WO2008033717A2 - Method of processing active materials for use in secondary electrochemical cells - Google Patents
Method of processing active materials for use in secondary electrochemical cells Download PDFInfo
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- WO2008033717A2 WO2008033717A2 PCT/US2007/077809 US2007077809W WO2008033717A2 WO 2008033717 A2 WO2008033717 A2 WO 2008033717A2 US 2007077809 W US2007077809 W US 2007077809W WO 2008033717 A2 WO2008033717 A2 WO 2008033717A2
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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
- H01M4/04—Processes of manufacture in general
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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
- H01M4/13—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
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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
- H01M4/58—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
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the processing of electroactive materials which are useful in producing electrodes and batteries.
- the electroactive materials are subjected to a mechanofusion process by which mechanical energy is applied to the electroactive particles which were produced by a carbothermal reduction process. This mechanofusion processing induces a mechano-chemical reaction whereby new electroactive particles are produced.
- batteries are devices that convert chemical energy into electrical energy, by means of an electrochemical oxidation-reduction reaction. Batteries are used in a wide variety of applications, particularly as a power source for devices that cannot practicably be powered by centralized power generation sources (e.g., by commercial power plants using utility transition lines).
- Batteries can generally be described as comprising three components: an anode that contains a material that is oxidized (yields electrons) during discharge of the battery; a cathode that contains a material that is reduced (accepts electrons) during discharge of the battery; and an electrolyte that provides for transfer of ions between the cathode and anode. Batteries can be more specifically characterized by the specific materials that make up each of these three components. Selection of these components can yield batteries having specific voltage and discharge characteristics .that can be optimized for particular applications. [0004]
- the electrodes of such batteries generally include an electroactive material. Recently a class of transition metal phosphates and mixed metal phosphates have been developed for use as electroactive material.
- transition metal phosphates and mixed metal phosphates are insertion based compounds and allow great flexibility in the design of lithium ion batteries.
- These phosphate compounds have a crystal lattice structure or framework from which ions, such as lithium ions, can be extracted and subsequently reinserted and/or from which ions such as lithium ions can be inserted or intercalated and subsequently extracted.
- a class of such materials is disclosed in U.S. 6,528,033 B1 (Barker et al.).
- the compounds therein are of the general formula Li a Ml b Mll c (PO 4 )d wherein Ml and Mil are the same or different.
- Ml is a metal selected from the group consisting of Fe, Co, Ni, Mn, Cu, V, Sn, Cr and mixtures thereof. Mil is optionally present, but when present is a metal selected from the group consisting of Mg, Ca, Zn, Sr, Pb 1 Cd, Sn, Ba, Be and mixtures thereof. More specific examples of such compounds include compounds wherein Mi is vanadium and more specifically includes Li 3 V 2 (PO ⁇ s. U.S. 6,528,033 B1 (Barker et al.) further discloses useful electroactive materials of the formula LiFei- x Mg x PO 4 .
- such an electroactive material must exhibit a low free energy of reaction with lithium, be able to intercalate a large quantity of lithium, maintain its lattice structure upon insertion and extraction of lithium, allow rapid diffusion of lithium, afford good electrical conductivity, not be significantly soluble in the electrolyte system of the battery, and be readily and economically produced.
- many of the electroactive materials known in the art lack one or more of these characteristics.
- Transition metal phosphates are typically synthesized in a solid state reaction. Starting materials in particle form are mixed to produce an intimate mixture of particles. When heat is applied to effect reaction, the solid particles react with one another through a variety of surface reactions accompanied by diffusion of reactive materials into and out of various particles in the mixture. For this reason, it is preferred to mix particle mixtures with as close a degree of contact as possible between the particles together with a desirable particle size. To accomplish this, the particle mixtures are typically prepared by methods such as ball milling or physical mixing.
- lithium metal phosphate made, for example, from
- LiH 2 P ⁇ 4 and a metai oxide via high calcination requires that starting materials be fine size particles. Intensive mixing is needed to insure complete conversion of the starting materials to the desired end product. Thus, it would be desirable and beneficial to have a process for preparing such intercalation materials more efficiently, at reduced cost and with less consumption of production space and reduction of production time.
- the inventors of the present invention have now found a reproducible, efficient and economical method for producing high density, high purity electroactive materials for use in the production of electrodes and in particular in the production of cathodes.
