WO2013052494A1 - Matières de cathode comprenant un composé d'absorption d'oxygène et un composé de stockage d'ions - Google Patents

Matières de cathode comprenant un composé d'absorption d'oxygène et un composé de stockage d'ions Download PDF

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Publication number
WO2013052494A1
WO2013052494A1 PCT/US2012/058476 US2012058476W WO2013052494A1 WO 2013052494 A1 WO2013052494 A1 WO 2013052494A1 US 2012058476 W US2012058476 W US 2012058476W WO 2013052494 A1 WO2013052494 A1 WO 2013052494A1
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Prior art keywords
compound
oxygen
lithium
lii
gettering
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PCT/US2012/058476
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English (en)
Inventor
Karen E. Thomas-Alyea
Sang-Young Yoon
Rocco Iocco
Jeong Ju CHO
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A123 Systems, Inc.
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Publication of WO2013052494A1 publication Critical patent/WO2013052494A1/fr

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—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 application is related to United States Patent Application Serial No. 10/329,046, filed on December 23, 2002, now United States Patent No. 7,338,734, the content of which is hereby incorporated by reference herein in its entirety.
  • the present application is also related to United States Patent Application Serial No. 12/868,530, filed on August 25, 2010, the content of which is hereby incorporated by reference herein in its entirety.
  • the present application is related to United States Provisional Patent Application Serial No. 61/511,280, filed on July 25, 2011, the content of which is hereby incorporated by reference herein in its entirety. Additionally, the present application is related to United States
  • Batteries produce energy from electrochemical reactions. Batteries typically include a positive electrode and a negative electrode; an ionic electrolyte solution that supports the movement of ions back and forth between the two electrodes; and a porous separator that ensures the two electrodes do not touch but allows ions to travel back and forth between the electrodes.
  • Lithium-ion battery or lithium ion cell refers to a rechargeable battery having a negative electrode capable of storing a substantial amount of lithium at a lithium chemical potential above that of lithium metal.
  • lithium ions travel from the positive electrode to the negative electrode. On discharge, these ions return to the positive electrode releasing energy in the process.
  • the cell includes lithium transition metal oxides for the positive electrode (or cathode), carbon/graphite for the negative electrode (or anode), and a lithium salt in an organic solvent for the electrolyte.
  • lithium transition metal oxides for the positive electrode (or cathode)
  • carbon/graphite for the negative electrode (or anode)
  • lithium salt in an organic solvent for the electrolyte.
  • lithium metal phosphates have been used as a cathode electroactive material.
  • lithium transition metal oxide materials although having higher energy density, usually result in battery with the problem of thermal run away under high temperatures.
  • ceramic resistive layers are coated on the separator or anode. This adds additional cost to the cell.
  • high energy density lithium ion battery material with improved thermal safety.
  • a positive electroactive material including:
  • an oxygen-gettering compound capable of trapping oxygen capable of trapping oxygen
  • an ion-storage compound capable of trapping oxygen
  • the oxygen-gettering compound is an ion-storage material.
  • the oxygen-gettering compound is orthorhombic alkali metal manganese oxide coated on the ion-storage compound.
  • the oxygen-gettering compound coating covers at least 50%, 60%, 70%, 80%, 90%, or 100% of the surface of the ion- storage compound.
  • the oxygen-gettering compound coating has at least 20%, 30%, 40%, 50%, 60%, 70%, or 80% porosity.
  • the oxygen-gettering compound has a formula of Li x Na y Mn0 4 , wherein 0 ⁇ x ⁇ 0.75, 0 ⁇ y ⁇ 0.75, and 0.2 ⁇ x + y ⁇ 0.75.
  • the oxygen-gettering compound is [0014] In any of the preceding embodiments, the oxygen-gettering compound is
  • the oxygen-gettering compound includes one or more transition metal oxide, wherein the transition metal is selected from the group consisting of Fe, Mn, Co, Ni, Ti, V, and a combination thereof.
  • the oxygen-gettering compound is one or more compounds selected from the group consisting of FeO, MnO, CoO, NiO, Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , Ni 3 0 4 , and vanadium oxide wherein the vanadium average valence is less than 5 + .
  • the oxygen-gettering compound is nanoscale alkali metal polyanion compound having a composition of ⁇ ⁇ ( ⁇ _ a M" a ) y (XD 4 ) z , A x (M'!_ a M” a ) y (DXD 4 ) z , or ⁇ ⁇ ( ⁇ JVI" a )y(X 2 D 7 ) z and a specific surface area of at least 5 m 2 /g, wherein A is at least one of an alkali metal or hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" is one or more metal selected form the group consisting of Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB metal and
  • the nanoscale alkali metal polyanion compound is LiFeP0 4 .
  • the nanoscale alkali metal polyanion compound include one or more electroactive materials selected from the group consisting of
  • the nanoscale alkali metal polyanion compound is one or more compounds selected from the group consisting of L1C0PO 4 , LiMnP0 4 , Li 3 V 2 (P0 4 )3, L1VPO 4 F, and mixed transition metal phosphate.
  • the ion-storage compound is one or more compounds selected from the group consisting of lithium cobalt oxide and lithium nickel oxide.
  • the lithium cobalt oxide or lithium nickel oxide further comprises one or more transition metal selected from the group consisting of Group IIA, A, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB metals and a combination thereof.
  • the lithium cobalt oxide further comprises a metal selected from the group consisting of Al, Mg, and a combination thereof.
  • the lithium nickel oxide further comprises a metal selected from the group consisting of Co, Mn, Al, Mg, and a combination thereof.
  • the lithium nickel oxide or the lithium nickel oxide has a nonuniform chemical composition across its particle radius.
  • a lithium ion battery including a positive electrode comprising the positive electrode active material of any of the preceding embodiments.
  • a "dopant metal” refers a metal that can be doped into (or substituted for an element of) an electroactive material of a positive electrode, either into the lattice sites of the electroactive material.
  • the dopant metal is present at a small concentration (relative to that of the electroactive metal) or has a redox potential significantly different from the electroactive metal so that the dopant metal does not significantly contribute to the electric storage capacity in an electrochemical cell.
  • a "olivine structure” refers to a compound composed of isolated tetrahedral A0 4 anionic groups and Ml and M2 cations surrounded by six oxygen ions.
  • the olivine structure exhibits orthorhombic 2mmm crystal symmetry and has a plurality of planes defined by zigzag chains and linear chains.
  • the Ml cations generally occupy the zigzag chains of octahedral sites and M2 cations generally occupy the linear chains of alternate planes of the octahedral sites.
  • the lattices sites can be doped with other dopant metals and nevertheless maintain the olivine structure.
  • an "olivinic phase” is any crystalline phase having the olivine structure.
  • the olivinic phase can include one or more dopant metals substituted into the lattice structure of the olivine structure.
  • the olivinic phase can be based on lithium-iron-manganese-phosphate (LFMP) material having an olivine structure that is doped with one or more dopant metals in the lattice sites of the olivine structure.
  • LFMP lithium-iron-manganese-phosphate
  • an "olivine compound” refers to a material having an olivine structure.
  • a "stoichiometric olivine compound” refers to the amount of lithium and/or phosphate that is in the material relative to the other metals. For example, if the olivine compound is LiFeP0 4 , the ratio of Li:Fe:P0 4 is 1 : 1 : 1 to form a stoichiometric olivine compound. If the olivine compound is Li-Fe-Mn-Co-Ni-V- P0 4 , the ratio of Li: Fe+Mn+Co+Ni+V: P0 4 is 1 : 1 : 1 to form a stoichiometric olivine compound.
  • excess lithium or “lithium rich” refers to the amount of lithium in the overall composition in excess of that needed to form the stoichiometric olivine compound.
  • excess phosphate or “phosphate-rich” refers to the amount of phosphate in the overall composition in excess of that needed to form the stoichiometric olivine compound.
  • solid solution refers a mixture of different atomic cations and anions that have arranged themselves into a single lattice structure, such as the olivine structure.
  • olivine compounds such as LFMP and dopant metals, existing together as an olivinic phase can be referred to as a solid solution.
  • the term "specific capacity” refers to the capacity per unit mass of the electroactive material in the positive electrode and has units of milliamps- hour/gram (mAh/g).
  • energy density refers the amount of energy a battery has in relation to its size. Energy density is the total amount of energy (in Wh) a battery can store per amount of the electroactive material in the positive electrode for a specified rate of discharge.
  • Figure 1 is a contour plot of specific energy of Ml (LiFeP0 4
  • Nanophosphate ® blends with lithium nickel cobalt manganese oxide (NCM).
  • Figure 2 is a contour plot of specific energy of Mix (LiMno. 5 Feo. 5 PC Nanophosphate ® ) blends with lithium nickel cobalt manganese oxide (NCM).
  • Figure 3 is a contour plot of DSC chart of Ml (LiFeP0 4 Nanophosphate ® ) blends with lithium nickel cobalt manganese oxide (NCM).
  • Figure 4 is a contour plot of DSC chart of Mix (LiMn 0 . 5 Feo. 5 P0 4
  • Nanophosphate ® blends with lithium nickel cobalt manganese oxide (NCM).
  • Figure 5 is a contour plot of DSC chart of Ml (LiFeP0 4 Nanophosphate ® ) blends with a lithium metal oxide cathode material.
  • Figure 6 is a contour plot of DSC chart of Mix (LiMn 0 . 5 Feo. 5 P0 4
  • Nanophosphate ® blends with a lithium metal oxide cathode material.
  • Positive electrode active material with high energy density and improved thermal safety is described.
  • the positive electrode active material includes an oxygen-gettering compound and an ion-storage compound.
  • One of the potential issues associated with high power and energy density ion-storage compound e.g., lithium cobalt oxide or lithium nickel oxide, is its poor thermal stability. These compounds may be thermally unstable at high states of charge and/or at high temperatures, e.g., temperatures above 150 °C. These compounds may release oxygen species, e.g., radical oxygen which will react with organic electrolyte in a cell at elevated temperature and produce heat and gas. The heat and gas generated can lead to fire and explosion. The decomposition also is one cause of poor cycle life, particularly if the material is cycled to high states of charge.
  • oxygen species e.g., radical oxygen which will react with organic electrolyte in a cell at elevated temperature and produce heat and gas. The heat and gas generated can lead to fire and explosion.
