US20150140206A1 - High energy materials for a battery and methods for making and use - Google Patents

High energy materials for a battery and methods for making and use Download PDF

Info

Publication number
US20150140206A1
US20150140206A1 US14/604,013 US201514604013A US2015140206A1 US 20150140206 A1 US20150140206 A1 US 20150140206A1 US 201514604013 A US201514604013 A US 201514604013A US 2015140206 A1 US2015140206 A1 US 2015140206A1
Authority
US
United States
Prior art keywords
coating
precursor material
metal
coating precursor
material comprises
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.)
Abandoned
Application number
US14/604,013
Other languages
English (en)
Inventor
Cory O'Neill
Steven Kaye
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.)
Wildcat Discovery Technologies Inc
Original Assignee
Wildcat Discovery Technologies Inc
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 Wildcat Discovery Technologies Inc filed Critical Wildcat Discovery Technologies Inc
Priority to US14/604,013 priority Critical patent/US20150140206A1/en
Publication of US20150140206A1 publication Critical patent/US20150140206A1/en
Assigned to WILDCAT DISCOVERY TECHNOLOGIES, INC reassignment WILDCAT DISCOVERY TECHNOLOGIES, INC ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KAYE, STEVEN, O'NEILL, Cory
Priority to US15/008,252 priority patent/US20160141601A1/en
Assigned to SILICON VALLEY BANK reassignment SILICON VALLEY BANK SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: WILDCAT DISCOVERY TECHNOLOGIES, INC.
Assigned to WILDCAT DISCOVERY TECHNOLOGIES, INC. reassignment WILDCAT DISCOVERY TECHNOLOGIES, INC. RELEASE BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: SILICON VALLEY BANK
Abandoned legal-status Critical Current