- the present invention provides a method for the processing of particles of meta! phosphates or particles of mixed metal phosphates and in particular lithiated metal phosphates and mixed metal phosphates.
- the processing occurs, for example using a mechanofusion system as depicted in Figures 1 and 2.
- the powder materials are placed in a rotary container and are subjected to centrifugal force and securely pressed against the wall of the container.
- the material then undergoes strong compression and shearing forces when it is trapped between the wall of the container and the inner piece of the rotor with a different curvature ( Figure 2). Particles of the material are brought together with such force that they adhere to one another.
- the powder material is delivered through slits on the rotary walls. It is carried up above the rotors by the rotor-mounted circulating blades. Subsequently, the material returns again to the rotors where it is are subjected to strong compression and shearing forces from the inner pieces of the rotor.
- This cycle of both three-dimensional circulation and effective compression/shearing of the powder material is repeated at high speeds, thereby forming it into a composite electroactive material (powder).
- This process improves the physical characteristics of as-synthesized electroactive materials. It tends to fuse the smaller particles to the outsides of the larger ones, and the composite particles thus produced tend to be spherical in shape.
- the powder resulting from this process has high density, uniform particle size and spherical particles with carbon enriched surfaces.
- Mechanofusion treatment improves the electrode-forming properties of the electroactive material, such that uniform, high density, high conductivity electrodes may be formed without the problems associated with excessive levels of fine particles or nonuniform particles. This process eliminates the need for intensive, time consuming, price increasing and space consuming steps of mulling and pelletizing needed in other commercial processes for preparing metal phosphate and mixed metal phosphate compounds.
- Figure 1 shows a typical mechanofusion mill wherein powders can are subjected to compressive and shearing forces.
- Figure 2 shows the inside rotor where the powders are processed in the mechanofusion mill of Figure 1.
- Figure 3 shows a scanning electron microscope (SEM) photograph of the porous powder produced by the wet ball milling method of Example 1
- Figure 4 shows a SEM photograph of the dense powder produced after streamlining the wetball milling process and subjecting the porous powder to mechanofusion (See Example 3).
- Figure 5 shows a SEM photograph of the rough/porous film produced with the porous powder produced by the method of Example 1 enlarged 100X.
- Figure 6 shows a SEM photograph of the smooth/dense film produced with the powder subjected to mechanofusion as in example 3 enlarged 100X.
- Figure 7 shows a SEM photograph of the rough/porous film produced with the porous powder produced by the method of Example 1 enlarged 1000X.
- Figure 8 shows a SEM photograph of the smooth/dense fiim produced with the powder subjected to mechanofusion as in example 3 enlarged 1000X.
- Figure 9 shows the capacity vs. voltage of a coin cell produced using the smooth/dense films containing the mechanofusion processed powder as the electroactive material.
- Electroactive material are materials which find use in the manufacture of electrodes, namely, cathodes and anodes.
- the useful electroactive materials are prepared by mixing a source of metal ion, a source of alkali metal ion, a source of phosphate, a source of carbon and optionally a source of a second metal ion. Such mixture is then heated in an inert atmosphere.
- LiFei -x Mg x PO 4 lithium iron magnesium phosphate
- LiH 2 PO 4 , Fe 2 O 3 , Mg(OH) 2 and carbon can be prepared by mixing the reactants LiH 2 PO 4 , Fe 2 O 3 , Mg(OH) 2 and carbon and heating said reaction mixture in an inert atmosphere.
- Li 3 V 2 (PO 4 J 3 (lithium vanadium phosphate can be prepared by ball milling V 2 O 5 , Li 2 CO 3 , (NH 4 ) 2 HPO 4 and carbon and then pelletizing the resulting powder. The pellet is then heated to 300 0 C to remove CO 2 from the LiCO 3 and to remove the NH 2. The pellet so reacted is then powderized and repelletized. The new pellet is then heated at 850 0 C for 8 hours to produce the desired electrochemicaliy active product.
- the precursor compounds such as a lithium compound, a phosphate compound, a metal compound and carbon are measured and wet ball mixed.
- the reaction mixture is then spray dried by commercially known spray drying methods.
- the spray dried mixture is then mulled and pelletized.
- the pellet is then fired to form the electroactive material in its first form.