  • the decomposition also is one cause of poor cycle life, particularly if the material is cycled to high states of charge.
  • the ion-storage compound may include lithium cobalt oxide or lithium nickel oxide.
  • the lithium cobalt oxide or lithium nickel oxide may further includes one or more transition metal selected from the group consisting of Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB metals and a combination thereof.
  • the lithium cobalt oxide further comprises a metal selected from the group consisting of Al, Mg, and a combination thereof.
  • the lithium nickel oxide further comprises a metal selected from the group consisting of Co, Mn, Al, Mg, and a combination thereof.
  • an oxygen-gettering compound is included in the electrode to trap oxygen species potentially released by the ion-storage compound.
  • the oxygen-gettering compound can form a barrier which physically impedes the transport of oxygen to the electrolyte, thereby reducing the rate of reaction of oxygen with the electrolyte and/or the rate of oxygen release from the oxide structure.
  • the oxygen-gettering compound may physically absorb the oxygen generated or chemically bind to the oxygen. In some instances, the amount of oxygen released by the ion-storage compound is reduced so that the heat and gas and other harmful effects due to the reaction between the oxygen and electrolyte can be ameliorated or eliminated.
  • the oxygen released by the ion-storage compound is trapped by the oxygen-gettering compound so that the speed by which the oxygen reacts with the electrolyte is reduced so that the heat and gas and other harmful effects due to the reaction between the oxygen and electrolyte can be ameliorated.
  • the oxygen-gettering compound acts as a physical barrier to prevent the rapid release of the oxygen.
  • the oxygen- gettering compound traps or absorbs the oxygen through physical interactions.
  • the oxygen-gettering compound reacts with the oxygen chemically to absorb the released oxygen.
  • the oxygen-gettering compound may also act with more than one mechanism to prevent or delay the release of oxygen. For instance, the oxygen-gettering compound may act as a transport barrier and also physically absorb oxygen. In other instances, the oxygen-gettering compound may act as a transport barrier and also chemically react with oxygen to form one or more stable compounds.
  • the oxygen-gettering compound is capable of chemically reacting with the oxygen species, e.g., radical oxygen, so that the oxygen reaction with the electrolyte is reduced or completely eliminated.
  • oxygen- gettering compound may contain transitional meal in a reduced oxidation state capable of reacting with oxygen.
  • the oxygen-gettering compound includes one or more transition metal oxide, wherein the transition metal is selected from the group consisting of Fe, Mn, Co, Ni, Ti, V, and a combination thereof.
  • the transitional metal may be in a reduced oxidation state which could be oxidized by oxygen, thus eliminating or reducing the oxygen generated by the ion-storage compound and resulting in a safer cell.
  • suitable transitional metal with proper oxidation state include Fe 2+ , Mn 2+ , Mn 3+ , Co 2+ , Co 3+ , Ni 2+ , Ni 3+ , Ti 2+ , V 2+ , and V 3+ .
  • the oxygen-gettering compound is one or more transitional metal oxides selected from the group consisting of FeO, MnO, CoO, NiO, Fe 3 0 4 , Mn 3 0 4 , Co 3 0 4 , Ni 3 0 4 , and vanadium oxide wherein the vanadium average valence is less than 5 + .
  • the oxygen-gettering compound is nanoscale alkali metal polyanion compound having a composition of A x (M' i_ a M" a ) y (XD 4 ) z , ⁇ ⁇ ( ⁇ _ a M" a ) y (DXD 4 ) z , or A x (M' i_ a M" a )y(X 2 D 7 ) z , wherein A is at least one of an alkali metal or hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, boron, aluminum, silicon, vanadium, molybdenum and tungsten, M" is one or more metal selected form the group consisting of Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, VIB metal and a combination thereof, D is at least one of oxygen, 10 nitrogen
  • the nanoscale alkali metal polyanion compound is one or more compounds selected from the group consisting of L1C0PO4, LiMnP0 4 , Li 3 V2(P0 4 )3, L1VPO 4 F, and mixed transition metal phosphate. In some specific embodiments, the nanoscale alkali metal polyanion compound is doped or undoped LiFeP0 4 .
  • the oxygen-gettering compound the nanoscale alkali metal is one or more electroactive materials selected from the group consisting of
  • the ion-storage compound is coated with the oxygen-gettering compound.
  • the oxygen-gettering compound coating is inert where it acts as a physical barrier to the oxygen generated and delays its release and/or transport to the electrolyte but does not react with oxygen.
  • the oxygen-gettering compound may reduce the speed by which the oxygen is released and in turn reduce the speed of the possible detrimental reactions between the oxygen species and the electrolyte. As a result, the amount of heat generated due to these detrimental reactions is reduced and the safety profile of the cell is improved.
  • the oxygen-gettering compound in the coating is capable of reacting with oxygen and binds to the oxygen.
  • the oxygen- gettering compound coating may have dual functions, i.e., trapping and delaying oxygen release; and chemically reacting with oxygen.
  • the oxygen-gettering-compound coating has a thickness of from about 0.1 ⁇ to about 10 ⁇ , from about 0.5 ⁇ to about 5 ⁇ , or from about 1 ⁇ to about 5 ⁇ . In some embodiments, the oxygen-gettering- compound coating has a thickness of about 0.1 ⁇ , about 0.5 ⁇ , about 1 ⁇ , about 1.5 ⁇ , about 2 ⁇ , about 3 ⁇ , about 5 ⁇ , or about 10 ⁇ . In some embodiments, the oxygen-gettering-compound coating has a thickness from about 0.1 ⁇ to about 2 ⁇ .
  • the oxygen-gettering compound coating covers at least 50%, 60%, 70%, 80%, 90%, or 100% of the surface of the ion-storage compound. In some embodiments, the oxygen-gettering compound coating has at least 20%, 30%, 40%, 50%, 60%, 70%, or 80% porosity.
  • the oxygen-gettering-compound coatings may serve as a physical barrier between the electrolyte and the oxygen released by the ion-storage compound (e.g., LiCo0 2 or LiNi0 2 ).
  • the oxygen generated has to transport to the electrolyte before it can react with the electrolyte.
  • the rate of oxygen transport may be slowed.
  • Oxygen may transport through the coating either via solid-phase diffusion or through fluid-phase transport through cracks in the coating. By slowing the rate of transport, one slows the rate of reaction with the electrolyte. Additionally, increasing concentration of products should slow down rate of reaction. Thus, slowing the rate of transport may also increase the concentration of oxygen (the product of lithium metal oxide decomposition) adjacent to the lithium metal oxide electroactive material (reaction starting material), which may slow down the rate of the decomposition reaction.
  • the oxygen generated has to get through the gettering compound physical barrier and thus its release speed is reduced. As a result, the detrimental reaction between the oxygen and the electrolyte is ameliorated. Still alternatively, the oxygen-gettering-compound may react chemically with the oxygen species and form a stable compound. As a result, the oxygen generated is reduced or eliminated and the detrimental reaction between the oxygen and the electrolyte is ameliorated or avoided.
  • lithium metal oxide can be coated with materials such as AI2O3, Zr0 2 , or MgO. While the AI2O3, Zr0 2 , or MgO coatings have been shown to improve the thermal stability and cycle life of LiCo0 2 and LiNi0 2 , they have the disadvantage of being electrical insulators and electrochemically inactive. Coating the active electrode material with an insulator causes an increase in cell impedance, which is undesirable for high-power applications. Coating the active electrode material with an electrochemically inactive component adds dead weight to the cell, reducing the energy and power density.
  • orthorhombic alkali metal manganese oxide can be used as the oxygen-gettering-compound coating. It is believed that orthorhombic alkali metal manganese oxide can be coated on the surface of the ion- storage compound and the coating is stable during cycling of the cell. That is, the orthorhombic alkali metal manganese oxide will maintain its crystallite structure during cycling. For instance, when the ion storage compound coated with
  • orthorhombic alkali metal manganese oxide is used as a cathode active material in a lithium ion battery, lithium ion will exchange with the alkali metal in the coating during cycling, and yet the coating layer still maintains its orthorhombic crystalline structure.
  • the ion-storage compound is initially coated with orthorhombic sodium manganese oxide to use in a lithium ion cell. During cell cycling, a portion or all of the sodium is replaced by lithium while the orthorhombic crystallite structure of the coating layer is maintained. The orthorhombic crystallite structure of the coating is desirable since the crystalline structure is stable throughout the cell cycling.
  • layered or spinel alkali metal manganese oxide coating material will gradually loose its crystalline structure upon lithium-alkali metal exchange during cell cycling, and eventually result in the loss of the coating layer.
  • Layered or spinel alkali metal manganese oxide coating material can suffer from metal dissolution which degrades cell cycle life and calendar life.
  • the orthorhombic alkali metal manganese oxide has a formula of Li x Na y Mn0 4 , wherein 0 ⁇ x ⁇ 0.44, 0 ⁇ y ⁇ 0.44, and 0.2 ⁇ x + y ⁇ 0.75.
  • the orthorhombic alkali metal manganese oxide is Nao. 44 Mn0 4 which can be coated onto the surface of the ion-storage compound.
  • the orthorhombic alkali metal manganese oxide is Lio. 44 Mn0 4 .
  • the orthorhombic alkali metal manganese oxide contains both Li and Na.
  • the orthorhombic alkali metal manganese oxide coating materials as described herein have the following advantages.
  • the orthorhombic alkali metal manganese oxide is electronic- and ion-conductive.
  • the resulting coated ion- storage compound still maintains good electronic conductivity and ion conductivity.
  • the orthorhombic alkali metal manganese oxide coating material may also act as a cathode active material and thus contribute to the overall energy density of the cell. Accordingly, a cell including orthorhombic alkali metal manganese oxide coated ion-storage compound as the cathode active material will have high power and energy density and low impedance.
  • the orthorhombic alkali metal manganese oxide can be synthesized first and then coated onto the ion-storage compound.
  • orthorhombic sodium manganese oxide is synthesized.
  • the precursors for the orthorhombic alkali metal manganese oxide can be mixed with particles of the ion- storage compound and the orthorhombic alkali metal manganese oxide coating on the ion-storage compound is formed in situ.
  • the alkali metal precursor e.g., sodium source such as Na 2 C03
  • a manganese precursor e.g., MnC0 3
  • the ion-storage compound may be powders insoluble in the solvent.
