US20070160519A1 - Method Of Making Active Materials For Use In Secondary Electrochemical Cells - Google Patents

Method Of Making Active Materials For Use In Secondary Electrochemical Cells Download PDF

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US20070160519A1
US20070160519A1 US11/682,339 US68233907A US2007160519A1 US 20070160519 A1 US20070160519 A1 US 20070160519A1 US 68233907 A US68233907 A US 68233907A US 2007160519 A1 US2007160519 A1 US 2007160519A1
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Prior art keywords
precursor
vpo
carbon
mixture
temperature
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Jeremy Barker
Richard Gover
Paul Burns
Aiden Bryan
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Valence Technology Inc
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Valence Technology Inc
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Priority claimed from US11/277,746 external-priority patent/US20090220838A9/en
Application filed by Valence Technology Inc filed Critical Valence Technology Inc
Priority to US11/682,339 priority Critical patent/US20070160519A1/en
Assigned to VALENCE TECHNOLOGY, INC. reassignment VALENCE TECHNOLOGY, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BRYAN, AIDEN, BURNS, PAUL, BARKER, JEREMY, GOVER, RICHARD
Publication of US20070160519A1 publication Critical patent/US20070160519A1/en
Priority to KR1020097018485A priority patent/KR101524883B1/ko
Priority to CA002679048A priority patent/CA2679048A1/en
Priority to EP08731351.6A priority patent/EP2115802A4/en
Priority to CN200880007225A priority patent/CN101627493A/zh
Priority to PCT/US2008/055801 priority patent/WO2008109602A2/en
Priority to US13/106,196 priority patent/US8313719B2/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/455—Phosphates containing halogen
    • 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
    • H01M4/36—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • 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 relates to the novel preparation of a nanocrystalline VPO 4 precursor and in another embodiment to an amorphous V—P—O/C precursor (or V—P—O-carbon composite material/precursor).
  • the invention further relates to the use of this VPO 4 precursor or V—P—O/C precursor in methods for making vanadium phosphate compounds.
  • Such methods for making vanadium phosphates are beneficial in that the methods proceed at faster reaction rates and at lower temperatures then known methods for making vanadium phosphates.
  • Such precursors also produce a purer product.
  • the vanadium phosphate compounds so prepared are electroactive and are useful in making electrochemical cells.
  • a battery pack consists of one or more electrochemical cells or batteries, wherein each cell typically includes a positive electrode, a negative electrode, and an electrolyte or other material for facilitating movement of ionic charge carriers between the negative electrode and positive electrode.
  • each cell typically includes a positive electrode, a negative electrode, and an electrolyte or other material for facilitating movement of ionic charge carriers between the negative electrode and positive electrode.
  • cations migrate from the positive electrode to the electrolyte and, concurrently, from the electrolyte to the negative electrode.
  • cations migrate from the negative electrode to the electrolyte and, concurrently, from the electrolyte to the positive electrode.
  • lithium ion batteries are prepared from one or more lithium ion electrochemical cells containing electrochemically active (electroactive) materials.
  • Such cells typically include, at least, a negative electrode, a positive electrode, and an electrolyte for facilitating movement of ionic charge carriers between the negative and positive electrode.
  • a negative electrode typically includes, at least, a negative electrode, a positive electrode, and an electrolyte for facilitating movement of ionic charge carriers between the negative and positive electrode.
  • lithium ions are transferred from the positive electrode to the electrolyte and, concurrently from the electrolyte to the negative electrode.
  • the lithium ions are transferred from the negative electrode to the electrolyte and, concurrently from the electrolyte back to the positive electrode.
  • Such lithium ion batteries are called rechargeable lithium ion batteries or rocking chair batteries.
  • the electrodes of such batteries generally include an electroactive material having a crystal lattice structure or framework from which ions, such as lithium ions, can be extracted and subsequently reinserted and/or from which ions such as lithium ions can be inserted or intercalated and subsequently extracted.
  • ions such as lithium ions
  • a class of such materials is disclosed in U.S. Pat. No. 6,528,033 B1 (Barker et al.).
  • the compounds therein are of the general formula Li a MI b MII c (PO 4 ) d wherein MI and MII are the same or different.
  • MI is a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Cr and mixtures thereof.
  • MII is optionally present, but when present is a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be and mixtures thereof. More specific examples of such compounds include compounds wherein MI is vanadium and more specifically includes Li 3 V 2 (PO 4 ) 3 .
  • U.S. Pat. No. 6,645,452 B1 (Barker et al.) further discloses electroactive vanadium phosphates such as LiVPO 4 F and LiV 0.9 Al 0.1 PO 4 F.
  • the present invention provides for the preparation of an “optimized” VPO 4 phase or V—P—O/C precursor.
  • the VPO 4 precursor is an amorphous or nanocrystalline powder.
  • the V—P—O/C precursor is amorphous in nature and contains finely divided and dispersed carbon.
  • the VPO 4 precursor and the V—P—O/C precursor materials can be used interchangeably to produce the final vanadium phosphates, with the V—P—O/C precursor material being the preferred precursor.
  • the precursors can subsequently be used to make vanadium based electroactive materials and use of such precursor materials offers significant advantages over other processes known for preparing vanadium phosphate compounds.
  • FIG. 1 is a schematic cross-sectional diagram illustrating the structure of a non-aqueous electrolyte cylindrical electrochemical cell of the present invention.
  • FIG. 2 is a representative X-ray pattern for a sample of an amorphous V—P—O/C sample prepared at 700° C. for 4 hours as in Example 1.
  • FIG. 3 is an X-ray powder pattern for a sample of LiVPO 4 F for a product prepared according to Example 2.
  • FIG. 4 is observed, difference and calculated plot obtained from Rietveld analysis of an optimized sample of LiVPO 4 F prepared in Example 2.
  • FIG. 5 shows a schematic representation of the structure of LiVPO 4 F projected down the c-axis.
  • FIG. 6 shows the first cycle current data for a Li//LiVPO 4 F cell made with the LiVPO 4 F prepared in Example 2.
  • FIG. 7 shows a representative X-ray powder patterns for LiV 1 ⁇ x Al x PO 4 F made by the process according to Example 3.
  • FIG. 8 shows the unit cell volume versus Al content for LiV 1 ⁇ x Al x PO 4 F made by the process according to Example 3.
  • FIG. 9 shows a comparison of the electrochemical response of Li//LiVPO 4 F, Li//LiAl 0.25 V 0.75 PO 4 F and Li//LiAl 0.5 V 0.5 PO 4 F cells made by the process of Example 3.