- This product is then milled and sieved to give the electroactive materials in a more desirable form for producing electrodes.
- Such products produced on a small scale have not always provided an optimal eiectroactive material for producing electrodes at a commercial scale.
- processing the electroactive material in its first form in a mechanfusion system can produce the electroactive material in a more desirable form.
- more desirable is meant better purity, higher tap density, uniform particle size and the like.
- mechanofusion processing can eliminate the pelletizing and sieving processes which were originally performed on the electroactive material in its first form.
- the precursor compounds such as a lithium compound, a phosphate compound, a metal compound, carbon and optionally a second metal compound are measured and wet ball mixed.
- the reaction mixture is then spray dried by commercially known spray drying methods,
- the spray dried mixture is then fired (heated) to form the electroactive product in its first form.
- a mechanofusion process involves subjecting one or more powders
- the final electroactive powder has high density and uniform particle size and may be used to form high quality electrodes.
- the metal phosphates or mixed metal phosphates are first prepared by weighing and wet ball milling the precursor materials.
- the wet ball milled mixture is then spray dried and the spray dried material fired.
- the resulting electroactive material in its first form is then milled, at least once, and then processed in a mechanofusion type mixer capable of applying shear and compression forces to the particles (such as commercially available products of Hosokawa Micron Corporation).
- the operational conditions of such mixers are not specifically limited but usually the rotation speed is from about 800 rpm to about 3,000 rpm and more preferably from about 900 rpm to about 2650 rpm.
- the mixing time likewise is not specifically limited but typically is about 5 minutes to about 90 minutes and more preferably is from about 20 minutes to about 30 minutes.
- electroactive materials electroactive materials
- electrode active materials comprising at least lithium or other alkali metals, a transition metal and a phosphate or similar moiety.
- Such electrode active materials include those of the nominal general formula A a M b ⁇ XY 4 ) c Z d , wherein a, b and c are greater than zero and d is greater than or equal to zero.
- a a M b ⁇ XY 4 a M b ⁇ XY 4
- c Z d a M b ⁇ XY 4
- a, b and c are greater than zero and d is greater than or equal to zero.
- A is selected from the group consisting of Li (lithium), Na (sodium), K
- A is Li, or a mixture of Li with Na, a mixture of Li with K, or a mixture of Li, Na and K.
- A is Na, or a mixture of Na with K.
- Preferably "a" is from about 0.1 to about 6, more preferably from about 0.2 to about 6.
- M comprises one or more metals, comprising at least one transition metal capable of undergoing oxidation to a higher valence state.
- removal of alkali metal from the electrode active material is accompanied by a change in oxidation state of at least one of the metals comprising M.
- the amount of said metal that is available for oxidation in the electrode active material determines the amount of alkali metal that may be removed.
- M may be, in general, a metal or other element, selected from the group consisting of elements from Groups 2 - 14 of the Periodic Table.
- Group refers to the Group numbers ⁇ i.e., columns) of the Periodic Table as defined in the current IUPAC Periodic Table. See, e.g., U.S. Patent 6,136,472, Barker et al., issued October 24, 2000, hereby incorporated by reference.
- transition metal will refer to elements of Groups 4-11 of the Periodic Table, while “non-transition metal” will refer to elements from Groups 2, 3, 12, 13, or 14 of the Periodic Table, excluding C and Si, and to Sb, Bi, Te, and Po from Groups 15 and 16.
- M comprises one or more transition metals from Groups 4 to 11.
- IvI further comprises one or more non- transition metals.
- the non-transition metals include those that have a +2 or a +3 oxidation state.
- M may be represented by Ml x Miii -X , where Ml comprises a transition metal and Mil a non-transition metal, and x is greater than zero.
- x is greater than or equal to about 0.5, more preferably greater than or equal to about 0.8, and more preferably greater than or equal to about 0.9.
- Preferred transition metals include the first row transition series (the 4th Period of the Periodic Table), selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and mixtures thereof. Particularly preferred transition metals include Fe, Co, Mn, Cu, V, Cr, and mixtures thereof. Mixtures of transition metals may also be used. Although, a variety of oxidation states for such transition metals are available, in some embodiments it is preferred that the transition metals have a +2 oxidation state. In other embodiments, the transition metals have a +3 oxidation state. In a preferred embodiment, the transition metal includes Fe. [0034] M may also comprise non-transition metals and metalloids.