  • the solvent can be aqueous or non-aqueous.
  • Non-limiting examples of the non-aqueous solvents include methanol, ethanol, isopropanol, and acetone.
  • the resulting slurry can then be dried to leave a coating of the precursors on the surface of the ion-storage compound.
  • This precursor-ion-storage compound mixture is then heated to high temperature for a time sufficient to produce the desired orthorhombic alkali metal manganese oxide phase on the particle of the ion-storage compound.
  • the mixture can be heated to about 500 °C, about 600 °C, about 700 °C, about 800 °C, or about 900 °C. Other suitable temperatures are contemplated.
  • the mixture can be heated for about 30 min, 1 h, 2 h, or 3 h. Other suitable heating times are contemplated.
  • the ion-storage compound is blended with the oxygen-gettering compound.
  • a coating of the oxygen-gettering compound may be synthesized via a solution-based chemical synthesis step on lithium metal oxide particles.
  • the oxygen-gettering compound coating may be formed via mechanical milling of small getter particles onto larger lithium metal oxide particles.
  • a positive electroactive material comprising a mixture of a alkali transition metal polyanion compound as the oxygen-gettering compound and a lithium metal oxide as the ion-storage compound is described.
  • the positive electrode material mixture as described herein has higher energy density than alkali transition metal polyanion compound and better thermal safety than lithium metal oxide.
  • an electroactive material formed by blending an alkali transition metal polyanion compound and a lithium metal oxide has improved energy density and better thermal safety.
  • the positive electroactive material is formed by blending a lithium transition metal phosphate compound and a lithium metal oxide. The resulting mixture has higher energy density than the lithium transition metal phosphate compound but can reduce or minimize the thermal run away issue of the lithium metal oxide or improved thermal safety.
  • alkali transition metal polyanion compound : lithium metal oxide molar ratios can be used.
  • the alkali transition metal polyanion compound : lithium metal oxide molar ratio is about 1 :99, 5:95, 10:90, 15:85, 20:80, 25:75, 30:70, 35:65; 40:60, 45:55, 50:50, 55:45, 60:40, 65:35, 70:30, 75:25, 80:20, 85: 15, 90: 10, 95:5, or 99: 1.
  • alkali transition metal polyanion compound and lithium metal oxide are mixed according to the ratios disclosed herein.
  • the two compounds can be mixed using a mill.
  • a planetary mixer is used to mix a slurry comprising alkali transition metal polyanion compound and lithium metal oxide.
  • Other way of mixing powders known in the art are contemplated.
  • the alkali transition metal polyanion compound is subjected to a wet-mill, and then the resulting compounds are combined with lithium transition metal oxide such as NCM into a mixer, e.g., a planetary mixer.
  • dry-mixing methods are used where the lithium metal oxide particles are coated with lithium transitional metal phosphate material coating.
  • the mixed positive electroactive material comprising alkali transition metal poly anion compound and lithium metal oxide has improved energy density and capacity.
  • the mixed positive electroactive material has a charge capacity of more than about 150 mAh/g, 155 mAh/g, 160 mAh/g, 165 mAh/g, 170 mAh/g, 175 mAh/g, or 180 mAh/g.
  • the mixed positive electroactive material has a specific energy of more than about 500 mWh/g, 550 mWh/g, or 600m Wh/g.
  • the powder density using the mixed positive electroactive material disclosed herein is increased due to higher material density of oxide cathode material.
  • the powder density of the mixed positive electroactive material is about 4.5-4.8g/cc.
  • the powder density of lithium iron phosphate (LFP) is about 3.5-3.66g/cc and the powder density of lithium iron manganese phosphate (LFMP) is about 3.4-3.5g/cc.
  • the mixed positive electroactive material as disclosed herein has also improved safety and abuse tolerance compared with lithium transition meal oxide material.
  • the mixed positive electroactive materials do not show the exthothermic peak around 260 °C as shown in a DSC spectrum. The absence of this peak can be expected to correspond to better safety profile under high temperature conditions. This is highly surprising since a component of the mixed positive electroactive material is lithium transition metal oxide material, which is known to have an exthothermic peak around 260 °C in a DSC spectrum. Without wishing to be bound by any particular theory, the absence of this peak around 260 °C may be related to better thermal safety of the material.
  • the mixed positive electrode comprising lithium metal oxide material and lithium transitional metal phosphate material exhibits improved safety profile as shown by Figures and 5 and 6.
  • a lithium metal oxide cathode has a thermal peak shown on the DSC chart indicating an exothermic output between 250 to 300 °C.
  • thermal peak between 250 to 300 °C is no longer present.
  • a Mix oxide blend cathode
  • thermal peak between 250 to 300 °C is no longer present. The disappearance of this thermal peak indicates that the mix cathode materials have a better safety as the cathode no longer has an exothermic reaction at the temperature range between about 250 to about 300 °C.
  • the presence of the exothermic peak on the DSC chart for lithium metal oxide material is associate with the release of radical oxygen by the lithium metal oxide at high temperatures.
  • These generated radical oxygen species are highly reactive and may oxidize other components and materials of the cell, e.g., the electrolyte.
  • Suitable materials for use in an electrolyte may include various organic carbonates which may react with the radical oxygen species, resulting in exothermal reactions damaging the cell.
  • the Fe in LFP or LFMP maybe be in its charged, delithiated state which is easily transformable to iron oxide, e.g. Fe 2 0 3 , by the radical oxygen.
  • the mix cathode material comprises at least about 10% of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 20% of the doped, undoped, or mixed metal lithium iron phosphate material.
  • the mix cathode material comprises at least about 30% of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 40%> of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 50% of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 60%> of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 70% of the doped, undoped, or mixed metal lithium iron phosphate material. In some embodiments, the mix cathode material comprises at least about 80% of the doped, undoped, or mixed metal lithium iron phosphate material. Alkali Transition Metal Polyanion Compound as the oxygen-gettering compound
  • the oxygen-gettering compound is alkali transition metal polyanion compound as disclosed in United States Patent No. 7,338,734 is used in the mixture with lithium transition metal oxide to produce the mixed positive electroactive material.
  • lithium transition metal polyanion compound as disclosed in United States Patent Serial No. 12/868,530, filed on August 25, 2010, is used in the mixture with lithium transition metal oxide to produce the mixed positive electroactive material.
  • the oxygen-gettering compound is alkali transition metal polyanion compound with a formula A x (M'i_ a M" a ) y (XD 4 ) z , ⁇ ⁇ ( ⁇ _
  • a x (M'i_ a M” a ) y (X2D 7 ) z has specific surface area of at least 10 m 2 /g, wherein A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum and tungsten, M" is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0 ⁇ a ⁇ 0.1, and x, y, and z have values such that x plus the quantity y(l-a) times a formal valence or valences of M', plus the quantity ya times a formal valence or valence of M", is
  • the conductivity of the compound can be at least about 10 "5 S/cm, at least about 10 "4 S/cm, and, in some cases, at least about 10 "2 S/cm.
  • A is lithium and x/(x+y+z) can range from about zero to about one third, or about zero to about two thirds.
  • X is phosphorus
  • M' is iron.
  • M" can be any of aluminum, titanium, zirconium, niobium, tantalum, tungsten, or magnesium. M" can be substantially in solid solution in the crystal structure of the compound.
  • the compound has at least one of an olivine (e.g., AMP0 4 ), NASICON (e.g., A 2 M 2 (P0 4 ) 3 ), VOP0 4 , LiFe(P 2 0 7 ) or Fe 4 (P 2 0 7 ) 3 structure, or mixtures thereof.
  • an olivine e.g., AMP0 4
  • NASICON e.g., A 2 M 2 (P0 4 ) 3
  • VOP0 4 e.g., LiFe(P 2 0 7 ) or Fe 4 (P 2 0 7 ) 3 structure, or mixtures thereof.
  • the alkali transition metal polyanion compound is a compound with a formula A x (M'i_ a M" a ) y (XD 4 )z, A x (M'i_ a M" a ) y (DXD 4 ) z , or ⁇ ⁇ ( ⁇ _ a M" a ) y (X 2 D 7 ) z , has a conductivity at about 27° C of at least about 10 "8 S/cm, wherein A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum and tungsten, M" is any of a Group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen,
  • A is lithium and x/(x+y+z) can range from about zero to about one third, or about zero to about two thirds.
  • X is phosphorus
  • M' is iron.
  • M" can be any of aluminum, titanium, zirconium, niobium, tantalum, tungsten, or magnesium. M" can be substantially in solid solution in the crystal structure of the compound.
  • the compound has at least one of an olivine (e.g., AMP0 4 ), NASICON (e.g., A 2 M 2 (P0 4 ) 3 ), VOP0 4 , LiFe(P 2 0 2 ) or Fe 4 (P 2 0 7 ) 3 structure, or mixtures thereof.
  • the alkali transition metal polyanion compound is a lithium-transition metal-phosphate compound.
  • the lithium-transition metal- phosphate compound may be optionally doped with a metal, metalloid, or halogen.
  • the positive electroactive material is an olivine structure compound LiMP0 4 , where M is one or more of V, Cr, Mn, Fe, Co, and Ni, in which the compound is optionally doped at the Li, M or O-sites. Deficiencies at the Li-site are compensated by the addition of a metal or metalloid, and deficiencies at the O-site are compensated by the addition of a halogen.
  • the positive active material is a thermally stable, transition-metal-doped lithium transition metal phosphate having the olivine structure and having the formula (Lii_ x Z x )MP0 4 , or Li(Mi- x Z x )P0 4 where M is one or more of V, Cr, Mn, Fe, Co, and Ni, and Z is a non- alkali metal dopant such as one or more of Ti, Zr, Nb, Al, Ta, W or Mg, and x ranges from 0.005 to 0.05.
  • the electroactive material is (Lii_ x Z x )MP0 4 , where Z is Zr, Nb or Ti.
  • the alkali transition metal phosphate composition has an overall composition of (Ai_ a M" a ) x M' y (XD 4 ) z , (Ai_ a M" a ) x M' y (DXD 4 ) z , or (Ai_ a M” a ) x M' y (X 2 D 7 ), and has a conductivity at 27° C of at least about 10 "8 S/cm, wherein A is at least one of an alkali metal and hydrogen, M' is a first-row transition metal, X is at least one of phosphorus, sulfur, arsenic, molybdenum, and tungsten, M" any of a Group IIA, A, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB metal, D is at least one of oxygen, nitrogen, carbon, or a halogen, 0.0002 ⁇ a ⁇
  • the conductivity of the compound can be at least about 10 ⁇ 5 S/cm, at least about 10 ⁇ 4 S/cm, and, in some cases, at least about 10 ⁇ 2 S/cm.