  • FIG. 10 shows a representative X-ray powder pattern for LiVP 2 O 7 made by the process of Example 5.
  • FIG. 11 shows the observed, difference and calculated plots obtained for a sample of LiVP 2 O 7 made by the process of Example 5.
  • FIG. 12 shows a schematic representation of the structure of LiVP 2 O 7 made by the process of Example 5.
  • FIG. 13 shows a first cycle constant current data for a Li//LiVP 2 O 7 cell.
  • FIG. 14 shows EVS data for a representative Li//LiVP 2 O 7 cell cycled between 2.5-4.7 V. Left: EVS Voltage profile. Right: EVS Differential Capacity Profile.
  • FIG. 15 shows EVS data for a representative graphite//LiVP 2 O 7 lithium ion cell cycled between 2.5-4.6 V. The data shown is for the tenth cycle. Left: EVS Voltage Profile. Right EVS Differential Capacity Profile.
  • FIG. 16 shows the life cycle data collected for LiVP 2 O 7 //graphite cell.
  • FIG. 17 shows X-ray patterns for samples of LiV 1 ⁇ x Al x PO 4 F prepared according to the process of Example 10.
  • FIG. 18 shows the electrochemical results for samples of LiV 1 ⁇ x Al x P 2 O 7 prepared according to Example 10.
  • FIG. 19 shows a comparison of a sample of LVP prepared using conventional known methods and prepared using the VPO 4 process according to Example 11.
  • FIG. 20 shows the EVS electrochemical response for LVP sample prepared according to Example 11
  • FIG. 21 shows the X-ray powder pattern for the sample of Na 3 V 2 (PO 4 ) 2 F 3 prepared according to the method of Example 12.
  • battery refers to a device comprising one or more electrochemical cells for the production of electricity.
  • Each electrochemical cell comprises an anode, a cathode and an electrolyte.
  • anode and “cathode” refer to the electrodes at which oxidation and reduction occur, respectively, during battery discharge. During charging of the battery, the sites of oxidation and reduction are reversed.
  • nominal formula or “nominal general formula” refer to the fact that the relative proportion of atomic species may vary slightly on the order of 2 percent to 5 percent, or more typically, 1 percent to 3 percent.
  • the cell 10 includes a spirally coiled or wound electrode assembly 12 enclosed in a sealed container, preferably a rigid cylindrical casing 14 .
  • the electrode assembly 12 includes: a positive electrode 16 consisting of, among other things, an electrode active material described herein below; a counter negative electrode 18 ; and a separator 20 interposed between the first and second electrodes 16 , 18 .
  • the separator 20 is preferably an electrically insulating, ionically conductive microporous film, and composed of a polymeric material selected from the group consisting of polyethylene, polyethylene oxide, polyacrylonitrile and polyvinylidene fluoride, polymethyl methacrylate, polysiloxane, copolymers thereof, and admixtures thereof.
  • Each electrode 16 , 18 includes a current collector 22 and 24 , respectively, for providing electrical communication between the electrodes 16 , 18 and an external load.
  • Each current collector 22 , 24 is a foil or grid of an electrically conductive metal such as iron, copper, aluminum, titanium, nickel, stainless steel, or the like, having a thickness of between 5 ⁇ m and 100 ⁇ m, preferably 5 ⁇ m and 20 ⁇ m.
  • the current collector may be treated with an oxide-removing agent such as a mild acid and the like, and coated with an electrically conductive coating for inhibiting the formation of electrically insulating oxides on the surface of the current collector 22 , 24 .
  • suitable coatings include polymeric materials comprising a homogenously dispersed electrically conductive material (e.g.
  • polymeric materials including: acrylics including acrylic acid and methacrylic acids and esters, including poly (ethylene-co-acrylic acid); vinylic materials including poly(vinyl acetate) and poly(vinylidene fluoride-co-hexafluoropropylene); polyesters including poly(adipic acid-co-ethylene glycol); polyurethanes; fluoroelastomers; and mixtures thereof.
  • the positive electrode 16 further includes a positive electrode film 26 formed on at least one side of the positive electrode current collector 22 , preferably both sides of the positive electrode current collector 22 , each film 26 having a thickness of between 10 ⁇ m and 150 ⁇ m, preferably between 25 ⁇ m an 125 ⁇ m, in order to realize the optimal capacity for the cell 10 .
  • the positive electrode film 26 is preferably composed of between 80% and 99% by weight of an electrode active material described herein below as general formula (I), between 1% and 10% by weight binder, and between 1% and 10% by weight electrically conductive agent.
  • Suitable binders include: polyacrylic acid; carboxymethylcellulose; diacetylcellulose; hydroxypropylcellulose; polyethylene; polypropylene; ethylene-propylene-diene copolymer; polytetrafluoroethylene; polyvinylidene fluoride; styrene-butadiene rubber; tetrafluoroethylene-hexafluoropropylene copolymer; polyvinyl alcohol; polyvinyl chloride; polyvinyl pyrrolidone; tetrafluoroethylene-perfluoroalkylvinyl ether copolymer; vinylidene fluoride-hexafluoropropylene copolymer; vinylidene fluoride-chlorotrifluoroethylene copolymer; ethylenetetrafluoroethylene copolymer; polychlorotrifluoroethylene; vinylidene fluoride-pentafluoropropylene copolymer; propylene-tetra
  • Suitable electrically conductive agents include: natural graphite (e.g. flaky graphite, and the like); manufactured graphite; carbon blacks such as acetylene black, Ketzen black, channel black, furnace black, lamp black, thermal black, and the like; conductive fibers such as carbon fibers and metallic fibers; metal powders such as carbon fluoride, copper, nickel, and the like; and organic conductive materials such as polyphenylene derivatives.
  • natural graphite e.g. flaky graphite, and the like
  • manufactured graphite carbon blacks such as acetylene black, Ketzen black, channel black, furnace black, lamp black, thermal black, and the like
  • conductive fibers such as carbon fibers and metallic fibers
  • metal powders such as carbon fluoride, copper, nickel, and the like
  • organic conductive materials such as polyphenylene derivatives.
  • the negative electrode 18 is formed of a negative electrode film 28 formed on at least one side of the negative electrode current collector 24 , preferably both sides of the negative electrode current collector 24 .
  • the negative electrode film 28 is composed of between 80% and 95% of an intercalation material, between 2% and 10% by weight binder, and (optionally) between 1% and 10% by weight of an electrically conductive agent.