Links

Images

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0641—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0694—Halides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0421—Methods of deposition of the material involving vapour deposition
    • H01M4/0423—Physical vapour deposition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention is in the field of battery technology, and more particularly in the area of materials for making high-energy electrodes for batteries, including metal-fluoride materials.
  • One type of battery consists of a negative electrode made primarily from lithium and a positive electrode made primarily from a compound containing a metal and fluorine.
  • a negative electrode made primarily from lithium
  • a positive electrode made primarily from a compound containing a metal and fluorine.
  • lithium ions and electrons are generated from oxidation of the negative electrode while fluoride ions are produced from reduction of the positive electrode.
  • the generated fluoride ions react with lithium ions near the positive electrode to produce a compound containing lithium and fluorine, which may deposit at the positive electrode surface.
  • Metal fluoride based batteries are an attractive energy storage technology because of their extremely high theoretical energy densities.
  • certain metal fluoride active materials can have theoretical energy densities greater than about 1600 Wh/kg or greater than about 7500 Wh/L.
  • metal fluorides have a relatively low raw material cost, for example less than about $10/kg.
  • a number of technical challenges currently limit their widespread use and realization of their performance potential.
  • metal fluoride active materials have electrochemical potentials greater than about 2.5 V because of their relatively large bandgap produced by the highly ionic bonding between the metal and fluorine, and in particular between a transition metal and fluorine.
  • one of the drawbacks to wide bandgap materials is the intrinsically low electronic conductivity that results from the wide bandgap. As a result of this low conductivity, discharge rates of less than 0.1 C are required in order to obtain full theoretical capacity. More typically, discharge rates of 0.05 C to 0.02 C are reported in the literature. Such low discharge rates limit the widespread use of metal fluoride active materials.
  • the second limitation to extended cycle life is the mechanical stress imparted to the binder materials by the metal fluoride particles as a result of the volume expansion that occurs during the conversion reaction. Over time, the binder is pulverized, compromising the integrity of the cathode. Notably, for the metal fluoride CuF 2 , no demonstrations of rechargeability have been reported.
  • CuF 2 For CuF 2 , an additional challenge prevents rechargeability.
  • the potential required to recharge a CuF 2 electrode is 3.55V.
  • Cu metal oxidizes to Cu 2+ at approximately 3.4 V vs. Li/Li + .
  • the oxidized copper can migrate to the anode, where it is irreversibly reduced back to Cu metal.
  • Cu dissolution competes with the recharge of Cu+2LiF to CuF 2 , preventing cycling of the cell.
  • the Cu metal accumulating on the anode surface can increase the impedance and/or destroy the solid-electrolyte interphase (SEI) on the anode.
  • SEI solid-electrolyte interphase
  • Certain embodiments of the present invention can be used to form electrochemical cells having metal fluoride active material that exhibit improved rate performance, improved energy efficiency, and improved cycle life when compared to prior batteries.
  • Certain embodiments of the invention include a method of making a composition for use in forming a cathode for a battery.
  • the method includes coating a metal fluoride material with a coating precursor material including a metal or a metal complex and annealing coated metal fluoride material, wherein at least a portion of the metal fluoride material and at least a portion of the coating undergo a phase change.
  • the metal fluoride material is preferably CuF 2 .
  • the metal can be, for example, Ni, Ba, or Ta.
  • the metal complex can be, for example a metal oxide, such as A 12 O 3 , SiO 2 , Ta 2 O 5 , TiO 2 ; a metal nitride, such as AlN, TaN; a metal silicate, such as ZrSiO 4 ; or other materials that are volatile enough to be evaporated and re-condensed onto a substrate.
  • the annealing temperature is less than 450 degrees C, less than 400 degrees C, less than 325 degrees C, or less than 200 degrees C. Preferably, the annealing temperature is about 325 degrees C. The temperature is chosen such that it is sufficiently high for the metal complex to react with the metal fluoride, but not high enough to decompose the metal fluoride. Without such heat treatment and the resulting reaction, the material is not rechargeable, as is demonstrated by experiments described herein.
  • Certain embodiments of the invention include a composition formed by the methods disclosed herein.
  • the composition is characterized by having reversible capacity.
  • the composition can include particles with a grain size greater than 100 nm, 110 nm, 120 nm, or 130 nm.
  • the composition can include a particle having a first phase and a coating on the particle having a second phase.
  • the first phase includes the metal fluoride and the second phase includes the metal oxide.
  • the coating can be covalently bonded to the particle.
  • Certain embodiments of the invention include batteries having electrodes formed from the compositions disclosed herein, the method of making such batteries, and the method of use of such batteries.
  • FIG. 1 illustrates electrochemical characterization of different hybrid cathode formulations according to embodiments of the invention in which the content of a conductive precursor material is varied in the cathode.
  • FIG. 2 illustrates electrochemical characterization of a cathode formulation from FIG. 1 in which the voltage of a hybrid cathode according to embodiments of the invention is plotted against the capacity for the first and second cycles.
  • FIG. 3 illustrates electrochemical characterization of different hybrid cathode formulations according to embodiments of the invention in which the discharge is plotted as a function of cycle for 10 cycles.
  • FIG. 4 illustrates electrochemical characterization of a hybrid cathode formed from a metal fluoride and a reactant material according to certain embodiments.
  • the cathode demonstrates rechargeability.
  • FIG. 5 illustrates a powder X-ray diffraction pattern of a material used to form a rechargeable metal fluoride cathode.
  • FIG. 6 illustrates second cycle discharge capacity for a variety of hybrid cathode materials used according to embodiments of the invention.