  • A is lithium and x/(x+y+z) can range from about zero to about one third.
  • X is phosphorus
  • M' is iron.
  • M" can be any of aluminum, titanium, zirconium, niobium, tantalum, tungsten, or magnesium. M" can be substantially in solid solution in the crystal structure of the compound.
  • the compound has at least one of an olivine, NASICON, VOP0 4 ,
  • M is at least partially in solid solution in the crystal structure of the compound at a concentration of at least 0.01 mole % relative to the concentration of M', the balance appearing as an additional phase, at least 0.02 mole % relative to the concentration of M', the balance appearing as an additional phase, and in yet other embodiments, at least 0.05 mole % relative to the concentration of M', the balance appearing as an additional phase and, in still other embodiments, at a concentration of at least 0.1 mole % relative to the concentration of M', the balance appearing as an additional phase.
  • Doped lithium iron phosphate compounds may be prepared from starting materials of lithium salts, iron compounds and phosphorous salts including, but not limited to, lithium carbonate, ammonium phosphate and iron oxalate, to which a low additional concentration of dopant metal such as Mg, Al, Ti, Fe, Mn, Zr, Nb, Ta and W have been added, typically as a metal oxide or metal alkoxide.
  • the powder mixture is heated under a low oxygen environment at a temperature of 300 °C to 900 °C. These compounds exhibit increased electronic conductivity at and near room temperature, which is particularly advantageous for their use as lithium storage materials. Further details regarding the composition and preparation of these compounds are found in United States Published Application 2004/0005265
  • the lithium transition metal phosphates include those described in U.S. Patent Application No. 11/396,515, filed April 3, 2006 entitled "Nanoscale Ion Storage Materials” which is incorporated herein in its entirety by reference.
  • Examples include nanoscale ordered or partially disordered structures of the olivine (A x MP0 4 ), NASICON (A x (M',M") 2 (P0 4 ) 3 ), VOP0 4 , LiVP0 4 F, LiFe(P 2 0 7 ) or Fe 4 (P 2 0 7 ) 3 structure types, wherein A is an alkali ion, and M, M' and M" are metals.
  • the lithium transition metal phosphate composition has the formula LiMP0 4 (i.e., an olivine structure type), where Mis one or more transition metals.
  • the lithium transition metal phosphate composition is an ordered olivine (Lii_ x MX0 4 ), where M is at least one first row transition metal (e.g., one or more of V, Cr, Mn, Fe, Co and Ni), and x can range from zero to one, during lithium insertion and deinsertion reactions.
  • M is Fe. In the as-prepared state, x is typically about one.
  • the special properties of the lithium transition metal phosphate may be augmented by doping with foreign ions, such as metals or anions.
  • Such materials are expected to exhibit similar behavior to that demonstrated herein for Lii_ x FeP0 4 at the nanoscale, based on the scientific principles underlying such behavior.
  • doping is not required for a material to exhibit special properties at the nanoscale.
  • the lithium transition metal phosphate material has an overall composition of Lii_ x _ z Mi_ Z P0 4 , where M comprises at least one first row transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co and Ni, where x is from 0 to 1 and z can be positive or negative. In some embodiments, M includes Fe, and z is between about 0.15 and -0.15.
  • the lithium transition metal phosphate material can exhibit a solid solution over a composition range of 0 ⁇ x ⁇ 0.30, for example 0 ⁇ x ⁇ 0.15.
  • the material exhibits a stable solid solution over a composition range of x between 0 and at least about 0.15.
  • the lithium transition metal phosphate material exhibits a stable solid solution over a composition range of x between 0 and at least about 0.07 or between 0 and at least about 0.05 at room temperature (22-25 °C).
  • the lithium transition metal phosphate material can also exhibit a stable solid solution at low lithium content; e.g., where 0.8 ⁇ x ⁇ l or where 0.9 ⁇ x ⁇ l, or where 0.95 ⁇ x ⁇ l .
  • the lithium transition metal phosphate has a lithium-rich transition metal phosphate phase and a lithium-poor transition metal phosphate phase.
  • the lithium-rich transition metal phosphate phase has the composition Li y MP0 4 and the lithium-poor transition metal phosphate phase has the composition Lii_ x MP0 4 , and 0.02 ⁇ y ⁇ 0.2 and
  • the material can exhibit a solid solution over a composition range of 0 ⁇ x ⁇ 0.15 and 0.02 ⁇ y ⁇ 0.10.
  • the nanoscale lithium transition metal phosphate materials are also based on the alkali transition metal phosphates, such as those described in U.S. Patent Application No. 10/329,046.
  • the alkali transition metal phosphates such as those described in U.S. Patent Application No. 10/329,046.
  • the electroactive material has an overall composition of Li x Fei_ a M" a P0 4 , and a conductivity at 27° C, of at least about 10 "8 S/cm.
  • the conductivity is at least about at least about 10 ⁇ 7 S/cm, in other cases, at least about 10 " 6 S/cm, in yet other cases, at least about 10 "5 S/cm, in still other cases, at least about 10 "4 S/cm, in some cases, at least about 10 "3 S/cm, and in other cases, at least about 10 ⁇ 2 S/cm.
  • the lithium transition metal phosphate composition has an overall composition of Li x Fei_ a M" a PO y , the compound having a gravimetric capacity of at least about 80 mAh/g while the device is charging/discharging at greater than about C rate.
  • the capacity is at least about 100 mAh/g, or in other embodiments, at least about 120 mAh/g, in some embodiments, at least about 150 mAh/g, and in still other embodiments, at least about 160 mAh/g.
  • the lithium transition metal phosphate composition has an overall composition of Li x _ a M" a FeP0 4 .
  • the lithium transition metal phosphate composition has an overall composition of Li x _ a M" a FeP0 4 , and a conductivity at 27° C of at least about 10 "8 S/cm.
  • the conductivity is at least about at least about 10 ⁇ 7 S/cm, in other cases, at least about 10 "6 S/cm, in yet other cases, at least about 10 "5 S/cm, in still other cases, at least about 10 "4 S/cm, and in some cases, at least about 10 "3 S/cm, and in further cases, at least about 10 ⁇ 2 S/cm.
  • the lithium transition metal phosphate composition has an overall composition of Li x _ a M" a FeP0 4 , the compound having a gravimetric capacity of at least about 80 mAh/g while the device is charging/discharging at greater than about C rate.
  • the capacity is at least about 100 mAh/g, or in other embodiments, at least about 120 mAh/g; in some embodiments, at least about 150 mAh/g and in still other embodiments, at least about 170 mAh/g.
  • the present invention can, in some embodiments, also provide a capacity up to the theoretical gravimetric capacity of the compound.
  • the nanoscale lithium transition metal phosphate is LiFeP0 4 .
  • M" is at least partially in solid solution in the crystal structure of the compound at a concentration of at least 0.01 mole % relative to the concentration of M', the balance appearing as an additional phase, at least 0.02 mole % relative to the concentration of M', the balance appearing as an additional phase, and in yet other embodiments, at least 0.05 mole % relative to the
  • concentration of M' the balance appearing as an additional phase and, in still other embodiments, at a concentration of at least 0.1 mole % relative to the concentration of M', the balance appearing as an additional phase.
  • the lithium transition metal phosphate composition has a suitable electronic conductivity greater than about 10 "8 S/cm.
  • the alkali transition metal phosphate composition can be a composition of Li x (Mi_ a M" a )P0 4 or L x - a " a M'P0 4 , and can crystallize in the ordered-olivine or triphylite structure, or a structure related to the ordered olivine or triphylite structure with small displacements of atoms without substantial changes in the coordination number of anions around cations, or cations around anions.
  • Li + substantially occupies the octahedral site typically designated as Ml
  • a substantially divalent cation M' substantially occupies the octahedrally-coordinated site typically designated as M2, as described in the olivine structure given in "Crystal Chemistry of Silicate Minerals of Geophysical Interest," by J. J. Papike and M. Cameron, Reviews of Geophysics and Space Physics, Vol. 14, No. 1, pages 37-80, 1976.
  • the exchange of Li and the metal M' between their respective sites in a perfectly ordered olivine structure is allowed so that M' may occupy either site.
  • M' is typically one or more of the first-row transition metals, V, Cr, Mn, Fe, Co, or Ni.
  • M" is typically a metal with formal valence greater than I+as an ion in the crystal structure.
  • M', M", x, and a are selected such that the electroactive material is a crystalline compound that has in solid solution charge compensating vacancy defects to preserve overall charge neutrality in the compound.
  • this condition can be achieved when a times the formal valence of M" plus (1-a) times the formal valence of M' plus x is greater than 3+, necessitating an additional cation deficiency to maintain charge neutrality, such that the crystal composition is Li x (M'i_ a _
  • the dopant can be supervalent and can be added under conditions of temperature and oxygen activity that promote ionic compensation of the donor, resulting in nonstoichiometry.
  • the vacancies can occupy either Ml or M2 sites.
  • the compound When x ⁇ l, the compound also has additional cation vacancies on the Ml site in a crystalline solid solution, said vacancies being compensated by increasing the oxidation state of M" or M'.
  • a suitable concentration of said cation vacancies should be greater than or equal to 10 18 per cubic centimeter.
  • the lithium transition metal phosphate composition has an olivine structure and contains in crystalline solid solution, amongst the metals M' and M", simultaneously the metal ions Fe 2+ and Fe 3+ , Mn 2+ and Mn 3+ , Co 2+ and Co 3+ , Ni 2+ and Ni , V and V , or Cr and Cr , with the ion of lesser concentration being at least 10 parts per million of the sum of the two ion concentrations.
  • the alkali transition metal phosphate composition has an ordered olivine structure and A, M', M", x, and a are selected such that there can be Li substituted onto M2 sites as an acceptor defect.
  • typical corresponding crystal compositions are Li x (M'i_ a _ y M" a Liy)P0 4 or Li x _ a M" a M'i_ y Li y P0 4 .