- Group 2 elements particularly Be (Beryllium), Mg (Magnesium), Ca (Calcium), Sr (Strontium), Ba (Barium); Group 3 elements, particularly Sc (Scandium), Y (Yttrium), and the lanthanides, particularly La (Lanthanum), Ce (Cerium), Pr (Praseodymium), Nd (Neodymium), Sm (Samarium); Group 12 elements, particularly Zn (zinc) and Cd (cadmium); Group 13 elements, particularly B (Boron), Al (Aluminum), Ga (Gallium), In (Indium), Tl (Thallium); Group 14 elements, particularly Si (Silicon), Ge (Germanium), Sn (Tin), and Pb (Lead); Group 15 elements, particularly As (Arsenic), Sb (Antimony), and Bi (Bismuth); Group 16 elements, particularly Te (Teilurium); and mixtures thereof.
- Group 2 elements particularly Be (Beryllium), Mg (Magnesium), Ca (
- Preferred non-transition metals include the Group 2 elements, Group 12 elements, Group 13 elements, and Group 14 elements. Particularly preferred non-transition metals include those selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Ai, and mixtures thereof.
- non-transition metals are selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof. More preferably, the non-transition metal is Mg.
- ⁇ b" is selected so as to maintain electroneutrality of the electrode active material.
- b may range from about 0.8 to about 3, more preferably from about 0.8 to 2.
- c 2, b is from about 2 to about 3, preferably about 2.
- XY 4 is selected from the group consisting of X'O ⁇ Y'x, XO 4- yY' 2 y, X"S 4) and mixtures thereof, where X' is P (phosphorus), As (arsenic), Sb (antimony), Si (silicon), Ge (germanium), V (vanadium), S (sulfur), or mixtures thereof; X" is P, As, Sb, Si, V, Ge or mixtures thereof.
- X 1 and X" are, respectively, selected from the group consisting of P, Si, and mixtures thereof.
- X' and X" are P.
- Y' is halogen (preferably fluorine), N, or S.
- moieties XY 4 include, without limitation, phosphate, silicate, sulfate, and arsenate.
- Other non-limiting examples include germanate, antimonate, and vanadate, as well as sulfur containing analogs of any of the foregoing.
- XY 4 is X 1 O 4 , where X' is preferably P or Si, more preferably P.
- Z is OH 1 halogen, or mixtures thereof.
- Z is selected from the group consisting of OH (hydroxyl), F (fluorine), Cl (chlorine), Br (bromine) and mixtures thereof.
- Z is OH.
- Z is F, or mixtures of F with OH, Cl 1 or Br.
- the composition of M, X, Y, and Z, and the values of a, b, c, d, x and y, are selected so as to maintain electroneutrality of the electrode active material.
- electroneutrality is the state of the electrode active material wherein the sum of the positively charged species (e.g., M and X) in the material is equal to the sum of the negatively charged species (e.g., Y and Z) in the material.
- the XY 4 moieties are comprised to be, as a unit moiety, an anion having a charge of -2, -3, or -4, depending on the selection of X.
- the negative charge contributed by the XY 4 groups may take on non-integer values.
- the electroactive materials are lithium metal phosphates of general formula with M as defined above.
- a is from about 0.3 to about 1.2, preferably from about 0.8 to 1.2, and b is about 0.8 to about 1.2.
- a and b are both about 1.
- the active materials may be written as LJ a Ml x MIh -X PO 4 , where x is greater than zero.
- Mi comprises a transition metal, preferably V, Cr, Mn, Fe, Co, Ni, Mo or combinations thereof, and more preferably Fe. Ml!
- x comprises a non-transition metal, preferably Be, Mg, Ca, Sr, Ba, Zn, or combinations thereof, and more preferably Mg.
- Ml is Fe
- MIi is Mg
- x is greater than 0.5.
- x is greater than or equal about 0,8; in yet another embodiment, x is greater than or equal about 0.9.
- x is less than or equal to about 0.95.
- A is an alkali metal or mixture of alkali metals
- M comprises at least one transition metal capable of undergoing oxidation to a higher oxidation state than in the general formula
- Z is selected from the group consisting of halogen, hydroxide, and combinations thereof, a, b, and c are greater than zero and d is zero or greater.