  • Intercalation materials suitable herein include: transition metal oxides, metal chalcogenides, carbons (e.g. graphite), and mixtures thereof capable of intercalating the alkali metal-ions present in the electrolyte in the electrochemical cell's nascent state.
  • the intercalation material is selected from the group consisting of crystalline graphite and amorphous graphite, and mixtures thereof, each such graphite having one or more of the following properties: a lattice interplane (002) d-value (d (002) ) obtained by X-ray diffraction of between 3.35 ⁇ to 3.34 ⁇ , inclusive (3.35 ⁇ d (002) ⁇ 3.34 ⁇ ), preferably 3.354 ⁇ to 3.370 ⁇ , inclusive (3.354 ⁇ d (002) ⁇ 3.370 ⁇ ; a crystallite size (L c ) in the c-axis direction obtained by X-ray diffraction of at least 200 ⁇ , inclusive (L c ⁇ 200 ⁇ ), preferably between 200 ⁇ and 1,000 ⁇ , inclusive (200 ⁇ L c ⁇ 1,000 ⁇ ); an average particle diameter (P d ) of between 1 ⁇ m to 30 ⁇ m, inclusive (1 ⁇ m ⁇ P d ⁇ 30 ⁇ m); a lattic
  • the separator 20 “overhangs” or extends a width “a” beyond each edge of the negative electrode 18 .
  • the negative electrode 18 “overhangs” or extends a width “b” beyond each edge of the positive electrode 16 .
  • the cylindrical casing 14 includes a cylindrical body member 30 having a closed end 32 in electrical communication with the negative electrode 18 via a negative electrode lead 34 , and an open end defined by crimped edge 36 .
  • the cylindrical body member 30 and more particularly the closed end 32 , is electrically conductive and provides electrical communication between the negative electrode 18 and an external load (not illustrated).
  • An insulating member 38 is interposed between the spirally coiled or wound electrode assembly 12 and the closed end 32 .
  • a positive terminal subassembly 40 in electrical communication with the positive electrode 16 via a positive electrode lead 42 provides electrical communication between the positive electrode 16 and the external load (not illustrated).
  • the positive terminal subassembly 40 is adapted to sever electrical communication between the positive electrode 16 and an external load/charging device in the event of an overcharge condition (e.g. by way of positive temperature coefficient (PTC) element), elevated temperature and/or in the event of excess gas generation within the cylindrical casing 14 .
  • PTC positive temperature coefficient
  • Suitable positive terminal assemblies 40 are disclosed in U.S. Pat. No. 6,632,572 to Iwaizono, et al., issued Oct. 14, 2003; and U.S. Pat. No. 6,667,132 to Okochi, et al., issued Dec. 23, 2003.
  • a gasket member 42 sealingly engages the upper portion of the cylindrical body member 30 to the positive terminal subassembly 40 .
  • a non-aqueous electrolyte (not shown) is provided for transferring ionic charge carriers between the positive electrode 16 and the negative electrode 18 during charge and discharge of the electrochemical cell 10 .
  • the electrolyte includes a non-aqueous solvent and an alkali metal salt dissolved therein capable of forming a stable SEI layer on the negative electrode (most preferably, a lithium salt).
  • the non-aqueous electrolyte contains one or more metal-ion charge carriers.
  • Suitable solvents include: a cyclic carbonate such as ethylene carbonate, propylene carbonate, butylene carbonate or vinylene carbonate; a non-cyclic carbonate such as dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate or dipropyl carbonate; an aliphatic carboxylic acid ester such as methyl formate, methyl acetate, methyl propionate or ethyl propionate; a .gamma.-lactone such as ⁇ -butyrolactone; a non-cyclic ether such as 1,2-dimethoxyethane, 1,2-diethoxyethane or ethoxymethoxyethane; a cyclic ether such as tetrahydrofuran or 2-methyltetrahydrofuran; an organic aprotic solvent such as dimethylsulfoxide, 1,3-dioxolane, formamide, acetamide, dimethylformamide, dioxolane, acet
  • Suitable alkali metal salts include: LiClO 4 ; LiBF 4 ; LiPF 6 ; LiAlCl 4 ; LiSbF 6 ; LiSCN; LiCF 3 SO 3 ; LiCF 3 CO 2 ; Li(CF 3 SO 2 ) 2 ; LiAsF 6 ; LiN(CF 3 SO2) 2 ; LiB 10 Cl 10 ; a lithium lower aliphatic carboxylate; LiCl; LiBr; Lil; a chloroboran of lithium; lithium tetraphenylborate; lithium imides; LiBOB (lithium bis(oxalate)borate) and mixtures thereof.
  • the electrolyte contains at least LiPF 6 .
  • One embodiment of the invention involves the production of a nanocrystalline and/or amorphous VPO 4 .
  • This material can be used a precursor for preparing various vanadium based products. This material is very reactive and allows for the preparation of various vanadium based products at low temperatures and with very fast kinetics. Additionally this VPO 4 is useful as a precursor of vanadium based products in that other processes for making the vanadium based products may cause production of unwanted impurity phases, such as V 2 O 3 , in the vanadium based products.
  • the invention involves the production of a amorphous V—P—O/C precursor with no “definite” composition (see FIG. 2 ).
  • This V—P—O/C precursor has the correct ratio of V and PO 4 to make the final product (e.g. LiVPO 4 F), is close to X-ray amorphous (see FIG. 2 ) and it contains finely divided and dispersed carbon.
  • This material can be used a precursor for preparing various vanadium based products This material is very reactive and allows for the preparation of various vanadium based products at low temperatures and with very fast kinetics. Additionally this V—P—O/C precursor is useful as a precursor of vanadium based products in that other processes for making the vanadium based products may cause production of unwanted impurity phases, such as V 2 O 3 , in the vanadium based products.
  • VPO 4 and V—P—O/C precursor materials can be used interchangeably in the reactions described herein.
  • the V—P—O/C precursor is the preferred precursor.
  • VPO 4 is used the V—P—O/C precursor could alternately be used and vice versa.
  • either precursor may be referred to as a vanadium phosphate precursor.
  • the vanadium phosphate precursor is made for example by mixing vanadium pentoxide (V 2 O 5 ), ammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 or (NH 4 )H 2 PO 4 ] and a source of carbon, such as Enasco carbon.
  • V 2 O 5 vanadium pentoxide
  • ammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 or (NH 4 )H 2 PO 4 ]
  • a source of carbon such as Enasco carbon.