  • the subvalent Li substituted onto M2 sites for M' or M" can act as an acceptor defect.
  • a suitable concentration of said Li on M2 sites should be greater than or equal to 10 18 per cubic centimeter.
  • the nanoscale lithium transition metal phosphate is a p-type semiconducting composition, for example Li x (M'i_ a M" a )P0 4 , Li x M" a M'P0 4 , Li x (M'i_ a _ y M" a vac y )P0 4 , Li x _ a M" a M'i_ y vac y P0 4 , Li x (M'i_ a _ y M" a Li y )P0 4 or Li x _ a M" a M'i_ y Li y P0 4 .
  • M is a group IIA, IIIA, IVA, VA, VIA, VIIA, VIIIA, IB, IIB, IIIB, IVB, VB, and VIB element of the Periodic Table (catalog number S- 18806, published by the Sargent- Welch company in 1994).
  • Magnesium is an example of a dopant from Group IIA
  • Y is an example of a dopant from Group IIIA
  • Ti and Zr are examples of dopants from Group IVA
  • Nb and Ta are examples of dopants from Group VA
  • W is an example of a dopant from Group VIA
  • Fe is an example of a metal from Group VIII A
  • Al is an example of a dopant from Group IIIB.
  • x can have a value between zero and 1.1 in the initially prepared material. During its use as a lithium ion storage compound, x can vary between about zero and about 1.1. In the nanoscale materials described herein, a can have a value between about 0.0001 and 0.1. In some embodiments, out of the total amount a of M", at least 0.0001 is in solid solution in the crystalline structure of the compound.
  • M' is Fe and the solubility of M" in the lattice can be improved if M" has an ionic radius, in octahedral coordination, that is less than that of Fe 2+ .
  • Achieving solid solubility sufficient to increase the electronic conductivity above 10 "8 S/cm can require that processing conditions (for example, temperature, atmosphere, starting materials) allow M" to be stabilized in a particular valence state that would provide an ionic radius less than that of Fe 2+ .
  • the M" ion may occupy the Ml site, or it may preferentially occupy the M2 site and cause Fe 2+ or Fe 3+ , which would normally occupy the M2 site, to occupy the Ml site.
  • Li x _ a M" a M'P0 4 , M" typically has an ionic radius that is less than the average ionic radius of ions M' at the Li concentration x at which the compound is first synthesized.
  • Electrochemical insertion and removal can later change the valence distribution amongst the M' and M" ions.
  • M can be in the desired valence state and concentration by adding, to the starting material, a salt of M" having the desired final valence.
  • the desired valence distribution amongst metals M' and M" can be obtained by synthesizing or heat treating under appropriate conditions of temperature and gas atmosphere. For example, if M' is Fe, heat treatment should be conducted under temperature and atmosphere conditions that preserve a predominantly 2+ valence state, although some Fe 3+ is allowable and can even be beneficial for increasing conductivity.
  • the olivine composition according to some embodiments of the present invention may have a lithium deficiency that can result in a Li x _ a M" a M'P0 4 crystal composition.
  • M are not limited to those Groups of the Periodic Table that were previously identified, rather, M" can be any metal that satisfies the above requirements of size and valence.
  • M may be Mg 2+ , Mn 2+ , Fe 3+ , Al 3+ , Ce 3+ , Ti 4+ , Zr 4+ , Hf ⁇ , Nb 5+ , Ta 5+ , W 4+ , W 6+ , or combinations thereof.
  • the lithium transition-metal phosphate compounds e.g., doped or undoped LiFeP0 4
  • the lithium transition-metal phosphate compounds can be prepared with a markedly smaller particle size and much larger specific surface area than previously known positive active materials, such as LiCo0 2 , LiNi0 2 or LiMn 2 0 4 and, thus improved transport properties. Improved transport properties reduce impedance and may contribute to low impedance growth.
  • the lithium transition-metal phosphate compounds consist of powder or particulates with a specific surface area of greater than about 5 m 2 /g, greater than about 10 m 2 /g, greater than about 15 m 2 /g, greater than about 20 m 2 /g, greater than about 30 m 2 /g, 35 m 2 /g, 40 m 2 /g, or 50 m 2 /g.
  • lithium transition metal oxide usually has specific surface areas of less than about 10 m 2 /g.
  • LiFeP0 4 having the olivine structure and made in the form of very small, high specific surface area particles is exceptionally stable in delithiated form even at elevated temperatures and in the presence of oxidizable organic solvents, e.g., electrolytes, thus enabling a safer Li-ion battery having a very high charge and discharge rate capability.
  • the small-particle-size, high specific-surface-area LiFeP0 4 material exhibits not only high thermal stability, low reactivity and high charge and discharge rate capability, but it also exhibits excellent retention of its lithium intercalation and deintercalation capacity during many hundreds, or even thousands, of high-rate cycles.
  • lithium transition metal phosphate has the formula LiMP0 4 , where M is one or more transition metals.
  • the nanoscale alkaline transition metal phosphate is doped at the Li site. In some embodiments, the nanoscale alkaline transition metal phosphate is doped at the M site. It has been unexpectedly discovered that these ion storage materials having
  • the nanoscale materials are compositionally and structurally distinct from, and provide different and improved electrochemical utility and performance compared to, the coarse-grained materials.
  • the difference in relevant physical properties arises because the nanoscale materials are sufficiently small in at least one dimension (for instance, the diameter of an equi-axed particle, the diameter of a nanorod, or the thickness of a thin film) that they have different defect and thermodynamic properties.
  • the lithium transition metal phosphate has a BET (Brunauer-Emmett-Teller method) specific surface area of at least about 5 m 2 /g, at least about 10 m 2 /g, at least about 15 m 2 /g, at least about 20 m 2 /g, at least about 25 m 2 /g, at least about 30 m 2 /g, at least about 35 m 2 /g, at least about 40 m 2 /g, at least about 45 m 2 /g, or at least about 50 m 2 /g.
  • BET Brunauer-Emmett-Teller method
  • lithium transition metal phosphate includes approximately equi-axed particles having an "equivalent spherical particle size" (number-averaged mean particle diameter that would result in the measured surface area if the material were in the form of identically-sized spherical particles) of about 100 nm or less, for example, about 75 nm or less, about 70 nm or less, about 60 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, or about 35 nm or less.
  • "equivalent spherical particle size" number-averaged mean particle diameter that would result in the measured surface area if the material were in the form of identically-sized spherical particles
  • the material includes anisometric particles or a thin film or coating having a smallest cross-sectional dimension that is, on a number-averaged basis to provide a mean value, about 100 nm or less, for example, about 75 nm or less, about 70 nm or less, about 60 nm or less, about 50 nm or less, about 45 nm or less, about 40 nm or less, or about 35 nm or less.
  • These dimensions can be measured using various methods, including direct measurement with an electron microscope of the transmission or secondary-electron type, or with atomic force microscopy.
  • Such nanoscale ion storage materials are described in more detail in U.S. Application No. 10/329,046, supra.
  • alkali transition metal polyanion compound with smaller specific surface areas can be used for the mixed positive electroactive material disclosed herein.
  • the alkali transition metal polyanion compound is lithium transition metal phosphate with a BET (Brunauer-Emmett-Teller method) specific surface area of at least about 0.5 m 2 /g, at least about 1 m 2 /g, at least about 2 m 2 /g, at least about 3 m 2 /g, at least about 5 m 2 /g, at least about 7 m 2 /g, at least about 9 m 2 /g, or at least about 10 m 2 /g.
  • BET Brunauer-Emmett-Teller method
  • the lithium transition metal phosphate described herein are prepared from conventional materials by size-reduction processes (e.g. , milling) to reduce the particle dimensions into the desired range.
  • size-reduction processes e.g. , milling
  • the materials also can be synthesized in the nanoscale state, by methods including, but not limited to, solid-state reactions between metal salts, wet-chemical methods, such as co-precipitation, spray-pyrolysis, mechanochemical reactions, or combinations thereof.
  • Nanoscale materials with the desired particle sizes and specific surface areas are obtained by using homogeneous reactants, minimizing the reaction or crystallization temperature (in order to avoid particle coarsening), and avoiding formation of liquid phases in which the product is highly soluble (which also tends to lead to particle coarsening).
  • Specific processing conditions can typically be established for a given process without undue
  • nanoscale lithium transition metal phosphate materials are prepared by non-equilibrium, moderate temperature techniques, such as wet-chemical or low temperature solid-state reactions or thermochemical methods.
  • the materials thus prepared can acquire properties such as increased
  • nonstoichiometry and disorder and increased solubility for dopants because they are synthesized in a metastable state or because kinetic pathways to the final product differ from those in conventional high temperature processes.
  • Such disorder in the nanoscale form can also be preserved substantially under electrochemical use conditions and provide benefits as described herein.
  • (Fe+Mn+D) ranges from about 1.0 to about 1.05, the ratio of the amount of P0 4 : (Fe+Mn+D) ranges from about 1.0 to about 1.025
  • D is one or more metals selected from the group consisting of cobalt (Co), nickel (Ni), vanadium (V), niobium (Nb), and mixtures thereof
  • Mn ranges from 0.350 to less than 0.600, or 0.400 to less than 0.600, or 0.400 to 0.550, or 0.450 to 0.550, or 0.450 to 0.500.
  • D is one or more metals selected from the group consisting of cobalt (Co), vanadium (V), or mixtures thereof.
  • the LFMP material can be further doped with fluorine (F).
  • the composition comprises up to about 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, 5 mol%, 6 mol%, 7, mol%, 8, mol%, 9 mol%, or 10 mol% of the one or more dopant metals.
  • the composition comprises up to 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, or 5 mol% of Co.
  • the composition comprises up to 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, or 5 mol% of Ni. In certain embodiments, the composition comprises up to 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, or 5 mol% of V.
  • the composition comprises up to 0.1 mol%, 0.5 mol%, 1 mol%, 1.5 mol%, 2 mol%, 2.5 mol%, 3 mol%, 3.5 mol%, 4 mol%, 4.5 mol%, or 5 mol% of F.