  • FIG. 7 illustrates second cycle discharge capacity for a hybrid cathode material used according to embodiments of the invention versus annealing temperature.
  • FIG. 8 illustrates second cycle the capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt % CuF 2 with 15 wt % of certain metal oxides (in this case NiO or TiO 2 ) at certain annealing temperatures.
  • certain metal oxides in this case NiO or TiO 2
  • FIG. 9 illustrates the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt % CuF 2 with 15 wt % of certain metal oxides (in this case NiO or TiO 2 ) for certain annealing times.
  • certain metal oxides in this case NiO or TiO 2
  • FIG. 10 illustrates the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, 90 wt %, or 95 wt % CuF 2 with 5 wt %, 10 wt %, 15 wt % of NiO.
  • FIG. 11 illustrates the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO as a function of milling energy.
  • FIG. 12 illustrates the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO as a function of milling time.
  • FIG. 13 illustrates the second cycle reversible capacity measured for various starting materials used to react with CuF 2 .
  • FIG. 14 illustrates the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting CuF 2 with nickel(II) acetylacetonate using various processing conditions.
  • FIG. 15 illustrates the capacity as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO and for a control material.
  • FIG. 16 illustrates a galvanostatic intermittent titration technique measurement for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • FIG. 17 illustrates the capacity of full cells and half cells as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • FIG. 18 illustrates voltage traces of the full cell and half cells prepared as described in relation to FIG. 17 .
  • FIG. 19 illustrates the capacity retention of full cells and half cells as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • FIG. 20 illustrates the second cycle reversible capacity measured for various coating precursor materials used to react with CuF 2 .
  • conductive refers to the intrinsic ability of a material to facilitate electron or ion transport and the process of doing the same.
  • the terms include materials whose ability to conduct electricity may be less than typically suitable for conventional electronics applications but still greater than an electrically-insulating material.
  • active material refers to the material in an electrode, particularly in a cathode, that donates, liberates, or otherwise supplies the conductive species during an electrochemical reaction in an electrochemical cell.
  • transition metal refers to a chemical element in groups 3 through 12 of the periodic table, including scandium (Sc), titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), yttrium (Y), zirconium (Zr), niobium (Nb), molybdenum (Mo), technetium (Tc), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), cadmium (Cd), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), mercury (Hg), rutherfordium (Rf), dubnium (Db), seaborgium (Sg), bohrium (Bh), hassium (H
  • halogen refers to any of the chemical elements in group 17 of the periodic table, including fluorine (F), chlorine (Cl), bromine (Br), iodine (I), and astatine (At).
  • chalcogen refers to any of chemical elements in group 16 of the periodic table, including oxygen (O), sulfur (S), selenium (Se), tellurium (Te), and polonium (Po).
  • alkali metal refers to any of the chemical elements in group 1 of the periodic table, including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and francium (Fr).
  • alkaline earth metals refers to any of the chemical elements in group 2 of the periodic table, including beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), and radium (Ra).
  • rare earth element refers to scandium (Sc), yttrium (Y), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), ytterbium (Yb), and lutetium (Lu).
  • a rate “C” refers to either (depending on context) the discharge current as a fraction or multiple relative to a “1 C” current value under which a battery (in a substantially fully charged state) would substantially fully discharge in one hour, or the charge current as a fraction or multiple relative to a “1 C” current value under which the battery (in a substantially fully discharged state) would substantially fully charge in one hour.
  • a novel active material is prepared for use in a cathode with metal fluoride (MeF x ) active materials.
  • the novel active material sometimes referred to herein as a hybrid material, is prepared by combining a metal fluoride and a metal complex, followed by heat treatment of the mixture under an inert atmosphere according to the Formula (I)
  • the heat treatment of the metal fluoride and metal complex causes a reaction to form a new phase according to the formula (II)
  • the heat treatment causes the formation of covalent bonds between the metal fluoride and the metal complex, improving conductivity and passivating the surface.
  • Suitable metal complexes which can act as precursors for the reaction described herein, for use in synthesizing the active material include, but are not limited to, MoO 3 , MoO 2 , NiO, CuO, VO 2 , V 2 O 5 , TiO 2 , A 12 O 3 , SiO 2 , LiFePO 4 , LiMe T PO 4 (where Me T is one or more transition metal(s)), metal phosphates, and combinations thereof. According to embodiments of the invention, these oxides can be used in Formula (I).
  • the synthetic route for achieving the active material may vary, and other such synthetic routes are within the scope of the disclosure.
  • the material can be represented by Me a Me′ b X c F and in the examples herein is embodied by a Cu 3 Mo 2 O 9 active material.
  • Other active materials are within the scope of this disclosure, for example, NiCuO 2 , Ni 2 CuO 3 , and Cu 3 TiO 4 .
  • the coating materials disclosed herein provide rechargeability to otherwise non-rechargeable metal fluoride materials.
  • the rechargeability may be due to the electrochemical properties of the novel hybrid material, the coating of the metal fluoride to prevent copper dissolution, or a more intimate interface between the metal fluoride and the coating material as a result of the heat treatment and reaction.
  • the novel hybrid material may provide a kinetic barrier to the Cu dissolution reaction, or to similar dissolution reactions for other metal fluoride materials to the extent such dissolution reactions occur in the cycling of electrochemical cells.
  • Suitable coating precursors include materials that decompose to form metal oxides (and in particular, transition metal oxides) as opposed to using a metal oxide to directly react with the metal fluoride.