  • the mixture is then milled and/or micronized (i.e. some form of high energy mixing/homogenizing), pelletized and heated at a temperature in the range from about 400° C. to about 900° C.
  • the milled mixture is heated in the temperature range from about 500° C. to about 800° C. and more preferably from about 600° C. to about 750° C.
  • the mixture is heated from about 30 minutes to about 16 hours and more preferably from about 1 to about 8 hours.
  • the amorphous V—P—O/C precursors may be produced at temperatures from 300-800° C. and more preferably at about 600° C. Reaction of these preferred amorphous V—P—O/C precursors with appropriate alkali metal compounds result in improved vanadium phosphate products which can be produced at lower temperatures than when using the crystalline VPO 4 precursors.
  • reaction proceeds according to the following equations: 0.5 V 2 O 5 +(NH 4 ) 2 HPO 4 +carbon ⁇ VPO 4 +2NH 3 +1.5 H 2 O+CO or 0.5 V 2 O 5 +(NH 4 )H 2 PO 4 +carbon ⁇ VPO 4 +NH 3 +1.5 H 2 O.
  • vanadium containing compounds such as V 2 O 3 , VO 2 , NH 4 VO 3 and the like can be used in the place of the V 2 O 5 .
  • lithium products are the desired end products LiVO 3 and the like may also be employed in place of the V 2 O 3 .
  • phosphate sources such as P 2 O 5 , H 3 PO 4 and the like can be used in place of the ammonium phosphate starting materials.
  • the source of carbon is provided by elemental carbon, preferably in particulate form such as graphites, amorphous carbon, carbon blacks and the like.
  • the source of carbon may also be provided by an organic precursor material, or by a mixture of elemental carbon and organic precursor material.
  • the organic precursor material will also be referred to in this application as an organic material.
  • the organic material or organic precursor material is one that is capable of forming a decomposition product that contains carbon. The carbon is formed in situ.
  • the source of carbon may be provided by an organic material.
  • the organic material is characterized as containing carbon and at least one other element, preferably hydrogen.
  • the organic material generally forms a decomposition product, referred to herein as a carbonaceous material, upon heating under the conditions of the reaction.
  • the organic precursor material may be any organic material capable of undergoing pyrolysis or carbonization, or any other decomposition process that leads to a carbonaceous material rich in carbon.
  • Such precursors include in general any organic material, i.e., compounds characterized by containing carbon and at least one other element.
  • the organic material may be a perhalo compound containing essentially no carbon-hydrogen bonds, typically the organic materials contain carbon and hydrogen.
  • Other elements such as without limitation, halogens, oxygen, nitrogen, phosphorus, and sulfur, may be present in the organic material, as long as they do not significantly interfere with the decomposition process.
  • One example of a preferred organic material is coke, which contains mostly carbon and hydrogen.
  • precursors include, without limitation, organic hydrocarbons, alcohols, esters, ketones, aldehydes, carboxylic acids, sulfonates, and ethers.
  • Preferred precursors include the above species containing aromatic rings, especially the aromatic hydrocarbons such as tars, pitches, and other petroleum products or fractions.
  • hydrocarbon refers to an organic compound made up of carbon and hydrogen, and containing no significant amounts of other elements. Hydrocarbons may contain impurities having some heteroatoms. Such impurities might result, for example, from partial oxidation of a hydrocarbon or incomplete separation of a hydrocarbon from a reaction mixture or natural source such as petroleum.
  • organic precursor materials include sugars and other carbohydrates, including derivatives and polymers.
  • polymers include, without limitation, starch, cellulose, and their ether or ester derivatives.
  • Other derivatives include, without limitation, the partially reduced and partially oxidized carbohydrates discussed below. On heating, carbohydrates readily decompose to form carbon and water.
  • carbohydrates as used here encompasses the D-, L-, and DL-forms, as well as mixtures, and includes material from natural or synthetic sources.
  • carbohydrates are organic materials that can be written with molecular formula (C) m (H 2 O) n , where m and n are integers.
  • C molecular formula
  • m and n are integers.
  • hexoses of formula C 6 H 12 O 6 include allose, altose, glucose, mannose, gulose, inose, galactose, talose, sorbose, tagatose, and fructose.
  • Pentoses of formula C 5 H 10 O 5 are represented by, without limitation, ribose, arabinose, and xylose.
  • Tetroses include erythrose and threose, while glyceric aldehyde is a triose.
  • Other carbohydrates include the two-ring sugars (di-saccharides) of general formula C 12 H 22 O 11 . Examples include, without limitation, sucrose, maltose, lactose, trehalose, gentiobiose, cellobiose, and melibiose. Three-ring (trisaccharides such as raffinose) and higher oligomeric and polymer carbohydrates may also be used. Non-limiting examples include starch and cellulose. As noted above, the carbohydrates readily decompose to carbon and water when heated to a sufficiently high temperature. The water of decomposition tends to turn to steam under the reaction conditions and volatilize.
  • Such materials include slightly reduced carbohydrates such as, without limitation, glycerol, sorbitol, mannitol, iditol, dulcitol, talitol, arabitol, xylitol, and adonitol, as well as “slightly oxidized” carbohydrates such as, without limitation, gluconic, mannonic, glucuronic, galacturonic, mannuronic, saccharic, manosaccharic, ido-saccharic, mucic, talo-mucic, and allo-mucic acids.
  • the formula of the slightly oxidized and the slightly reduced carbohydrates is similar to that of the carbohydrates.
  • sucrose is sucrose. Under the reaction conditions, sucrose melts at about 150-180° C. The liquid melt tends to distribute itself among the starting materials. At temperatures above about 450° C., sucrose and other carbohydrates decompose to form carbon and water. The as-decomposed carbon powder is in the form of fresh amorphous fine particles with high surface area and high reactivity.
  • the organic precursor material may also be an organic polymer.
  • Organic polymers include without limitation, polyolefins such as polyethylene and polypropylene, butadiene polymers, isoprene polymers, vinyl alcohol polymers, furfuryl alcohol polymers, styrene polymers including polystyrene, polystyrene-polybutadiene and the like, divinylbenzene polymers, naphthalene polymers, phenol condensation products including those obtained by reaction with aldehyde, polyacrylonitrile, polyvinyl acetate, as well as cellulose starch and esters and ethers thereof described above.
  • the organic precursor material is a solid available in particulate form. Particulate materials may be combined with the other particulate starting materials and reacted by heating according to the methods described above.
  • the organic precursor material may be a liquid.