  • lithium transition metal phosphate material comprises at least an olivinic phase that comprises lithium (Li), iron (Fe), manganese (Mn), one or more dopants (D) and phosphate (P0 4 ), where the overall composition has a ratio of Li : (Fe+Mn+D) ranging from about 1.000 to about 1.050, a ratio of (P0 4 ) : (Fe+Mn+D) ranging from about 1.000 to about 1.025, and D is one or more metals selected from the group consisting of cobalt (Co), nickel (Ni), vanadium (V), niobium (Nb), and mixtures thereof. In certain embodiments, D is one or more metals selected from the group consisting of cobalt (Co), vanadium (V), or mixtures thereof. In certain embodiments, the positive electrode material can be further doped with fluorine (F).
  • F fluorine
  • lithium transition metal phosphate material including a lithium and/or phosphate stoichiometric electroactive material, having one or more phases comprising lithium (Li), iron (Fe), manganese (Mn), one or more dopants (D) and phosphate (P0 4 ), where the overall composition has a ratio of Li : (Fe+Mn+D) that is about 1.000, a ratio of (P0 4 ) : (Fe+Mn+D) that is about 1.000, and D is one or more metals selected from the group consisting of cobalt (Co), nickel (Ni), vanadium (V), niobium (Nb), or mixtures thereof.
  • Li lithium
  • Fe iron
  • Mn manganese
  • D dopants
  • P0 4 phosphate
  • the overall composition has a ratio of Li : (Fe+Mn+D) that is about 1.000, a ratio of (P0 4 ) : (Fe+Mn+D) that is about 1.000
  • D is one or more metals selected from the group consisting of cobalt (Co), vanadium (V), or mixtures thereof.
  • D is one or more metals selected from the group consisting of cobalt (Co), vanadium (V), niobium (Nb). or mixtures thereof.
  • the presence of Nb may increase the electrical conductivity of the electroactive material.
  • the positive electrode material can be further doped with fluorine (F).
  • lithium transition metal phosphate material including a lithium-rich and/or phosphate -rich electroactive material
  • the electroactive material comprises at least an olivinic phase that includes lithium (Li), iron (Fe), manganese (Mn), one or more dopants (D) and phosphate (P0 4 ), where the overall composition has a ratio of Li : (Fe+Mn+D) ranging from about greater than 1.000 to about 1.050, a ratio of (PO 4 ) : (Fe+Mn+D) ranging from about greater than 1.000 to about 1.025, and D is one or more metals selected from the group consisting of cobalt (Co), nickel (Ni), vanadium (V), niobium (Nb), and mixtures thereof. In certain embodiments, D is one or more metals selected from the group consisting of cobalt (Co), vanadium (V), or mixtures thereof.
  • the positive electrode material can be further doped
  • the excess lithium and excess phosphate in the overall composition need not provide a non-stoichiometric olivine compound in a single olivinic structure or single olivinic phase. Rather, the excess lithium and/or phosphate may be present, for example, as secondary phases and the like in conjunction with an olivininc phase.
  • the dopants such as Co, Ni, V, Nb, and/or F, are doped into and reside on the lattice sites of the olivinic structure to form an olivinic phase.
  • lithium transition metal phosphate material that may provide improved energy density and power density include, but are not limited to:
  • Lii.ooo no. 45 oFeo. 53 oCoo.oioNio.oioP0 4
  • Mn-rich Li-Fe-Mn phosphate (LFMP) materials should achieve improved properties, such as energy density and specific capacity.
  • LFMP Mn-rich Li-Fe-Mn phosphate
  • others have focused on such Mn-rich phosphate materials.
  • improved properties of compounds can be obtained, such as energy density and specific capacity, of positive electrode LFMP material having lower levels of Mn, and, for example, where the molar amount of Mn in the LFMP is less than 60%, 55%, 50%, 45%, or 40%.
  • these dopant metals are not expected to directly contribute to the electric storage capacity of the material.
  • the redox potentials of Co and Ni are about at least 0.5V higher than that of manganese and at least 1.0V higher than that of iron, such dopant metals would not normally contribute significant electric storage capacity to a battery cell operating at or near the redox plateau for Fe 2+ ⁇ Fe 3+ .
  • the lithium transition metal phosphate including a doped olivine electroactive compound can be prepared from starting materials of lithium salts, iron compounds and phosphorous salts including, but not limited to, lithium carbonate, iron oxalate or carbonate, manganese carbonate, and ammonium phosphate to which a low additional concentration of dopant metal such as Co, Ni, V, and/or F have been added, such as using cobalt oxalate, nickel oxalate, vanadium oxide, and/or ammonia fluoride.
  • lithium transition metal phosphate is prepared from a lithium source, e.g., a lithium salt, and a transition meal phosphate.
  • the dried powder mixture is heated under a low oxygen, e.g., inert, environment at a temperature of 300 °C to 900 °C, and for example at a temperature of about 600-700°C. Further details regarding the composition and preparation of these compounds are found in United States Published Application 2004/0005265, US 2009/01238134, and US 2009/0186277, all of which are incorporated by reference herein in their entirety.
  • a low oxygen e.g., inert
  • control of the primary olivine crystallite size to ⁇ 100 nm dimensions may be beneficial in enhancing both lithium transport kinetics and conductivity of the LFMP materials.
  • Further details regarding the composition and preparation of such analogous compounds are found in United States Published Application 2004/0005265, now U.S. Patent No. 7,338,734, which is incorporated herein in its entirety by reference.
  • Doping with hypervalent transition metals such as Nb or V may further contribute to the advantageous application of the resulting olivine materials for rechargeable lithium ion battery applications.
  • the advantageous role of the dopant may be several fold and include the increased electronic conductivity of the olivine powder and may limit the sintering of the olivine nanophosphate particles to allow full utilization of the lithium capacity during fast charge/discharge of the battery.
  • Other non- limiting examples of lithium transition metal polyanion compounds include L1C0PO 4 , LiMnP0 4 , Li3V 2 (P0 4 )3, L1VPO 4 F and mixed transition metal phosphate.
  • lithium transition metal oxide for the mixed positive electroactive material is lithium nickel cobalt aluminum oxide (NCA), lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt magnesium oxide, spinel lithium manganese oxide (LMO), or LLC (Layered oxide cathode).
  • NCA lithium nickel cobalt aluminum oxide
  • NCM lithium nickel cobalt manganese oxide
  • LMO lithium nickel cobalt magnesium oxide
  • LMO lithium manganese oxide
  • LLC LLC (Layered oxide cathode).
  • Other non- limiting examples of lithium transition metal oxide include LCO (lithium cobalt oxide); high voltage, spinel Ni, Mn oxide; layered Mn oxide, and other lithium transition metal oxides known in the art can also be used in the mixture of the positive electroactive material as disclosed herein.
  • 7,041,239 (the content of which is hereby incorporated by reference herein in its entirety) are used in the mixture of the positive electroactive material as disclosed herein.
  • the oxygen atom in lithium transition metal oxide is substituted by an another atom such as F, CI, or Br.
  • the concentration of nickel, cobalt, manganese, aluminum, and/or magnesium changes across the radius of the particle.
  • the active material and a conductive additive are combined to provide an electrode layer that permits rapid lithium diffusion throughout the layer.
  • a conductive additive such as carbon or a metallic phase is included in order to improve its electrochemical stability, reversible storage capacity, or rate capability.
  • Exemplary conductive additives include graphite, carbon black, acetylene black, vapor grown fiber carbon (“VGCF”) and fullerenic carbon nanotubes.
  • Conductive diluents are present in a range of about l%-5% by weight of the total solid composition of the positive electrode.
  • the positive electrode (cathode) is manufactured by applying a semi-liquid paste containing the mix cathode active material and conductive additive
  • an adhesion layer e.g., thin carbon polymer intercoating
  • Exemplary adhesion layers include, without limitation, those described in U.S. Patent Application No. 11/515,633, entitled “Nanocomposite Electrodes and Related Devices," filed September 5, 2006, which is incorporated herein in its entirety by reference.
  • the dried layers are calendared to provide layers of uniform thickness and density.
  • the binder used in the electrode may be any suitable binder used as binders for non-aqueous electrolyte cells.
  • Exemplary materials include a
  • PVDF polyvinylidene fluoride-based polymers, such as poly(vinylidene fluoride) (PVDF) and its co- and terpolymers with hexafluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, poly(vinyl fluoride), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymers (ETFE), polybutadiene, cyanoethyl cellulose, carboxymethyl cellulose and its blends with styrene-butadiene rubber, polyacrylonitrile, ethylene propylene diene terpolymers (EPDM), styrene-butadiene rubbers (SBR), polyimides, ethylene-vinyl acetate copolymers.
  • PVDF poly(vinylidene fluoride)
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-tetrafluoroethylene copolymers
  • a positive electrode can have a thickness of less than 150 ⁇ , e.g., between about 50 ⁇ to 125 ⁇ , or between about 80 ⁇ to 100 ⁇ on each side of the current collector, and a pore volume fraction between about 30 and 70 vol. %.
  • the active material is typically loaded at about 10-20 mg/cm 2 , and typically about 11- 15 mg/cm 2 .
  • Other numerical ranges of thickness and material loadings are
  • a thicker electrode layer provides greater total capacity for the battery.
  • thicker layers also increase the electrode impedance.
  • the present inventors have surprisingly discovered that high capacity, thick layers may be used in a low impedance (high rate) cell. Use of a high specific surface area active material, while maintaining adequate pore volume, provides the desired capacity without increasing impedance to unacceptably high levels.
  • the electroactive material of the positive electrode includes a material that, while of high electronic conductivity, does not vary its conductivity by more than a factor of five, or factor of two, over the entire charge cycle.
  • This feature of the Li-ion cell is contrasted with conventional electroactive positive electrode materials such as LiCo0 2 , LiNi0 2 or LiMn 2 0 4 for which
  • the selection criteria for an anode are at two levels, the particle level and the electrode level. At the particle level, the particle size and the Li diffusion coefficient of the particle are selection criteria.
  • the negative active material is a carbonaceous material.
  • the carbonaceous material may be non- graphitic or graphitic.
  • a small-particle-size, graphitized natural or synthetic carbon can serve as the negative active material.
  • graphitic materials or graphite carbon materials may be employed, graphitic materials, such as natural graphite, spheroidal natural graphite, mesocarbon microbeads and carbon fibers, such as mesophase carbon fibers, are preferably used.
  • the carbonaceous material has a numerical particle size (measured by a laser scattering method) that is smaller than about 25 ⁇ , or smaller than about 15 ⁇ , or smaller than about 10 ⁇ , or even less than or equal to about 6 ⁇ .
