, applicability, or configuration of the invention in any way. Rather, the foregoing detailed description will provide those skilled in the art with a convenient road map for implementing an exemplary embodiment of the invention, it being understood that various changes may be made in the function and arrangement of elements described in an exemplary embodiment without departing from the scope of the invention as set forth in the appended claims and their legal equivalents.

Claims

CLAIMS What is claimed is:
1. A composition comprising: a chemical formula of:
AaBbCcMxMni-xOyOHzDd,
[Chemical Formula 1], wherein A in Chemical Formula l is a group I metal, group II metal, ammonium (NH4 +), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3, ‘c’ is between 0 to 5, and ‘x’ is between 0 to 0.5, and, wherein the composition includes at least two of A, B, C, and M.
2. The composition of claim 1 wherein A in Chemical Formula 1 is selected from the group consisting of: lithium, sodium, potassium, cesium, rubidium, beryllium, magnesium, calcium, strontium, barium, NR4+, and mixtures thereof, with R being, hydrogen, an alkyl group, an aryl group, or combinations thereof.
3. The composition of claim 1 wherein the charge balancing anionic species is selected from the group consisting of: fluorine (F-), chlorine (C1-), bromine (Br-), carbonate (C03-2), nitrate (N03-1), sulfide (S2-), bisulfide (HS-), and mixtures thereof.
4. The composition of claim 1, wherein C is copper; and, wherein c is between 0 and 0.8.
5. The composition of claim 1, wherein B is bismuth.
6. The composition of claim 1, wherein M is nickel.
7. The composition of any one of claims 1 to 6, wherein the composition has an x- ray powder diffraction pattern, showing no Bragg reflections with an I/Io >1, and only peaks with an I/Io less than 0.1 in a range of 54 to 592Q.
8. A method for forming a composition having a chemical formula of AaBbCcMxMni-xOyOHzDd, [Chemical Formula 1], wherein A in Chemical Formula l is a group I metal, group II metal, ammonium (NH4 +), an alkyl ammonium ion, a quaternary organic cation, or a mixture thereof, wherein B in Chemical Formula 1 is bismuth, lead, or a mixture thereof, wherein C in Chemical Formula 1 is copper, silver, gold, or a mixture thereof, wherein M in Chemical Formula 1 is nickel, cobalt, aluminum, scandium, vanadium, chromium, cerium, zinc, or a mixture thereof, wherein D in Chemical Formula 1 is a charge balancing anionic species, wherein a sum of an average valence of A multiplied by ‘a’, an average valence of B multiplied by ‘b’, an average valence of C multiplied by ‘c’, an average valence of M multiplied by ‘x’, and an average valence of Mn multiplied by (1-x) is equal to a sum of 2y, z, and an average valence of D multiplied by ‘d’, wherein ‘a’ is between 0 to 0.4, ‘b’ is between 0 to 0.3; ‘c’ is between 0 to 5 and ‘x’ is between 0 to 0.5, and wherein the composition comprises at least two of A, B, C, and M, and the method comprising: forming a slurry mixture comprising protic solvent and a source for each of Mn, A, B, C, and M; reacting the slurry mixture at elevated temperature with an autogenous pressure; and, then recovering a material comprising the composition from the slurry mixture.
9. The method of claim 8, wherein the elevated temperature is from 10°C to
150°C.
10. The method of claim 8 or 9, wherein the slurry mixture is held at a temperature in a range from 10°C to 150°C for a period of time in a range from 30 minutes to 14 days.
PCT/US2021/070860 2020-07-17 2021-07-12 Mixed metal manganese oxide material Ceased WO2022016179A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202063053302P 2020-07-17 2020-07-17
US63/053,302 2020-07-17

Publications (2)

Publication Number Publication Date
WO2022016179A1 true WO2022016179A1 (en) 2022-01-20
WO2022016179A9 WO2022016179A9 (en) 2022-02-24

Family

ID=79292879

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2021/070860 Ceased WO2022016179A1 (en) 2020-07-17 2021-07-12 Mixed metal manganese oxide material

Country Status (2)

Country Link
US (1) US20220020985A1 (en)
WO (1) WO2022016179A1 (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016061030A1 (en) * 2014-10-13 2016-04-21 Research Foundation Of The City University Of New York Mixed material cathode for secondary alkaline batteries
US20170352875A1 (en) * 2016-06-03 2017-12-07 Toyota Jidosha Kabushiki Kaisha Secondary battery system