  • the liquid precursor material is combined with the other particulate starting materials to form a mixture.
  • the mixture is heated, whereupon the organic material forms a carbonaceous material in situ.
  • the liquid precursor materials may also advantageously serve or function as a binder in the starting material mixture as noted above.
  • the vanadium phosphate precursor is made for example by mixing vanadium pentoxide (V 2 O 5 ), ammonium hydrogen phosphate [(NH 4 ) 2 HPO 4 or (NH 4 )H 2 PO 4 ].
  • the mixture is then milled and/or micronized (i.e. some form of high energy mixing/homogenizing), pelletized and heated at a temperature in the range from about 400° C. to about 900° C. in the presence of reducing gas or gases.
  • Non-limiting examples or reducing gases include hydrogen, methane, ammonia and carbon monoxide.
  • the reducing atmosphere may be provided as pure reducing gas, or as mixtures of reducing gas with other gases.
  • Non-limiting examples of reducing atmosphere mixtures include hydrogen-argon, hydrogen-nitrogen, carbon monoxide-hydrogen, carbon monoxide-argon, and the like.
  • the reducing gas may but need not be provided in molar excess.
  • the reducing gas may be used in partial pressures from about 0.01 atmosphere up to super-atmospheric, depending on such factors as the size of the sample, the volume of the heating chamber, and the excess of gas, if any, required for the reaction
  • the reaction is carried out in a reducing atmosphere in the presence of a reductant.
  • reductant includes, without limitation carbon and organic precursor materials as discussed above.
  • reducing atmosphere includes without limitation, the reducing gases and mixtures thereof discussed above.
  • the vanadium phosphate precursor is mixed with an alkali metal containing compound and optionally with another metal containing compound to produce alkali metal vanadium phosphate compounds.
  • alkali metal containing compounds include NaF, LiF, LiH 2 PO 4 , NaOH, Na 2 CO 3 , Li 3 PO 4 and the like and mixtures thereof.
  • suitable precursors can include NH 4 F and the like together with an appropriate alkali ion salt.
  • Preferred alkali metal containing compounds are compounds containing Na or Li and the more preferred alkali metal containing compounds contain Li.
  • the optional metal containing compounds are compounds containing a metal ion selected from the group consisting of Al, Ti, Cr, Fe Mn, Mo, Nb and the like.
  • metal containing compounds include for example AlPO 4 , Fe 2 O 3 , Mn 2 O 3 , Fe 3 O 4 , FeO, MnO 2 , MnO, CrPO 4 , FePO 4 MnPO 4 , aluminum hydroxide, aluminum oxide, aluminum carbonate, Cr 2 O 3 , Nb 2 O 5 and the like.
  • the vanadium phosphate precursors are then reacted with an appropriate alkali metal according to, for example the following reactions: 3 LiH 2 PO 4 +2 VPO 4 ⁇ Li 3 V 2 (PO 4 ) 3 +3H 2 O or VPO 4 +LiF ⁇ LiVPO 4 F or 3 NaF+2 VPO 4 ⁇ Na 3 V 2 (PO 4 ) 2 F 3 .
  • the alkali metal compound is a compound of lithium, sodium, or potassium.
  • the alkali metal compound serves as a source of alkali metal ion in particulate form.
  • Preferred alkali metal compounds are sodium compounds and lithium compounds. Examples of compounds include, without limitation, carbonates, metal oxides, hydroxides, sulfates, aluminates, phosphates and silicates. Examples of lithium compounds thus include, without limitation, lithium carbonates, lithium metal oxides, lithium mixed metal oxides, lithium hydroxides, lithium aluminates, and lithium silicates, while analogous sodium compounds are also preferred.
  • a preferred lithium compound is lithium carbonate. Sodium carbonate and sodium hydroxide are preferred sodium compounds.
  • VPO 4 precursor, alkali metal containing compound and optional other metal containing compound are milled and then pelletized.
  • the mixture is then heated at a temperature from about 500° C. to about 900° C. More preferably the mixture is heated from about 500° C. to about 800° C. and most preferably from about 600° C. to about 750° C.
  • the mixture is heated for about 30 minutes to about 16 hours and more preferably from about 1 to about 8 hours.
  • the reaction produces electrode active compounds represented by the nominal general formula (I): A a V 1 ⁇ x M x (PO 4 ) d Z f . (I) wherein A is selected from the group consisting of Li, Na, K and mixtures thereof;
  • Examples of such compounds include but are not limited to LiVPO 4 , LiV 1 ⁇ x Al x PO 4 F, Na x VPO 4 F x , Li 0.1 Na 0.9 VPO 4 F, NaVPO 4 F, NaVPO 4 OH, NaVPO 4 F, Li 3 V 2 (PO 4 ) 3 , LiV 0.75 Al 0.25 PO 4 F, LiV 0.5 Al 0.5 PO 4 F, Na 1.2 VPO 4 F 1.2 and Na 3 V 2 (PO 4 ) 2 F 3 , and the like.
  • the reaction produces electrode active compounds represented by the nominal general formula (I): A a V 1 ⁇ x M x P 2 O 7 (I)
  • the electrode active materials described herein are in their nascent or as-synthesized state, prior to undergoing cycling in an electrochemical cell.
  • the components of the electrode active material are selected so as to maintain electroneutrality of the electrode active material.
  • the stoichiometric values of one or more elements of the composition may take on non-integer values.
  • moiety Z is selected from the group consisting of OH (hydroxyl), a halogen, or mixtures thereof.
  • Z is selected from the group consisting of OH, F (Fluorine), Cl (Chlorine), and mixtures thereof.
  • Z is OH.
  • Z is F, or a mixture of F with OH or Cl.
  • composite electrodes were fabricated using 84-wt % active material, 6-wt % Super P (conductive carbon) and 10-wt % PVdf-HFP co-polymer (Elf Atochem) binder.
  • the electrolyte comprised a 1 M LiPF 6 solution in ethylene carbonate/dimethyl carbonate (2:1 by weight) while a dried glass fiber filter (Whatman, Grade GF/A) was used as the electrode separator.
  • a commercially available crystalline graphite or lithium metal foil were used as the anode active material.
  • High-resolution electrochemical measurements were performed using the Electrochemical Voltage Spectroscopy (EVS) technique. (J. Barker, Electrochim. Acta, 40, 1603 (1995)).
  • EVS is a voltage step method, which provides a high resolution approximation to the open circuit voltage curve for the electrochemical system under investigation. Cycling tests of the hybrid-ion cells were performed using a commercial battery cycler (Maccor Inc., Tulsa, Okla., USA).