- the electroactive material comprises a compound of the formula
- M is M ! i- m M" m , where M' is at least one transition metal from Groups 4 to 11 of the Periodic Table; M" is at least one element which is from Group 2, 12, 13, or 14 of the Periodic Table, 0 ⁇ m ⁇ 1 , and 1 ⁇ b ⁇ 3; and
- Z comprises halogen, and 0 ⁇ d ⁇ 4, preferably 0.1 ⁇ d ⁇ 4; wherein M, Z, a, b, and d are selected so as to maintain electroneutrality of said compound.
- M' is selected from the group consisting of Fe, Co, Ni, Mn, Cu 1 V, Zr, Ti, Cr 1 and mixtures thereof; more preferably M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Cr, and mixtures thereof.
- M is selected from the group consisting of Mg, Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al 1 and mixtures thereof; more preferably M" is selected from the group consisting of Mg, Ca, Zn, Ba, Al, and mixtures thereof.
- Z comprises F.
- Another preferred phosphate compound comprises a compound of the formula
- A is selected from the group consisting of Li 1 Na, K, and mixtures thereof;
- M is MVbM" b , where M' is at least one transition metal from Groups 4 to 11 of the Periodic Table; and M" is at least one element which is from Group 2, 3, 12, 13, or 14 of the Periodic Table, and 0 ⁇ b ⁇ 1 ; and
- (c) Z comprises halogen, and 0 ⁇ d ⁇ 2, preferably 0.1 ⁇ d ⁇ 2; and wherein M 1 Z, b, and d are selected so as to maintain electroneutrality of said compound.
- A is Li, or mixtures of Li with Na, K, or mixtures of Na and K.
- M' is selected from the group consisting of Fe, Co, Mn, Cu, V, Zr, Ti, Cr, and mixtures thereof; more preferably M' is selected from the group consisting of Fe 1 Co 1 Mn, Cu, V 1 Cr, and mixtures thereof.
- M" is selected from the group consisting of Mg 1 Ca, Zn, Sr, Pb, Cd, Sn, Ba, Be, Al, and mixtures thereof; more preferably, M" is selected from the group consisting of Mg, Ca, Zn, Ba, Al 1 and mixtures thereof.
- Z comprises F.
- M' comprises Fe 1 and M" is Mg.
- a particularly preferred embodiment is LiFei -x Mg x P ⁇ 4 and Li 2 Fei. x IVlg x PO 4 F.
- Preferred electrode active materials include for example LiFe ⁇ 5 Mg -05 PO 4
- Materials such as those above and others can be made by a process comprising the step of wet bail milling heating a particulate precursor composition in a solvent.
- the particulate precursor composition is provided in the form of particles, wherein the particles have an average size of less than 100 micrometers, and wherein at least a major fraction of the particles contain at least one compound that is a source of alkali metal and at least one compound that is a source of transition metal.
- the precursor composition particles further comprise a carbonaceous material, in a preferred embodiment, the particle average diameter is less than 50 micrometers.
- Preferred transition metal compounds include those of vanadium, chromium, manganese, iron, cobalt, nickel, molybdenum, titanium, and combinations thereof, while preferred alkali metal compounds include those of lithium.
- the particles further comprise at least one compound that is a source of an anion selected from the group consisting of phosphate, hydrogen phosphate, dihydrogen phosphate, and mixtures thereof.
- electroactive materials are prepared by spray drying the powder precursor composition, mulling the spray dried composition and then heating for a time and at a temperature sufficient to form an eiectroactive reaction product in a first form.
- the electroactive reaction product may in general be used directly as the active material in the electrodes and rechargeable batteries of the invention.
- subjecting such reaction product to mechanofusion processing results in a beneficial and .more desirable electroactive reaction product while eliminating some processing steps, improving processing time and efficiency and thereby simultaneously reducing costs.
- the powdered precursor composition is conveniently prepared by spray drying a slurry.
- slurry refers to a composition having a liquid phase and a solid phase.
- the liquid phase may contain one or more dissolved solids.
- the solid phase is dispersed or suspended in the liquid phase in such a way that the composition maintains a uniform structure or stable suspension for a time period sufficient for it to be subsequently used. In the present process, the slurry is to remain stable for a time sufficient for it to be used in the spray drying process.