  • Suitable coating precursors include, but are not limited to, metal acetates, metal acetylacetonates, metal hydroxides, metal ethoxides, and other similar organo-metal complexes.
  • the final rechargeable material is not necessarily a pure oxide or a purely crystalline material.
  • the reaction of Formula II predicts that there would not be a pure oxide or a purely crystalline material.
  • the metal oxide precursor or metal oxide material can form a coating, or at least a partial coating, on the metal fluoride active material.
  • the reaction of the metal oxide precursor or metal oxide material with the surface of the metal fluoride (and in particular copper fluoride) active material is important for generating a rechargeable electrode active material.
  • Milling vessels were loaded with CuF 2 at from about 85 wt % to about 95 wt % and reactant (metal oxide or metal oxide precursor) at from about 5 wt % to about 15 wt %, and the vessels were sealed. The mixture was milled. After milling, samples were annealed at from about 200 degrees C to about 575 degrees C for 1 to 12 hours under flowing N 2 . Specific hybrid-forming reactants were processed as described below.
  • Milling vessels were loaded with CuF 2 (85 wt %) and MoO 3 (15 wt %), sealed, and then milled. After milling, samples were annealed at 450 degrees C for 6 hours under flowing N 2 .
  • Milling vessels were loaded with CuF 2 (85 wt %) and NiO (15 wt %), sealed, and then milled. After milling, samples were annealed at 325 degrees C for 6 hours under flowing N 2 .
  • a fine dispersion of CuF 2 was prepared by milling in the presence of THF (40-120 mg CuF 2 /mL THF). The dispersed sample was then added to a solution of Ni(AcAc)2 in THF such that Nickel(II) acetylacetonate accounted for 15 wt % of the solids in the solution. The solution was then agitated by either shaking, sonication, or low energy milling for from about 1 to about 12 hours. The solution was then dried at room temperature under vacuum and the resulting solid was annealed at 450 degrees C for 6 hours under dry air.
  • the coating material (nickel metal) was vaporized and then physically condensed onto the substrate at 20 weight percent. X-ray diffraction measurements were performed on the coated material to confirm the bulk CuF 2 was not altered. The coated material was then annealed similarly to materials prepared by other methods.
  • CuF 2 was coated with TiO 2 by atomic layer deposition methods.
  • the expected coating thickness was about 8.5 nm based on ellipsometry measurements on a silicon witness sample, which represented a nominal 3 weight percent coating on the CuF 2 .
  • the coated material was then annealed similarly to materials prepared by other methods.
  • Cathodes were prepared using a formulation composition of 80:15:5 (active material:binder:conductive additive) according to the following formulation method: 133 mg PVDF (Sigma Aldrich) and about 44 mg Super P Li (Timcal) was dissolved in 10 mL NMP (Sigma Aldrich) overnight. 70 mg of coated composite powder was added to 1 mL of this solution and stirred overnight. Films were cast by dropping about 70 ⁇ L of slurry onto stainless steel current collectors and drying at 150 degrees C for about 1 hour. Dried films were allowed to cool, and were then pressed at 1 ton/cm 2 . Electrodes were further dried at 150 degrees C under vacuum for 12 hours before being brought into a glove box for battery assembly.
  • Electrodes and cells were electrochemically characterized at 30 degrees C with a constant current C/50 charge and discharge rate between 4.0 V and 2.0 V. A 3 hour constant voltage step was used at the end of each charge.
  • cathodes were lithiated pressing lithium foil to the electrode in the presence of electrolyte (1M LiPF 6 in 1:2 EC:EMC) for about 15 minutes. The electrode was then rinsed with EMC and built into cells as described above, except graphite was used as the anode rather than lithium.
  • FIG. 1 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the second cycle discharge capacity of three different cathode formulations containing a LiFePO 4 material is plotted as a function of LiFePO 4 content (labeled LFP) in the cathode in FIG. 1 . The dotted line depicts the theoretical capacity of LiFePO 4 .
  • One cathode formulation is 100% LiFePO 4 .
  • Another cathode formulation is a combination of CuF 2 and LiFePO 4 in which the content of LiFePO 4 was varied from 10% to 50% of the total weight of conductive material.
  • the third cathode formulation is a combination of CuF 2 and the conventional conductive oxide MoO 3 and LiFePO 4 in which the content of LiFePO 4 was varied from 10% to 50% of the total weight of conductive material.
  • FIG. 1 demonstrates that all of the CuF 2 /LiFePO 4 matrices are rechargeable.
  • the (CuF 2 /MoO 3 )/LiFePO 4 hybrid cathode containing 50% LiFePO 4 is also able to recharge.
  • FIG. 1 further demonstrates a direct relationship between the capacity and the percent content of LiFePO 4 .
  • FIG. 2 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the voltage of a hybrid cathode is plotted against the capacity for the first and second cycles. The dashed line indicates the expected theoretical capacity from the LiFePO 4 content in cathode.
  • the cathode formulation is the CuF 2 (70%)/LiFePO 4 (30%) hybrid cathode from FIG. 1 .
  • the first cycle very little discharge capacity is observed, indicating that the LiFePO 4 material is not capable of accepting charge on this cycle. Without being bound to a particular theory or mechanism of action, the LiFePO 4 material may not accept charge as a result of defects introduced during milling. This data suggests that all of the capacity observed during the first and second cycles can be attributed solely to the CuF 2 .
  • FIG. 3 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the discharge capacity for cells with a range of LiFePO 4 content is plotted as a function of cycle for 10 cycles.
  • the cathode formulation is CuF 2 with LiFePO 4 content ranging from 10% to 50% of the total weight of conductive material.
  • FIG. 4 demonstrates that the hybrid cathode is able to consistently recharge across a number of cycles. Based on data from FIG. 2 , it is expected that the discharge capacity is contributed solely by CuF 2 and not LiFePO 4 . This is a significant finding because CuF 2 has not been previously shown to have such significant reversible capacity.
  • the combination of certain conductive materials with CuF 2 renders the CuF 2 cathode material rechargeable.
  • FIG. 4 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the first and second cycle voltage traces for a cell containing a cathode formed from a metal fluoride and the new hybrid material.
  • the metal fluoride active material is CuF 2 and the hybrid material is Cu 3 Mo 2 O 9 .