  • the smaller particle size reduces lithium diffusion distances and increases rate capability of the anode, which is a factor in preventing lithium plating at the anode. In those instances where the particle is not spherical, the length scale parallel to the direction of lithium diffusion is the figure of merit. Larger particle sized materials may be used if the lithium diffusion coefficient is high.
  • the diffusion coefficient of MCMB is ⁇ 10 "10 cm 2 /s.
  • Artificial graphite has a diffusion coefficient of ⁇ 10 "8 cm 2 /s.
  • the anode materials include high capacity silicon tin alloy, other metal compound anode, lithium metal and lithium metal alloy, and lithium titanium oxide(LTO).
  • anode materials include high capacity of Silicon alloy, tin alloy, SiO nano compound, and other metal compound for higher capacity.
  • other oxide can be used such as LTO(lithium titanium oxide).
  • Other suitable anode materials known in the art are contemplated.
  • the anode is an alloy or compound of lithium with another metal or metalloid including Al, Si, Sn, Sb, B, Ag, Bi, Cd, Ga, Ge, In, Pb, or Zn.
  • Other anode materials include those disclosed in U.S. Patent Publication No. 2006/0292444, the content of which is hereby incorporated by reference herein in its entirety.
  • the negative active material consists of powder or particulates with a specific surface area measured using the nitrogen adsorption Brunauer-Emmett-Teller (BET) method to be greater than about 0.1 m 2 /g, 0.5 m 2 /g, 1.0 m 2 /g, 1.5 m 2 /g, 2 m 2 /g, 4 m 2 /g, 6 m 2 /g, 8 m 2 /g, 10 m 2 /g, 12 m 2 /g, 14 m 2 /g, or 16 m 2 /g.
  • BET nitrogen adsorption Brunauer-Emmett-Teller
  • the active material and a conductive additive are combined to provide an electrode layer that permits rapid lithium diffusion throughout the layer.
  • a conductive additive such as carbon or a metallic phase may also be included in the negative electrode.
  • Exemplary conductive additives include graphite, carbon black, acetylene black, vapor grown fiber carbon ("VGCF”) and fullerenic carbon nanotubes. Conductive diluents are present in a range of about 0%-5% by weight of the total solid composition of the negative electrode.
  • the negative electrode (anode) of the battery is manufactured by preparing a paste containing the negative active material, such as graphitic or non-graphitic carbon, and a conductive carbon additive homogeneously suspended in a solution of a polymer binder in a suitable casting solvent.
  • the paste is applied as a uniform- thickness layer to a current collector and the casting solvent is removed by drying.
  • a metallic substrate such as copper foil or grid is used as the negative current collector.
  • an adhesion promoter e.g., oxalic acid, may be added to the slurry before casting.
  • the binder used in the negative electrode may be any suitable binder used as binders for non-aqueous electrolyte cells.
  • Exemplary materials include a polyvinylidene fluoride (PVDF)- based polymers, such as poly(vinylidene fluoride) (PVDF) and its co- and terpolymers with hexafluoroethylene, tetrafluoroethylene, chlorotrifluoroethylene, poly( vinyl fluoride), polytetrafluoroethylene (PTFE), ethylene-tetrafluoroethylene copolymers (ETFE), polybutadiene, cyanoethyl cellulose, carboxymethyl cellulose and its blends with styrene-butadiene rubber, polyacrylonitrile, ethylene propylene diene
  • PVDF polyvinylidene fluoride
  • PVDF poly(vinylidene fluoride)
  • PTFE polytetrafluoroethylene
  • ETFE ethylene-tetrafluoroethylene copolymers
  • polybutadiene cyanoethyl cellulose, carboxymethyl cellulose and its
  • EPDM styrene-butadiene rubbers
  • SBR styrene-butadiene rubbers
  • polyimides ethylene-vinyl acetate copolymers
  • the negative electrode can have a thickness of less than about 200 ⁇ , about 150 ⁇ , about 100 ⁇ , about 90 ⁇ , or about 75 ⁇ , e.g., between about 20 ⁇ to about 65 ⁇ , or between about 40 ⁇ to about 55 ⁇ on both sides of the current collector, and a pore volume fraction between about 20 and about 40 vol. %.
  • the active material is typically loaded at about 1-20 mg/cm 2 , or about 4-5 mg/cm 2 .
  • a thicker electrode layer provides greater total capacity for the battery.
  • thicker layers also increase the electrode impedance by reducing the ease of lithium diffusion into the anode.
  • the present inventors have surprisingly discovered that high capacity, thick layers may be used in a low impedance cell through selection of active materials as indicated above and maintaining adequate pore volume.
  • a nonaqueous electrolyte is used and includes an appropriate lithium salt.
  • the salts include LiPF 6 , LiBF 4 , LiAsF 6 , or lithium bis(trifluoromethylsulfonimide) (LiTFMSI), lithium bis(oxalatoborate) (LiBOB), or lithium bis(pentafluoroethylsulfonyl)imide (LiBETI) dissolved in a nonaqueous solvent.
  • LiTFMSI lithium bis(trifluoromethylsulfonimide)
  • LiBOB lithium bis(oxalatoborate)
  • LiBETI lithium bis(pentafluoroethylsulfonyl)imide
  • One or more functional additives such as, for example, C0 2 , vinylene carbonate, ethylene sulfite, ethylene thiocarbonate, dimethyl dicarbonate, spirodicarbonate and propane sultone, can be included to modify the solid-electrolyte interface/interphase (SEI) that forms on the electrodes, particularly negative carbon electrodes.
  • SEI solid-electrolyte interface/interphase
  • the electrolyte may be infused into a porous separator that spaces apart the positive and negative electrodes.
  • a microporous electronically insulating separator is used.
  • Li- ion battery electrolytes notably a family of cyclic carbonate esters such as ethylene carbonate (EC), Fluoroethylene Carbonate (FEC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC), and their chlorinated or fluorinated derivatives, and a family of acyclic dialkyl carbonate esters, such as dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, dibutyl carbonate, butylmethyl carbonate, butylethyl carbonate and butylpropyl carbonate.
  • a family of cyclic carbonate esters such as ethylene carbonate (EC), Fluoroethylene Carbonate (FEC), propylene carbonate (PC), butylene carbonate (BC), and vinylene carbonate (VC), and their chlorinated or fluorinated derivative
  • solvents proposed as components of Li-ion battery electrolyte solutions include methyl acetate (MA), ethyl acetate (EA), methyl formate (MF), propyl acetate (PA), methyl butyrate (MB), ethyl butyrate (EB), ⁇ -butyrolactone ( ⁇ -BL), dimethoxy ethane, tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 4-methyl-l,3-dioxolane, diethyl ether, sulfolane, methylsulfolane, acetonitrile, propiononitrile, ethyl acetate, methyl propionate, ethyl propionate and the like. These nonaqueous solvents are typically used as multicomponent mixtures. Other solvents suitable for use as electrolytes known in the art are contemplated.
  • a cell exhibiting low impedance growth employs an electrolyte having the following composition: about 0.8 M to about 1.5 M LiPF 6 in an organic solvent made up of about 30 wt% to about 70 wt% ethylene carbonate, about 0 wt% to about 20 wt% propylene carbonate, about 0 wt% to about 60 wt% dimethyl carbonate, about 0 wt% to about 60 wt% ethyl methyl carbonate, about 0 wt% to about 60 wt% diethyl carbonate, and about 0 wt% to about 5 wt% vinylene carbonate.
  • the cell exhibiting low impedance growth and employing this electrolyte composition includes a cathode active material having an olivine structure and a formula L1MPO 4 , where M is one or more transition metals, and the material is doped or undoped at the lithium or M site.
  • the cell includes a carbonaceous anode active material, for example, a graphitic material such as mesocarbon microbeads (MCMB).
  • a cell exhibiting low impedance growth employs an electrolyte having the following composition: about 0.8 M to about 1.5 M LiPF 6 in an organic solvent made up of about 30 wt% to about 70 wt% ethylene carbonate, about 0 wt% to about 20 wt% propylene carbonate, about 0 wt% to about 60 wt% dimethyl carbonate, and about 0 wt% to about 60 wt% ethyl methyl carbonate.
  • the sum of the weight percents of ethylene carbonate and propylene carbonate is between about 30 wt% and about 70 wt% of the total organic solvent, and propylene carbonate represents about 30 wt% or less of this sum.
  • the cell exhibiting low impedance growth and employing this electrolyte composition includes a cathode material having an olivine structure and a formula L1MPO 4 , where M is one or more transition metals, and the material is doped or undoped at the lithium or M site.
  • the cell includes a carbonaceous anode material, for example, a graphitic material such as mesocarbon microbeads (MCMB).
  • a cell exhibiting low impedance growth employs an electrolyte having the following composition: about 0.8 M to about 1.5 M LiPF 6 in an organic solvent made up of about 30 wt% to about 70 wt% ethylene carbonate, about 0 wt% to about 20 wt% propylene carbonate, and about 0 wt% to about 70 wt% dimethyl carbonate and/or diethyl carbonate and/or ethyl methyl carbonate.
  • the sum of the weight percents of ethylene carbonate and propylene carbonate is between about 30 wt% and about 70 wt% of the total organic solvent, and propylene carbonate represents about 30 wt% or less of this sum.
  • the cell exhibiting low impedance growth and employing this electrolyte composition includes a cathode material having an olivine structure and a formula L1MPO 4 , where M is one or more transition metals, and the material is doped or undoped at the lithium or M site.
  • the cell includes a carbonaceous anode material, for example, a graphitic material such as mesocarbon microbeads (MCMB).
  • a cell exhibiting low impedance growth employs an electrolyte having the following composition: about 1.0 M to about 1.3 M LiPF 6 in an organic solvent made up of about 30 wt% to about 50 wt% ethylene carbonate, about 10 wt% to about 20 wt% propylene carbonate, about 20 wt% to about 35 wt% dimethyl carbonate, about 20 wt% to about 30 wt% ethyl methyl carbonate, and about 1 wt% to about 3 wt% vinylene carbonate.
  • the cell exhibiting low impedance growth and employing this electrolyte composition includes a cathode material having an olivine structure and a formula L1MPO 4 , where M is one or more transition metals, and the material is doped or undoped at the lithium or M site.