- the slurry is a physical mixture of dissolved and non-dissolved solids, distinguishing it from a true solution.
- the slurry can be separated into its liquid and solid components by a variety of physical processes such as centrifugation and filtration. In some embodiments, it may be susceptible to separating upon standing by the working of gravity on the solid particles in the solid phase.
- the slurries are preferably characterized in that when separation occurs such as by any of the mechanisms above, they can be readily re-suspended or re- dispersed by agitation.
- the slurry is preferably a stable, essentially uniform composition suitable for uses that take advantage of its uniform composition.
- the stability of the slurry may be maintained by physical processes such as constant agitation, or alternatively it may be enhanced by the addition of other compounds or compositions which act as a dispersing agent or suspending agent as known in the art.
- Slurries are prepared by combining a number of starting materials with a solvent.
- the solvent is preferably any liquid such as an organic liquid or water that will disperse or suspend the starting materials so that they may be used in a subsequent spray draying process.
- useful organic materials include without limitation ethanol, propanol, isopropanol. butanol, isobutanol, low molecular weight alkanes, low molecular weight ketones, and the like.
- a preferred solvent is water.
- starting materials are chosen that contain "a" moles of alkali metal A from all sources, “b” moles of metals M from all sources, “c” moles of phosphate (or other XY 4 species) from all sources, and “d” moles of halide or hydroxide Z, again taking into account all sources.
- a particular starting material may be the source of more than one of the components A, IvI 1 XY 4 , or Z. Alternatively, it is possible to run the reaction with an excess of one or more of the starting materials.
- the stoichiometry of the product will be determined by the limiting reagent among the components A, M, XY 4 , and Z. Because in such a case at least some of the starting materials will be present in the reaction product mixture, it is usually desirable to provide the starting materials in molar equivalent amounts.
- Sources of alkali metal include any of a number of salts or ionic compounds of lithium, sodium or potassium. Lithium compounds are preferred.
- the alkali metal source is provided in powder or particulate form. A wide range of such materials are well known in the field of inorganic chemistry.
- Non- limiting examples include the lithium, sodium, and/or potassium fluorides, chlorides, bromides, iodides, nitrates, nitrites, sulfates, hydrogen sulfates, sulfites, bisulfites, carbonates, bicarbonates, borates, phosphates, hydrogen ammonium phosphates, dihydrogen ammonium phosphates, silicates, antimonates, arsenates, germinates, oxides, acetates, oxalates, and the like. Hydrates of the above compounds may also be used, as well as mixtures. In particular, the mixtures may contain more than one alkali metal so that a mixed alkali metal active material will be produced in the reaction.
- Sources of metals M include salts or compounds of any of the transition metals, alkaline earth metals, or lanthanide metals, as well as of non- transition metals such as aluminum, gallium, indium, thallium, tin, lead, and bismuth.
- the metal compounds include, without limitation, fluorides, chlorides, bromides, iodides, nitrates, nitrites, sulfates, hydrogen sulfates, sulfites, bisulfites, carbonates, bicarbonates, borates, phosphates, hydrogen ammonium phosphates, dihydrogen ammonium phosphates, silicates, antimonates, arsenates, germanates, oxides, hydroxides, acetates, oxalates, and the like. Hydrates may also be used, as well as mixtures of metals, as with the alkali metals, so that alkali metal mixed metal active materials are produced.
- the metal M in the starting material may have any oxidation state, depending the oxidation state required in the desired product and the oxidizing or reducing conditions contemplated in the process.
- the metal sources are chosen so that at least one metal in the final reaction product is capable of being in an oxidation state higher than it is in the reaction product.
- Sources of the desired starting material anions such as the phosphates
- ha ⁇ des, and hydroxides include a number of salts or compounds containing positively charged cations in addition to the source of phosphate (or other XY4 species), halide, or hydroxide.
- Such cations include, without limitation, metal ions such as the alkali metals, alkaline metals, transition metals, or other non-transition metals, as well as complex cations such as ammonium or quaternary ammonium.
- the phosphate anion in such compounds may be phosphate, hydrogen ammonium phosphate, or dihydrogen ammonium phosphate. Hydrates of any of the above may be used, as can mixtures of the above.