  • VPO 4 was prepared according to the following reaction: 1 ⁇ 2 V 2 O 5 +(NH 4 ) 2 HPO 4 +1.0 C ⁇ VPO 4 +2 NH 3 +3/2 H 2 O+CO 9.1 g V 2 O 5 , 13.2 g of (NH 4 ) 2 HPO 4 and 1.32 g of carbon (10% mass excess) were used. Carbon was added to the reaction mixture so that the V 5+ in the V 2 O 5 was reduced to V 3+ in the product which is an example of carbothermal reduction. The excess carbon in the product helps act as a conducting agent in the vanadium phosphate electroactive materials produced therefrom, which improves the electrochemical properties of such electroactive materials.
  • VPO 4 materials prepared herein were prepared at a number of different temperatures in the range from about 650° C. to about 900° C.
  • the samples prepared at higher temperatures contained V 2 O 3 as an impurity. Such materials would be unsuitable as precursors since V 2 O 3 is known to be detrimental to the electrochemical performance in Li ion cells. It has been found that preparing these materials at low temperatures, typically about 700° C. for about 4 to about 16 hours under a flowing argon atmosphere can be used effectively for the preparation of a number of precursor materials.
  • the precursor materials on removal from the furnace range from dark brown to black in color. The color is dependent on the amount of carbon added in the initial reaction mixture.
  • FIG. 2 is a typical X-ray powder pattern obtained for a sample of V—P—O/C precursor made at 700° for 4 hours.
  • the powder pattern of these materials prepared at low temperature generally have a “featureless” powder pattern, which can be interpreted as being due to either the material being amorphous or that the obtained crystallites are very small nanoparticles.
  • LiVPO 4 was prepared according to the following reaction: LiF+VPO 4 ⁇ LiVPO 4 F
  • the LiF (2.6 g) and VPO 4 (1.46 g) were mixed and micronized.
  • the amount of LiF added is dependent on the amount of residual carbon present in the VPO 4 .
  • the stoichiometric amount of LiF is added based on the above reaction.
  • the mixture was then heated in the temperature range of about 600° to about 700° C. for up to about 1 hour. At temperatures in excess of 700° C., it is believed that VF 3 sublimation occurs which leads to the formation of Li 3 V 2 (PO 4 ) 3 (LVP-nasicon).
  • FIG. 3 shows an example of a powder pattern obtained for a sample of LiVPO 4 F.
  • Refinement of the XRD data for the LiVPO 4 F samples was carried out using the Rietveld method. H. M. Rietveld, J. Appl. Crystallograph, 2, (1969) 65. R. A. Young in “The Rietveld Method”, Chapter 1, Oxford Science Publications. A. C. Larsen and R. B. Von Dreele, Los Alamos Laboratory Report, NO-LA-U-86-746 (1987).
  • the X-ray data can be satisfactorily refined using a structural model based on either Tavorite, LiFePO 4 OH (U.S. Pat. No.
  • FIG. 4 shows the fit obtained for the LiVPO 4 F sample using the Rietveld analysis.
  • FIG. 5 shows a schematic representation (along the c axis) of the LiVPO 4 F based on the Amblygonite structural model.
  • the LiVPO 4 F structure comprises a three dimensional framework being built from [PO 4 ] tetrahedral and [VO 4 F 2 ] octahedral with the oxygen atoms shared between the PO 4 and VO 4 F 2 .
  • This model predicts the presence of two distinct crystallographic sites for alkali ions which explains the electrochemical lithium extraction behavior exhibited by this material.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and lithium anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • FIG. 6 shows the first cycle constant current data obtained for the cell built using the sample of LiVPO 4 F.
  • a slight inflection is seen in the data during the charge process, which is related to preferential depopulation of one of the Li sites within the structure. No such feature is observed during the discharge process, indicating that during reinsertion of the Li neither of the sites is preferred. This observation is clearly supported by the observation of two peaks in the differential capacity plot obtained during EVS measurement. Long term cycling of this material shows good electrochemical properties.
  • An electrode active material comprising LiV 1 ⁇ x Al x PO 4 F was made according to the following reaction scheme: (1 ⁇ x )VPO 4 +x AlPO 4 +LiF ⁇ LiV 1 ⁇ x Al x PO 4 F
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and a lithium anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • FIG. 7 shows the X-ray powder patterns for samples of LiV 1 ⁇ x Al x PO 4 F. The results shown in FIG. 7 show that high quality samples can be prepared relatively easily.
  • FIG. 8 is a plot of Al content versus unit cell volume, obtained from Rietveld analysis of several samples. The plot clearly shows a linear relationship between Al content and the unit cell volume which is consistent with Vegards law, i.e. formation of a solid solution series between the V and Al.
  • FIG. 9 shows a comparison of the electrochemical response of samples containing varying amounts of Al.
  • Addition of more Al to a sample has the effect of reducing the overvoltage (i.e. voltage polarization) and is thought to be related to the increase in substitutionial disorder of the material.
  • the addition of Al on the V sites upsets the ordering (V-V-etc) of the transition metal. This will affect the resultant voltage characteristics to some extent.
  • Al is electrochemically inactive it has the effect of reducing the overall capacity of the material. Life cycling data suggests that the Al doped samples have a lower fade rate then observed with LiVPO 4 F.
  • An electrode active material comprising Na 1.2 VPO 4 F 1.2 was made as follows.
  • a metal phosphate was made by carbothermal reduction of a metal oxide, here exemplified by vanadium pentoxide.
  • the overall reaction scheme of the carbothermal reduction is as follows. 0.5V 2 O 5 +NH 4 H 2 PO 4 +C ⁇ VPO 4 +NH 3 +1.5H 2 O+CO 9.1 grams of V 2 O 5 , 11.5 grams of NH 4 H 2 PO 4 and 1.2 grams of carbon (10% excess) are used.
  • the precursors were premixed using a mortar and pestle and then pelletized. The pellet was transferred to an oven equipped with a flowing argon atmosphere.
  • the sample was heated at a ramp rate of 2° per minute to an ultimate temperature of 300° C. and maintained at this temperature for three hours.
  • the sample was cooled to room temperature, removed from the oven, recovered, re-mixed and repelletized.
  • the pellet is transferred to a furnace with an argon atmosphere.
  • the sample is heated at a ramp rate of 2° per minute to an ultimate temperature 750° C. and maintained at this temperature for 8 hours.