  • the cell includes a carbonaceous anode material, for example, a graphitic material such as mesocarbon microbeads (MCMB).
  • a solid or gel electrolyte may also be employed.
  • the electrolyte may be an inorganic solid electrolyte, e.g., LiN or Lil, or a high molecular weight solid electrolyte, such as a gel, provided that the materials exhibits lithium conductivity.
  • Exemplary high molecular weight compounds include poly(ethylene oxide), poly(methacrylate) ester based compounds, or an acrylate-based polymer, and the like.
  • the lithium salt at least one compound from among L1CIO 4 , LiPF 6 , LiBF 4 , L1SO 3 CF 3 , LiN(S0 2 CF 3 ) 2 , LiN(S0 2 CF 2 CF 3 ) 2 LiAsF 6 , lithium
  • the lithium salt is at a concentration from about 0.5 to about 1.5 M, for example, in certain embodiments from about 1.0 to about 1.3 M.
  • the above described positive electrode is brought into intimate contact with the negative electrode through the separator layers, which are then spirally wound a number of times around a small-diameter mandrel to form the jelly-roll electrode-separator assembly.
  • the jelly-roll structure is inserted into a battery can, for example, made of nickel-plated steel or aluminum, current collector tabs are spot-welded to the battery can and can header, which is preferably equipped with a variety of safety features, such as positive-temperature coefficient elements, pressure burst disks, etc.
  • uncoated regions can be created along the edge of the electrode, thereby exposing bare metal foil.
  • One or preferably more metal foil strips or tabs can be attached to these bare regions using an ultrasonic welder. These tabs can then be attached to the can or header using an ultrasonic or spot (resistance) welder.
  • the nonaqueous electrolyte for example, including a solution of a lithium salt in a mixture of carbonate esters, is injected into the battery can, the can header is sealed to the battery can using a crimp seal or laser weld.
  • An alternative cell design is described in U.S. Patent No. 7927732, filed on September 5, 2006, entitled "Battery Cell Design and Method of Its Construction," which is incorporated in its entirety by reference herein.
  • Other non-limiting examples of cell types include pouch sealing type prismatic and Aluminum can or the other metal can type prismatic cells.
  • the cell is a pouch material sealing type of pouch cells.
  • a Li-ion battery contains an optionally doped lithium transition metal phosphate positive electrode, a highly microporous electronically insulating separator layer, a graphitized-carbon negative electrode, and a multicomponent liquid organic electrolyte solution in which a lithium salt is dissolved at a concentration from about 0.5 to about 1.5 M.
  • Both the positive and negative electrodes have high surface area and high pore volume. In order to reduce the chance of lithium plating at the anode, the lithium capacity of the negative electrode is higher than that of the positive electrode.
  • the battery is capable of being charged and discharged at a very high rate, due to having the above described relative electrode resistances, which is accomplished by the selection of appropriate active materials, e.g., composition, particle size, porosity, surface area, pore volume, etc., and by the addition of appropriate amounts of conductive diluents such as carbon to the positive or negative electrode.
  • active materials e.g., composition, particle size, porosity, surface area, pore volume, etc.
  • conductive diluents such as carbon
  • a process for the synthesis of a lithium electroactive metal phosphate includes the milling and heating a mixture of materials including a lithium source, an iron phosphate and one or more additional dopant metal sources under a reducing atmosphere.
  • Exemplary starting materials include, but are not limited to, lithium carbonate, ferric phosphate, and vanadium oxide.
  • the mixtures are heated at atmospheric pressures under a reducing atmosphere to temperatures of approximately 550-700°C, followed by cooling to room temperature, typically under inert atmospheres. Further details regarding the composition and preparation of these compounds are found in United States Patent No. 7,282,301, which is incorporated herein in its entirety by reference.
  • a process for the synthesis of a lithium electroactive metal phosphate includes the a water-based milling process, wherein starting materials, such as lithium carbonate, hydrated iron phosphate, hydrated manganese phosphate, lithium dihydrogen phosphate, hydrated cobalt oxalate, hydrated nickel oxalate, and ammonium metavanadate are mixed with water soluble vinyl based copolymers or sugar precursors for milling and subsequent drying. After drying, the power can be heated under desired temperature ramp-up conditions up to about 700 °C, followed by cooling to room temperature.
  • starting materials such as lithium carbonate, hydrated iron phosphate, hydrated manganese phosphate, lithium dihydrogen phosphate, hydrated cobalt oxalate, hydrated nickel oxalate, and ammonium metavanadate are mixed with water soluble vinyl based copolymers or sugar precursors for milling and subsequent drying.
  • the power can be heated under desired temperature ramp-up conditions up to about 700 °C, followed
  • the positive electrode (cathode) is manufactured by applying a semi-liquid paste containing the cathode active compound and conductive additive
  • a metallic substrate such as aluminum foil or expanded metal grid is used as the current collector.
  • an adhesion layer e.g., thin carbon polymer intercoating, may be applied.
  • the dried layers are calendared to provide layers of uniform thickness and density.
  • the binder used in the electrode may be any suitable binder used as binders for non-aqueous electrolyte cells.
  • the positive electrode active material can be incorporated into any battery shape.
  • various different shapes and sizes such as cylindrical (jelly roll), square, rectangular (prismatic) coin, button or the like may be used.
  • the precursors consisting of a sodium source such as Na 2 C0 3 and a manganese source such as MnC0 3 , are dissolved in the stoichiometric ratio in water, then mixed with LiCo0 2 or LiNi0 2 , which are insoluble powders. The resulting slurry is dried to leave a coating of the precursors on the surface of the lithium metal oxide. This precursor mix is then heated to about 800 °C for a time sufficient to produce the desired orthorhombic Na 0 . 44 MnO 2 phase on the particle of LiCo0 2 or LiNi0 2 .
  • Example 1 Producing Mixed Positive Electroactive Material
  • Lithium iron phosphate (Nano phosphate powder)) or lithium iron manganese phosphate powders were mixed together with lithium transition metal oxide cathode powders such as lithium nickel aluminum oxide (NCA), lithium nickel cobalt, manganese oxide (NCM), spinel lithium manganese oxide (LMO), and LLC (Layered oxide cathode) for use in the cathode.
  • NCA lithium nickel aluminum oxide
  • NCM lithium nickel cobalt
  • MCM manganese oxide
  • LMO spinel lithium manganese oxide
  • LLC Layerered oxide cathode
  • Graphite based anode was prepared and polyolefm type separator or ceramic-coated separator can be used to assemble the cell. Typical liquid electrolyte as described herein were used. After the battery is assembled, the cell was run from 2.4V to 4.2V range for cycling and operation.
  • the mixed positive electroactive materials exhibited high energy density and better abuse tolerance performances. Higher energy density was obtained with better cell safety (see the coin cell data for the cell energy in Figures 1, 2, and 3, and Tables 1 and 2).
  • Blend cathode of oxide NCM active material shows higher energy than 100% LFP (Ml, Mix) cathode cells.

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Abstract

La présente invention porte sur une matière électroactive positive comprenant : un composé d'absorption d'oxygène apte à piéger l'oxygène et un composé de stockage d'ions. Selon certains modes de réalisation, le composé de stockage d'ions est apte à libérer des espèces d'oxygène réactives, par exemple, l'oxygène radicalaire, lorsqu'il est chauffé. Le composé d'absorption d'oxygène est apte à piéger les espèces d'oxygène réactives soit par absorption physique, soit par réaction chimique.
PCT/US2012/058476 2011-10-03 2012-10-02 Matières de cathode comprenant un composé d'absorption d'oxygène et un composé de stockage d'ions WO2013052494A1 (fr)

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US20140209832A1 (en) * 2013-01-30 2014-07-31 Hitachi Metals, Ltd. Positive Electrode Active Material for Non-Aqueous Secondary Battery and Manufacturing Method Thereof, as well as Non-Aqueous Secondary Battery Using Positive Electrode Active Material
WO2015018751A1 (fr) * 2013-08-09 2015-02-12 Robert Bosch Gmbh Batterie lithium-ion
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US9502737B2 (en) 2013-05-23 2016-11-22 Ambri Inc. Voltage-enhanced energy storage devices
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JP2017103170A (ja) * 2015-12-04 2017-06-08 株式会社デンソー リチウムイオン二次電池用正極及びその製造方法
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CN109841801A (zh) * 2017-11-28 2019-06-04 中国科学院大连化学物理研究所 一种碳包覆NaxRyM2(PO4)3材料及其制备和应用
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WO2021048796A1 (fr) * 2019-09-12 2021-03-18 Saft America Matériaux actifs d'électrode positive pour une batterie secondaire au lithium-ion
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US10181800B1 (en) 2015-03-02 2019-01-15 Ambri Inc. Power conversion systems for energy storage devices
US10566662B1 (en) 2015-03-02 2020-02-18 Ambri Inc. Power conversion systems for energy storage devices
US11840487B2 (en) 2015-03-05 2023-12-12 Ambri, Inc. Ceramic materials and seals for high temperature reactive material devices
US10637015B2 (en) 2015-03-05 2020-04-28 Ambri Inc. Ceramic materials and seals for high temperature reactive material devices
US11289759B2 (en) 2015-03-05 2022-03-29 Ambri, Inc. Ceramic materials and seals for high temperature reactive material devices
US9893385B1 (en) 2015-04-23 2018-02-13 Ambri Inc. Battery management systems for energy storage devices
JP2017103170A (ja) * 2015-12-04 2017-06-08 株式会社デンソー リチウムイオン二次電池用正極及びその製造方法
US11929466B2 (en) 2016-09-07 2024-03-12 Ambri Inc. Electrochemical energy storage devices
US11411254B2 (en) 2017-04-07 2022-08-09 Ambri Inc. Molten salt battery with solid metal cathode
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CN109037684B (zh) * 2018-06-29 2021-08-03 天津市捷威动力工业有限公司 一种内部氧气自吸收安全锂电池
CN109037684A (zh) * 2018-06-29 2018-12-18 天津市捷威动力工业有限公司 一种内部氧气自吸收安全锂电池
CN114375515A (zh) * 2019-09-12 2022-04-19 帅福得美国有限公司 用于锂离子二次电池的正极活性材料
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US11804601B2 (en) 2019-09-12 2023-10-31 Saft America Cathode materials for lithium ion batteries
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