- phosphate, silicate, sulfate, and other similar moieties include the acids, which are usually available in a liquid form as either the pure compound or a concentrated aqueous solution.
- a preferred phosphate source for example, is concentrated orthophosphoric acid, available as approximately an 85% by weight solution in water.
- a starting material may provide more than one of the components A,
- starting materials are provided that combine, for example, the alkali metal and halide together, or the metal and the phosphate.
- lithium, sodium, or potassium fluoride may be combined with a metal phosphate such as vanadium phosphate or chromium phosphate, or with a mixture of metal compounds such as a metal phosphate and a metal hydroxide.
- a starting material is provided that contains alkali metal, metal, and phosphate.
- any anion may be combined with the alkali metal cation to provide the alkali metal source starting material, or with the metal M cation to provide the metal M starting material.
- any cation may be combined with the halide or hydroxide anion to provide the source of Z component starting material, and any cation may be used as counterion to the phosphate or similar XY4 component.
- starting materials with counterions that give rise to volatile by-products.
- ammonium salts, carbonates, oxides, hydroxides, and the like where possible.
- Starting materials with these counterions tend to form volatile by-products such as water, ammonia, and carbon dioxide, which can be readily removed from the reaction mixture.
- LiH 2 PO 4 or Li 2 HPO 4 is used as starting material to prepare a precursor slurry of the invention. Not only does such a starting material provide a convenient source of both lithium and phosphate - two important constituents of the active materials - but they are highly soluble in water, a preferred solvent for making the slurries of the invention.
- the active material to be made is an alkali metal phosphate material as described above, it is preferred to use an soluble alkali metal dihydrogen phosphate as a starting material.
- a preferred alkali metal dihydrogen phosphate is lithium dihydrogen phosphate.
- Lithium dihydrogen phosphate may be added directly to the slurry as described above, or it may be formed by combining other of the starting materials. For example, in a first step H3PO4 and Li2CO3 or LiOH may be combined together to form a lithium dihydrogen phosphate solution. Thereafter, an insoluble transition metal oxide such as iron oxide may be added to form a slurry which is subsequently spray dried to form a powder precursor composition.
- lithium carbonate or lithium hydroxide and an insoluble transition metal oxide may be combined in water to form a slurry to which phosphoric acid is subsequently added.
- a soluble lithium dihydrogen phosphate is formed in the liquid phase.
- Some iron phosphate may also be solubilized in the liquid phase.
- the solid phase contains unreacted transition metal oxide and any precipitating species.
- the slurry may also contain other soluble metals such as, without limitation, magnesium hydroxide.
- the slurries of the invention may also contain a carbonaceous compound, it is possible to use soluble carbonaceous compounds such as without limitation glycerol, starch, and a variety of sugars. Many useful carbonaceous compounds, however, are not soluble in water or other solvents. These insoluble carbonaceous materials include amorphous carbon, graphites, cokes, hydrocarbons, and the organic polymers noted above. In a preferred embodiment, effective dispersants are used along with insoluble carbonaceous material to form slurries of the invention.
- dispersants are used in the invention to maintain in suspension the solid phase, which generally contains an insoluble metal compound (usually at least one insoluble transition metal compound), an insoluble carbonaceous material, or both.
- Suitable dispersants include those that are capable of interacting both with the liquid phase and the solid phase of the slurry to maintain a relatively stable dispersion or suspension.
- dispersants will be those compounds or compositions having both a hydrophilic part and a hydrophobic part.
- Dispersants useful in industry and in forming the slurries of the invention are well known in the art and are selected from the group consisting of nonionic dispersants, anionic dispersants and cationic dispersants. Such materials are commercially available from a variety of sources.
- Dispersants used in the invention are generally organic materials that can carbonize and form reducing carbon material when heated in a powdered precursor composition as discussed above. As such, they can supplement or substitute for. other added sources of reducing carbon such as other organic precursor materials
- the slurries of the invention are spray dried by conventional means to yield a powder precursor composition.
- the slurry is spray dried by atomizing the slurry to form droplets and contacting the droplets with a stream of gas at a temperature sufficient to evaporate at least a major portion by weight of the solvent used in the slurry.
- air can be used to dry the slurries of the invention.
- it may be preferable to use a less oxidizing or perhaps an inert gas or gas mixture.