  • FIG. 4 demonstrates that the cell has about 140 mAh/g of reversible capacity. Previously known cathodes containing CuF 2 have not demonstrated such significant reversible capacity.
  • FIG. 5 illustrates the results of structural characterization of certain embodiments disclosed herein. Specifically, the powder X-ray diffraction pattern of the material forming the cathode tested in FIG. 4 is shown along with the powder X-ray diffraction patterns of CuF 2 and Cu 3 Mo 2 O 9 .
  • FIG. 5 demonstrates that the material contains phases rich in CuF 2 and phases rich in Cu 3 Mo 2 O 9 . Thus, FIG. 5 demonstrates a new hybrid material in combination with a metal fluoride active material.
  • grain size analysis of this powder X-ray diffraction data shows that the CuF 2 has a grain size greater than 130 nm. This is a significant finding since such comparatively large particles were thought to be too large to provide good electrochemical performance.
  • the reactions described herein yield a new material at least at the surface of the particles of the metal fluoride active material.
  • the novel material present at least at the surface of the particles of the metal fluoride active material is believed to provide many of the benefits disclosed herein.
  • FIG. 6 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the second cycle discharge capacity of CuF 2 with various materials and annealing temperatures. FIG. 6 shows many oxide materials that provide recharge capability, demonstrated by capacities greater than 100 mAh/g.
  • Table 1 presents the results of further electrochemical characterization of certain embodiments disclosed herein.
  • Table 1 shows that many metal oxide and metal oxide precursor starting materials can be used in the reactions described herein to yield rechargeable metal fluoride electrode materials.
  • the materials in Table 1 include metal oxides, metal phosphates, metal fluorides, and precursors expected to decompose to oxides. In particular, nickel oxide showed excellent performance.
  • FIG. 7 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, the second cycle discharge capacity for cells containing a cathode formed from a metal fluoride and the precursor material treated at different temperatures.
  • the metal fluoride active material is CuF 2 and the precursor material is NiO.
  • FIG. 7 shows a peak for cycle 2 capacity at about 325 degrees C for NiO precursors, with nearly 250 mAh/g discharge capacity.
  • FIG. 8 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt % CuF 2 with 15 wt % of certain metal oxides (in this case NiO or TiO 2 ) at certain annealing temperatures.
  • the mixtures were milled at high energy for about 20 hours.
  • the anneal temperatures ranged from about 225 degrees C to about 450 degrees C and the anneal time was 6 hours.
  • the 325 degree C anneal temperature for the NiO starting material generated the best performance.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.02 C and over a voltage range of 2.0 V to 4.0 V.
  • FIG. 9 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt % CuF 2 with 15 wt % of certain metal oxides (in this case NiO or TiO 2 ) for certain annealing times.
  • the mixtures were milled at high energy for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 1 hour, 6 hours, or 12 hours.
  • the 6 hour anneal time yielded the best results for both the NiO and TiO 2 starting materials, and the NiO starting material generated better performance.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.02 C and over a voltage range of 2.0 V to 4.0 V.
  • FIG. 10 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, 90 wt %, or 95 wt % CuF 2 with 5 wt %, 10 wt %, 15 wt % of NiO.
  • the mixtures were milled at high energy for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours.
  • Using 10 wt % or 15 wt % of the NiO starting material generated better performance.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.02 C and over a voltage range of 2.0 V to 4.0 V.
  • FIG. 11 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • the mixtures were milled at various energies comparable to milling on a Fritch Pulverisette 7 Planatery Mill at 305, 445, 595, and 705 RPM for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours. Performance improves with increasing milling energy, suggesting that intimate physical interaction of the materials is required.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.05 C and over a voltage range of 2.0 V to 4.0 V.
  • FIG. 12 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • the mixtures were milled for various times (3 hours, 20 hours, or 40 hours) at a high energy (comparable to 705 RPM on Fritch Pulverisette 7).
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours. Performance does not improve after 20 hours of milling.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.05 C and over a voltage range of 2.0 V to 4.0 V.
  • FIG. 13 illustrates the results of electrochemical characterization of certain embodiments disclosed herein. Specifically, FIG. 13 shows the second cycle reversible capacity measured for various starting materials used to react with CuF 2 .
  • the starting materials include NiO, nickel(II) acetylacetonate (Ni acac in Table 1), nickel acetate, nickel hydroxide, NiCO 3 *Ni(OH) 2 , Ni(C 2 O 2 ), Ni(CP) 2 , and Ni.
  • the starting materials react to form a new phase.
  • the materials react with the surface of the CuF 2 particles. Additionally, the anneal atmosphere was either N 2 or dry air.
  • the precursor starting materials decompose to NiO (although this depends on the atmosphere for some precursors) at or below the annealing temperatures used for the reaction.
  • the precursors that are soluble or have low boiling points can enable solution or vapor deposition processing methods.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a rate of 0.05 C and over a voltage range of 2.0 V to 4.0 V. Several materials show similar performance to the NiO baseline.
  • FIG. 14 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting CuF 2 with nickel(II) acetylacetonate using various processing conditions.
  • the CuF 2 was dispersed using methods described herein.
  • the coatings were applied using mill coating techniques (that is, agitating the mixture in a milling apparatus) or by solution coating techniques (including solution coating driven by physisorption). All samples were annealed under dry air.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC.
  • the testing was performed at a rate of 0.05 C and over a voltage range of 2.0 V to 4.0 V. Testing demonstrates that solution coating methods can provide similar performance to the mill coating techniques.