  • the vanadium phosphate made in the first step was reacted with an alkali metal halide, exemplified by sodium fluoride, according to the following reaction scheme.
  • xNaF+VPO 4 ⁇ Na x VPO 4 F x 14.6 grams of VPO 4 and 4.2 grams of NaF were used.
  • the precursors are pre-mixed using a mortar and pestle and then pelletized.
  • the pellet was transferred to an oven equipped with a flowing argon atmosphere. The sample was heated at a ramp rate of 2° per minute to an ultimate temperature of 750° C. and maintained at this temperature for an hour. The sample was cooled and removed from the furnace.
  • the reaction is repeated with a 20% mass excess of sodium fluoride over the previous reaction.
  • the precursors were pre-mixed using a mortar and pestle and pelletized as before.
  • the sample was heated to an ultimate temperature of 700° C. and maintained at this temperature for 15 minutes.
  • the sample was cooled and removed from the oven. There is only a small weight loss during reaction, indicating almost full incorporation of the NaF.
  • To make an active material of formula Na 1.5 VPO 4 F 1.5 the reaction is repeated with an approximate 50% mass excess of sodium fluoride over the first reaction.
  • the sample is heated at 700° C. for 15 minutes, cooled, and removed from the oven.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and lithium foil as anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • An electrode active material comprising LiVP 2 O 7 was made according to the following reaction scheme. LiH 2 PO 4 +VPO 4 ⁇ LiVP 2 O 7 +H 2 O LiH 2 PO 4 (10.39 g) and VPO 4 (14.59 g) were used. The precursors were mixed using a mortar and pestle and then pelletized. The pellet was transferred to an oven equipped with a flowing argon atmosphere. The sample was heated at a ramp rate of 2° per minute to an ultimate temperature of 750° C. and maintained at this temperature for an hour. It has been found that this material can be prepared in temperatures ranging from about 650° C. to about 850° C. The sample is cooled and removed from the furnace.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and carbon intercalation anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • FIG. 10 is a representative X-ray powder pattern for LiVP 2 O 7 .
  • the structure of this material has been examined using the Rietveld method using the model presented by Rousse. Rousse et al., Int. J. Inorg. Mat., 3, 881 (2001). The obtained fit is presented in FIG. 11 .
  • LiVP 2 O 7 can be described as a 3-D framework of corner sharing VO 6 octahedra and P 2 O 7 groups. This framework arrangement provides tunnels in which Li ions are coordinated tetrahedrally, as shown in FIG. 12 .
  • FIG. 13 shows a discharge capacity in the region of about 68 MAh/g. Taking into account the residual carbon this discharge capacity has a value closer to about 71 mAh/g. Although this would appear to be only a modest improvement over that reported by Uebou and Wum, these experiments were performed at a rate in the region of C/15. It is believed that some of the irreversibility is due to the upper voltage limit used in this experiment.
  • FIG. 14 shows the results of an EVS experiment performed using voltage limits of 2.5 to 4.7 volts (versus Li).
  • the reversible specific capacity for LiVP 2 O 7 is 93 mAh/g. It was noted however, that the capacity increased slowly over the first ten cycles, reaching 101 mAh/g after the tenth cycle. Examination of the differential capacity versus cell voltage plot shows that this system works with relatively low polarization. The differential capacity plot shows some evidence of decomposition at voltages greater than approximately 4.35 volts.
  • FIG. 16 shows the results of life cycle experiments performed with this material.
  • An electrode active material comprising Li 0.1 Na 0.9 VPO 4 F was made according to the following reaction scheme. xLiF+(1 ⁇ x)NaF+VPO 4 ⁇ Li x Na 1 ⁇ x VPO 4 F As an alternative to using alkali fluorides, a reaction between VPO 4 and NH 4 F and a mixture of Li 2 CO 3 and Na 2 CO 3 may also be used.
  • Li 0.1 Na 0.9 VPO 4 F 1.459 grams VPO 4 , 0.026 grams of LiF, and 0.378 grams of NaF were premixed, pelletized, placed in an oven and heated to an ultimate temperature of 700° C. The temperature is maintained for fifty minutes after which the sample is cooled to room temperature and removed from the oven.
  • Li 0.95 Na 0.05 VPO 4 F 1.459 grams of VPO 4 , 0.246 grams of LiF, and 0.021 grams of NaF are mixed together and heated in an oven as in the previous step.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and carbon intercalation anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • An electrode active material comprising NaVPO 4 F is made hydrothermally according to the following reaction scheme.
  • NaF+VPO 4 ⁇ NaVPO 4 F 1.49 grams of VPO 4 and 1.42 grams of NaF are premixed with approximately 20 milliliters of deionized water, transferred and sealed in a Parr Model 4744 acid digestion bomb, which is a Teflon lined stainless steel hydrothermal reaction vessel.
  • the bomb is placed in an oven and heated at a ramp rate of 5° per minute to an ultimate temperature of 250° C. to create an internal pressure and maintained at this temperature for forty-eight hours.
  • the sample is slowly cooled to room temperature and removed from the furnace for analysis.
  • the product sample is washed repeatedly with deionized water to remove unreacted impurities.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and carbon intercalation anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • An electrode active material of formula NaVPO 4 OH is made according to the following reaction scheme. NaOH+VPO 4 ⁇ NaVPO 4 OH
  • Example 7 the reaction of the Example 7 is repeated, except that an appropriate molar amount of sodium hydroxide is used instead of sodium fluoride.
  • the reaction is carried out hydrothermally as in Example 7.
  • the hydroxyl group is incorporated into the active material at the relatively low temperature of reaction.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and carbon intercalation anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • An electrode active material comprising NaVPO 4 F is made according to the following reaction scheme. 0.5Na 2 CO 3 +NH 4 F+VPO 4 ⁇ NaVPO 4 F+NH 3 +0.5CO 2 +0.5H 2 O
  • Electrode active materials comprising compounds of the formula LiV 1 ⁇ x Al x PO 4 were made according to the following reaction scheme: (1 ⁇ x) VPO 4 +x AlPO 4 +LiH 2 PO 4 ⁇ LiV 1 ⁇ x Al x P 2 O 7 +H 2 O
  • the precursors were mixed using a mortar and pestle and then palletized.
  • the pellet was transferred to an oven equipped with a flowing argon atmosphere.
  • the samples were heated at a ramp rate of 2° per minute to an ultimate temperature of about 650° C. to about 850° C. and maintained at these temperatures for about 4 to about 8 hours.