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR950001661B1 (en) * 1990-03-27 1995-02-28 아사히가세이고오교가부시끼가이샤 Aluminum oxide, molded article thereof, and method for producing aluminum oxide
US7585474B2 (en) * 2005-10-13 2009-09-08 The Research Foundation Of State University Of New York Ternary oxide nanostructures and methods of making same
JP2022013953A (en) * 2018-10-26 2022-01-19 株式会社豊田自動織機 Electrodes and solid-state lithium-ion secondary batteries

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016061030A1 (en) * 2014-10-13 2016-04-21 Research Foundation Of The City University Of New York Mixed material cathode for secondary alkaline batteries
US20170352875A1 (en) * 2016-06-03 2017-12-07 Toyota Jidosha Kabushiki Kaisha Secondary battery system

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EIN-ELI YAIR, LU SHARON H, RZEZNIK MARIA A, MUKERJEE SANJEEV, XIAO Q. YANG, MCBREEN JAMES: "LiCuJvtn2_O4 Spinels (0.1 x 0.5): A New Class of Cathode Materials for Li Batteries ", J. ELECTROCHEM. SOC., 31 October 1998 (1998-10-31), XP055898338, Retrieved from the Internet <URL:https://www.northeastern.edu/nucret/wp-content/uploads/2017/04/LiCuxMn2-xO4-Spinels-0.1-x-0.5-A-New-Class-of-Cathode-Material-for-Li-Batteries.-II-In-situ-Measurements.pdf> *
WEIFENG WEI, XINWEI CUI, WEIXING CHEN, DOUGLAS G. IVEY: "Manganese oxide-based materials as electrochemical supercapacitor electrodes", CHEMICAL SOCIETY REVIEWS, ROYAL SOCIETY OF CHEMISTRY, UK, vol. 40, no. 3, 1 January 2011 (2011-01-01), UK , pages 1697 - 1721, XP055321876, ISSN: 0306-0012, DOI: 10.1039/C0CS00127A *

Also Published As

Publication number Publication date
WO2022016179A9 (en) 2022-02-24
US20220020985A1 (en) 2022-01-20

Similar Documents

Publication Publication Date Title
AU2023200149B2 (en) Battery including beta-delithiated layered nickel oxide electrochemically active cathode material
Seo et al. Intercalation and conversion reactions of nanosized β-MnO2 cathode in the secondary Zn/MnO2 alkaline battery
US11302917B2 (en) Process for making manganese dioxide and its polymorphs reversible
CN101821878B (en) Positive electrode active material, method for producing same, and electrochemical device
US11276877B2 (en) Stabilized birnessite cathode for high power and high energy density applications
JP2003017057A (en) Lithium vanadium composite oxide for negative electrode active material of lithium secondary battery, method for producing the same, and lithium secondary battery using the same
JP4318002B2 (en) Method for producing positive electrode active material for non-aqueous electrolyte secondary battery
CN110911633A (en) β -delithiated layered nickel oxide electrochemically active cathode material and battery comprising said material
JP5644273B2 (en) Titanium oxide, method for producing the same, and electrochemical device using the same as member
EP3186410A1 (en) Crystalline transition metal oxide particles and continuous method of producing the same
JP2896510B1 (en) Method for producing layered rock salt type lithium cobalt oxide by hydrothermal oxidation method
JP4686871B2 (en) Lithium secondary battery
JP6466074B2 (en) Cathode active material for sodium ion secondary battery
CA3090016A1 (en) Manganese oxide composition and method for preparing manganese oxide composition
JP5819786B2 (en) Lithium cuprate positive electrode material, method for producing the positive electrode material, and lithium secondary battery containing the positive electrode material as a positive electrode active material
US20220020985A1 (en) Mixed metal manganese oxide material
US20220115654A1 (en) Mixed metal manganese oxide material
JP7206808B2 (en) Cobalt-manganese composite oxide, production method thereof, and use thereof
US20230039527A1 (en) Cathode and electrolyte chemistry for scalable zinc ion battery
JP5120919B2 (en) Active material for lithium battery, method for producing the same, and lithium battery using the active material
JP2018043889A (en) Manganese oxide, manganese oxide mixture, and lithium secondary battery using the same
Imai et al. Soft chemistry-derived Al-substituted hydrated nickel hydroxide electrodes for rechargeable aqueous batteries
JP2002075358A (en) Material for positive electrode of lithium ion secondary battery and method for producing the same
JP2006040572A (en) Cathode active material for aqueous lithium secondary battery and aqueous lithium secondary battery
CN112830525B (en) Cathode active material and lithium ion electrochemical system including same

Legal Events

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

Ref document number: 21842179

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 21842179

Country of ref document: EP

Kind code of ref document: A1