  • FIG. 20 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the second-cycle capacity retention and reversible capacity for cathode active materials formed from reacting CuF 2 with coatings formed from various coating methods and from various precursors.
  • the precursors included NiO, Ni, TiO 2 , nickel(II) acetylacetonate, and nickel acetate. All five precursor types were applied according to the mill coating techniques (that is, agitating the mixture in a milling apparatus). Solution coating techniques were used for nickel(II) acetylacetonate, and nickel acetate.
  • PVD Physical vapor deposition
  • ALD atomic layer deposition
  • the solution, vapor, and atomic layer deposition methods can provide comparatively more uniform coatings on metal fluoride particles than the coatings obtained by milling methods.
  • a comparatively thinner, more uniform coatings can provide the benefits of the coating material, such as more complete protection of the metal fluoride particle, with less precursor material.
  • thin, conformal coatings can provide an advantage in terms of weight-normalized reversible capacity.
  • FIG. 20 shows that although absolute reversible capacity was inferior for solution and vapor coatings as compared to milled coatings, the reversible capacity per weight percentage of coating was significantly improved.
  • the atomic layer deposition coating method yielded greater than about 60% more reversible capacity per coating weight than the milled coating method.
  • the ALD coated material had a coating that was about 8 nm thick and less than about 3 weight percent of the coated particle.
  • the non-milling coating methods shown in FIG. 20 are compatible with a subset of the metal complexes disclosed herein.
  • a variety of coating materials is possible with atomic layer deposition methods including metals (e.g., Ni), metal oxides (e.g., A 12 O 3 , SiO 2 , Ta 2 O 5 , TiO 2 ), metal nitrides (e.g., AlN, TaN), and others.
  • Physical vapor deposition techniques can also deposit coatings of a wide number of materials including metals (e.g., Ni, Ba, Ta), metal oxides (e.g., SiO 2 , Ta 2 O 5 , TiO 2 , NiO), metal nitrides (e.g., TiN, AlN), metal silicates (e.g., ZrSiO 4 ) or other materials that are volatile enough to be evaporated and re-condensed onto a substrate.
  • metals e.g., Ni, Ba, Ta
  • metal oxides e.g., SiO 2 , Ta 2 O 5 , TiO 2 , NiO
  • metal nitrides e.g., TiN, AlN
  • metal silicates e.g., ZrSiO 4
  • FIG. 15 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the capacity as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO and for a control material.
  • the NiO/CuF 2 mixture was milled at high energy for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed at a cycle 1 rate of 0.02 C, a cycle 2 rate of 0.05 C, and a cycle 3 through cycle 25 rate of 0.5 C and over a voltage range of 2.0 V to 4.0 V.
  • the cell cycles reversibly for extended cycling with capacity greater than 100 mAh/g for 25 cycles. Further, the reacted NiO/CuF 2 active material demonstrates retention of 80% of cycle 3 capacity as far out as cycle 15.
  • the control material which was prepared according to the process described in Badway, F. et al., Chem. Mater ., 2007, 19, 4129, does not demonstrate any rechargeable capacity. Thus, the material prepared according to embodiments described herein is significantly superior to known materials processed according to known methods.
  • FIG. 16 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, a galvanostatic intermittent titration technique (GITT) measurement for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO and for a control material.
  • the NiO/CuF 2 mixture was milled at high energy for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC. The testing was performed over a voltage range of 2.0 V to 4.0 V at a rate of 0.1 C and with a 10 hour relaxation time.
  • GITT galvanostatic intermittent titration technique
  • the GITT measurement relaxation points show low voltage hysteresis (about 100 mV), which indicate that the overpotential and/or underpotential are likely caused by kinetic and not thermodynamic limitations. This is consistent with other properties and characteristics observed for the reacted NiO/CuF 2 active material.
  • FIG. 17 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the capacity of full cells and half cells as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • the NiO/CuF 2 mixture was milled at high energy for about 20 hours.
  • the anneal temperature was 325 degrees C and the anneal time was 6 hours.
  • the label “Cu+2LiF” indicated that the NiO/CuF 2 electrode was lithiated by pressing Li foil to CuF2 electrode in the presence of electrolyte as described above.
  • the other half cell was lithiated electrochemically in the initial cycles.
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC.
  • the testing was performed over a voltage range of 2.0 V to 4.0 V.
  • Half cell performance is essentially identical between the two lithiation methods after cycle 2, while full cell shows additional irreversible capacity loss as compared to the half cells but similar capacity retention.
  • FIG. 18 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the voltage traces of the full cell and half cells prepared as described in relation to FIG. 17 .
  • the full cell has similar charge capacity to the half cells, but larger irreversible capacity loss and lower discharge voltage (which can indicate increased cell impedance).
  • FIG. 18 demonstrates that the full cell has about 250 mAh/g of reversible capacity and about 500 mV hysteresis between charge and discharge plateau voltages.
  • FIG. 19 illustrates the results of electrochemical characterization of certain embodiments disclosed herein, specifically, the capacity retention of full cells and half cells as a function of cycle for cathode active materials formed from reacting 85 wt %, CuF 2 with 15 wt % of NiO.
  • the results from a control material are also depicted.
  • the full cell and half cells were prepared as described in relation to FIG. 17 .
  • the cells used a Li anode and an electrolyte containing 1M LiPF 6 in EC:EMC.
  • the testing was performed at a cycle 1 rate of 0.1 C and over a voltage range of 2.0 V to 4.0 V.
  • the capacity retention is essentially identical for the full and half cells of the NiO/CuF 2 active material.
  • the control material shows essentially no rechargeable capacity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
US14/604,013 2013-03-15 2015-01-23 High energy materials for a battery and methods for making and use Abandoned US20150140206A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/604,013 US20150140206A1 (en) 2013-03-15 2015-01-23 High energy materials for a battery and methods for making and use
US15/008,252 US20160141601A1 (en) 2013-03-15 2016-01-27 High energy materials for a battery and methods for making and use