  • the sample is cooled and removed from the furnace.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% polyvinylidene difluoride.
  • a cell with that electrode as cathode and lithium anode is constructed with an electrolyte comprising 1M LiPF 6 dissolved in 2:1 by weight ethylene carbonate to dimethyl carbonate is constructed and tested.
  • Al 3+ is electrochemically inactive and therefore reduces the amount of Li that can be extracted.
  • many of the samples prepared were lower Al content samples, typically in the range of 5-15% Al doping.
  • the X-ray patterns for a selection of samples so prepared are shown in FIG. 17 .
  • An electrode active material comprising Li 3 V 2 (PO 4 ) 3 was made according to the following reaction scheme. Li 3 PO 4 +2VPO 4 ⁇ Li 3 V 2 (PO 4 ) 3 LiPO 4 (11.58 g) and VPO 4 (29.18 g) were used. The precursors were mixed using a mortar and pestle and then pelletized. The pellet was transferred to an oven equipped with a flowing argon atmosphere. The samples were heated at a ramp rate of 2° per minute to an ultimate temperature of about 650° C. to about 850° C. and preferably 700 to 750° C. and maintained at these temperatures for about 1 to about 8 hours. The sample is cooled and removed from the furnace.
  • FIG. 19 shows a representative X-ray pattern of a sample prepared as above.
  • An electrode is made with 84% of the active material, 6% of Super P conductive carbon, and 10% poly vinylidene difluoride.
  • a cell with that electrode as cathode and a lithium anode is constructed with an electrolyte comprising 1 M LiPF 6 dissolved in 2:1 by weight mixture of ethylene carbonate:dimethyl carbonate.
  • FIG. 20 shows the electrochemical properties of the sample.
  • An electrode active material comprising Na 3 V 2 (PO 4 ) 2 F 3 is made as follows.
  • a VPO 4 precursor is made according to the following reaction scheme.
  • a mixture of 18.2 g (0.1 mol) of V 2 O 5 , 26.4 g (0.2 mol) of (NH 4 ) 2 HPO 4 , and 2.64 g (0.2 mol+10% mass excess) of elemental carbon was made, using a mortar and pestle.
  • the mixture was pelletized, and transferred to a box oven equipped with an argon gas flow.
  • the mixture was heated to a temperature of about 350° C., and maintained at this temperature for 3 hours.
  • the mixture was then heated to a temperature of about 750° C., and maintained at this temperature for 8 hours.
  • the product is then cooled to ambient temperature (about 21° C.).
  • Na 3 V 2 (PO 4 ) 2 F 3 was then made from the VPO 4 precursor.
  • the material was made according to the following reaction scheme. 2 VPO 4 +3 NaF ⁇ Na 3 V 2 (PO 4 ) 2 F 3
  • a mixture of VPO 4 (2.918 g) and NaF (1.26 g) was made, using a mortar and pestle.
  • the mixture was pelletized, and transferred to a temperature-controlled tube furnace equipped with an argon gas flow.
  • the mixture is heated at a ramp rate of about 2°/minute to an ultimate temperature of about 750° C. for 1 hour
  • Temperatures can be in the region of 700-800° C. for these samples and can be heated in this region for about one to about four hours.
  • the product is then cooled to ambient temperature (about 20° C.).
  • FIG. 21 A representative X-ray powder pattern is shown in FIG. 21 X-ray powder diffraction analysis for the Na 3 V 2 (PO 4 ) 2 F 3 material indicated the material to be single phase with a tetragonal structure (space group P42/mnm).
  • Vanadium oxide (V 2 O 5 ; 9.10 g), diammonium hydrogen phosphate (13.2 g) and elemental carbon (1.32 g, 10% mass excess) were weighed and poured into a micronising pot. The materials were then micronised for 15 minutes. This process step has the dual purpose of providing intimate mixing and dispersion of the raw materials to produce a homogenous mixture and reducing particles size of the material due to the grinding/milling action. After micronising, the resulting powder was pressed to form a pellet. The pellet was placed in a crucible and placed in a tube furnace. The pellet was fired at 700° C. at a ramp rate of 2° C./minute with a 16 hour dwell under an inert atmosphere.
  • FIG. 23 shows the X-rd trace for the resulting VPO 4 .
  • the trace shows that the VPO 4 is an amorphous V—P—O/C precursor.
  • the VPO 4 (1.46 g) precursor so obtained was then micronised for 15 minutes with LiF (0.26 g). After micronising, the resultant powder was pressed to form a pellet was placed in a crucible, sealed by a second crucible and placed in a tube furnace. The pellet is fired at 700° C. at a ramp rate of 2° C./minute with a one hour dwell under an inert atmosphere. After firing, the pellet was broken up and ground to produce the final LiVPO 4 F material.
  • FIG. 24 shows the Xrd trace for the resulting LiVPO 4 F.

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US9312534B2 (en) 2010-12-09 2016-04-12 Nec Corporation Nonaqueous electrolytic solution secondary battery, and positive electrode and negative electrode used in the same
EP2573046A1 (en) * 2011-09-21 2013-03-27 Fuji Jukogyo Kabushiki Kaisha Positive electrode active material (LiVPO4F - Lithium vanadium fluorophosphate) production method, positive electrode, and storage device
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EP3595061A4 (en) * 2017-03-10 2020-12-16 Industry-Academia Cooperation Group of Sejong University POSITIVE ELECTRODE ACTIVE MATERIAL FOR A POTASSIUM SECONDARY BATTERY AND THEREFORE POTASSIUM SECONDARY BATTERY
US20210202946A1 (en) * 2019-12-09 2021-07-01 Soochow University Iron-based cathode material for sodium-ion battery, preparation method thereof, and corresponding sodium-ion full battery
CN111606314A (zh) * 2020-06-04 2020-09-01 哈尔滨工业大学 一种钠离子电池正极材料三氟磷酸钒钠的制备方法
CN115472814A (zh) * 2021-09-03 2022-12-13 中国科学院物理研究所 一种新型水系二次锂电池及其负极材料和制备方法及用途

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US8313719B2 (en) 2012-11-20
EP2115802A4 (en) 2013-10-30
WO2008109602A2 (en) 2008-09-12
KR101524883B1 (ko) 2015-06-01
EP2115802A2 (en) 2009-11-11
CA2679048A1 (en) 2008-09-12
WO2008109602A3 (en) 2008-10-30
US20110210288A1 (en) 2011-09-01
KR20090120476A (ko) 2009-11-24
CN101627493A (zh) 2010-01-13

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