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US201361786602P 2013-03-15 2013-03-15
PCT/US2014/028506 WO2014144202A1 (en) 2013-03-15 2014-03-14 High energy materials for a battery and methods for making and use
US14/604,013 US20150140206A1 (en) 2013-03-15 2015-01-23 High energy materials for a battery and methods for making and use

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2014/028506 Continuation-In-Part WO2014144202A1 (en) 2011-09-13 2014-03-14 High energy materials for a battery and methods for making and use

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US15/008,252 Continuation US20160141601A1 (en) 2013-03-15 2016-01-27 High energy materials for a battery and methods for making and use

Publications (1)

Publication Number Publication Date
US20150140206A1 true US20150140206A1 (en) 2015-05-21

Family

ID=51537644

Family Applications (2)

Application Number Title Priority Date Filing Date
US14/604,013 Abandoned US20150140206A1 (en) 2013-03-15 2015-01-23 High energy materials for a battery and methods for making and use
US15/008,252 Abandoned US20160141601A1 (en) 2013-03-15 2016-01-27 High energy materials for a battery and methods for making and use

Family Applications After (1)

Application Number Title Priority Date Filing Date
US15/008,252 Abandoned US20160141601A1 (en) 2013-03-15 2016-01-27 High energy materials for a battery and methods for making and use

Country Status (6)

Country Link
US (2) US20150140206A1 (ja)
EP (1) EP2973804B1 (ja)
JP (2) JP6474779B2 (ja)
KR (2) KR20150120498A (ja)
CN (1) CN105051955B (ja)
WO (1) WO2014144202A1 (ja)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10707526B2 (en) 2015-03-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050191554A1 (en) * 2002-10-31 2005-09-01 Mitsubishi Chemical Corporation Additive for positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery, and positive electrode and lithium secondary battery using the positive electrode material for lithium secondary battery
US20080199772A1 (en) * 2007-02-02 2008-08-21 Glenn Amatucci Metal Fluoride And Phosphate Nanocomposites As Electrode Materials
US8119285B2 (en) * 2003-10-27 2012-02-21 Mitsui Engineering & Shipbuilding Co., Ltd. Cathode material for secondary battery, method for producing cathode material for secondary battery and secondary battery
US20120305855A1 (en) * 2011-05-31 2012-12-06 Korea Electronics Technology Institute Positive electrode material for secondary battery and method for manufacturing the same

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3680441B2 (ja) * 1996-10-03 2005-08-10 株式会社デンソー 非水電解液二次電池
US6777132B2 (en) * 2000-04-27 2004-08-17 Valence Technology, Inc. Alkali/transition metal halo—and hydroxy-phosphates and related electrode active materials
JP2002015727A (ja) * 2000-06-29 2002-01-18 Toyo Kohan Co Ltd リチウム系二次電池
JP2002198061A (ja) * 2000-11-17 2002-07-12 Wilson Greatbatch Ltd 二重集電体カソード構造を用いた短絡安全特性を有するアルカリ金属電気化学セル
US9065137B2 (en) * 2002-10-01 2015-06-23 Rutgers, The State University Of New Jersey Copper fluoride based nanocomposites as electrode materials
TWI240555B (en) * 2004-07-01 2005-09-21 Primax Electronics Ltd Image scanner
JP2008186595A (ja) * 2007-01-26 2008-08-14 Toyota Motor Corp ２次電池
WO2009048146A1 (ja) * 2007-10-10 2009-04-16 Kobelco Research Institute, Inc. 二次電池用負極活物質及びこれを用いた二次電池並びに空気二次電池

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050191554A1 (en) * 2002-10-31 2005-09-01 Mitsubishi Chemical Corporation Additive for positive electrode material for lithium secondary battery, positive electrode material for lithium secondary battery, and positive electrode and lithium secondary battery using the positive electrode material for lithium secondary battery
US8119285B2 (en) * 2003-10-27 2012-02-21 Mitsui Engineering & Shipbuilding Co., Ltd. Cathode material for secondary battery, method for producing cathode material for secondary battery and secondary battery
US20080199772A1 (en) * 2007-02-02 2008-08-21 Glenn Amatucci Metal Fluoride And Phosphate Nanocomposites As Electrode Materials
US20120305855A1 (en) * 2011-05-31 2012-12-06 Korea Electronics Technology Institute Positive electrode material for secondary battery and method for manufacturing the same

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10707526B2 (en) 2015-03-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
US11271248B2 (en) 2015-03-27 2022-03-08 New Dominion Enterprises, Inc. All-inorganic solvents for electrolytes
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
US12119452B1 (en) 2016-09-27 2024-10-15 New Dominion Enterprises, Inc. All-inorganic solvents for electrolytes

Also Published As

Publication number Publication date
JP2017092042A (ja) 2017-05-25
CN105051955B (zh) 2018-04-03
KR20150120498A (ko) 2015-10-27
US20160141601A1 (en) 2016-05-19
CN105051955A (zh) 2015-11-11
KR20170117237A (ko) 2017-10-20
EP2973804B1 (en) 2018-06-13
WO2014144202A1 (en) 2014-09-18
EP2973804A4 (en) 2017-01-18
JP2016516281A (ja) 2016-06-02
EP2973804A1 (en) 2016-01-20
JP6474779B2 (ja) 2019-02-27

Similar Documents

Publication Publication Date Title
US9490475B2 (en) High energy cathode for a battery
CN108539139B (zh) 锂离子二次电池用正极材料及其制造方法
US9159994B2 (en) High energy materials for a battery and methods for making and use
JP4575597B2 (ja) リチウムイオン電池に使用するためのリチウム基剤リン酸塩
US9793538B2 (en) LMFP cathode materials with improved electrochemical performance
KR101925105B1 (ko) 양극 활물질, 이의 제조방법 및 이를 포함하는 리튬 이차 전지
Applestone et al. Cu 2 Sb–Al 2 O 3–C nanocomposite alloy anodes with exceptional cycle life for lithium ion batteries
US8916062B2 (en) High energy materials for a battery and methods for making and use
JP2019164961A (ja) 合金、負極活物質、負極及び非水電解質蓄電素子
US20230343954A1 (en) Cathode coating
US12002955B2 (en) Cathode active material for lithium secondary battery
JP2000512425A (ja) リチウム―金属―カルコゲン化物混合陰極を有するリチウムセル
CN117916908A (zh) 具有涂覆的无序岩盐材料的阴极
KR101584114B1 (ko) 금속이 코팅된 전극 활물질의 전구체 및 그의 제조방법
US9985280B2 (en) High energy materials for a battery and methods for making and use
US10903483B2 (en) High energy materials for a battery and methods for making and use
US20160141601A1 (en) High energy materials for a battery and methods for making and use
US20150372302A1 (en) High energy cathode materials and methods of making and use
KR20220088884A (ko) Lmo 캐소드 조성물
US9093703B2 (en) High energy materials for a battery and methods for making and use
US20220166057A1 (en) Solid ion conductor, solid electrolyte and electrochemical device including the same, and method of preparing the solid ion conductor
US10205167B2 (en) High energy materials for a battery and methods for making and use
CN103700852A (zh) 用于电化学氧化还原反应中的组合物和电池
US20220263074A1 (en) Positive electrode active material for lithium secondary battery

Legal Events

Date Code Title Description
AS Assignment

Owner name: WILDCAT DISCOVERY TECHNOLOGIES, INC, CALIFORNIA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:O'NEILL, CORY;KAYE, STEVEN;SIGNING DATES FROM 20150609 TO 20150813;REEL/FRAME:036381/0592

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION

AS Assignment

Owner name: SILICON VALLEY BANK, CALIFORNIA

Free format text: SECURITY INTEREST;ASSIGNOR:WILDCAT DISCOVERY TECHNOLOGIES, INC.;REEL/FRAME:041255/0427

Effective date: 20160926

AS Assignment

Owner name: WILDCAT DISCOVERY TECHNOLOGIES, INC., CALIFORNIA

Free format text: RELEASE BY SECURED PARTY;ASSIGNOR:SILICON VALLEY BANK;REEL/FRAME:060063/0733

Effective date: 20220512