- an inert gas is preferred when the slurry being dried contains organic solvents.
- hot air may be suitable for drying aqueous slurries.
- spray drying is preferably conducted using a variety of methods that cause atomization by forcing the slurry under pressure at a high degree of spin through a small orifice, including rotary atomizers, pressure nozzles, and air (or two- fluid) atomizers.
- the slurry is thereby dispersed into fine droplets. It is dried by a relatively large volume of hot gases sufficient to evaporate the volatile solvent, thereby providing very fine particles of a powdered precursor composition.
- the particles contain the precursor starting materials intimately and essentially homogeneously mixed.
- the spray-dried particles appear to have the same uniform composition regardless of their size.
- each of the particles contains all of the starting materials in the same proportion.
- the volatile constituent in the slurry is water.
- the spray drying may take place preferably in air or preferably in an inert hot gas stream.
- a preferred hot drying gas is argon, though other inert gases may be used.
- the inlet gas stream is at an elevated temperature sufficient to remove a major portion of the water with a reasonable drier volume, for a desired rate of dry powder production and particle size.
- Air inlet temperature, atomize droplet size, and gas flow are factors which may be varied and affect the particle size of the spray dry product and the degree of drying.
- the drying step reduce the moisture content of the material to less than 10% by weight.
- the amount of solvent removed depends on the flow rate, residence time of the solvent water particles, and contact with the heated air, and also depends on the temperature of the heated air.
- Techniques for spray drying are well known in the art. In a non-limiting example, spray drying is carried out in a commercially available spray dryer such as an APV-I nvensys PSD52 Pilot Spray Dryer. Typical operating conditions are in the following ranges: inlet temperature 250 - 35O 0 C; outlet temperature: 100 - 12O 0 C; feed rate: 4 - 8 liters (slurry) per hour.
- the spray dried composition is the mulled and pelletized and then such pelletized product is fired (heated) to effect the reaction.
- electroactive materials are prepared by heating the spray dried powdered precursor composition as described above for a time and at a temperature sufficient to form a reaction product.
- the reaction mixture is heated in an oven, generally at a temperature of about 400 0 C or greater until a reaction product forms.
- the reaction temperature is preferably less than about 400 0 C and more preferably about 250 0 C or less.
- the reaction may be carried out without redox or if desired under reducing or oxidizing conditions.
- the reaction is done without redox, the oxidation state of the metal or mixed metals in the reaction product is the same as in the starting materials in the powdered precursor composition.
- Oxidizing conditions may be provided by heating the powder precursor composition in the presence of oxygen or air.
- the reaction may also be carried out with reduction.
- the reaction may be carried out in a reducing atmosphere such as hydrogen, ammonia, methane, or a mixture of reducing gases.
- the reaction may also be carried out with reduction in the case where the powdered precursor composition contains a carbonaceous material as discussed above. In that situation, the powdered precursor composition contains a reductant that will participate in the reaction to reduce a transition metal, but that will produce by-products that will not interfere with the active material when used later in an electrode or an electrochemical ceil.
- an inert atmosphere such as argon, nitrogen or carbon dioxide.
- the reducing agent is generally used in excess.
- any excess reducing agent does not present a problem in the active materials.
- the gas is volatile and is readily separated from the reaction mixture.
- the excess carbon in the reaction product does not harm the properties of the active material, because carbon is generally added to the active material to form an electrode material for use in the electrochemical cells and batteries of the invention.
- the by-products carbon monoxide or carbon dioxide (in the case of a reducing carbon) or water (in the case of hydrogen) are readily removed from the reaction mixture.
- the carbothermal reduction method of synthesis of mixed metal phosphates has been described in PCT Publication WO/01/53198, Barker et al., incorporated by reference herein.
- the carbothermal method may be used to react starting materials in the presence of reducing carbon to form a variety of products.
- the carbon functions to reduce a metal ion in the starting material metal M source.
- the reducing carbon for example in the form of elemental carbon powder, is mixed with the other starting materials in the preparation of slurries of the invention, as discussed above.
- the temperature should be about 400 0 C or greater, and up to about 950 0 C. Higher temperatures may be used, but are usually not required.
- the present invention also provides electrodes comprising an electrode active material made by the process of the present invention.
- the electrodes of the present invention comprise an electrode active material made by the process of this invention, a binder; and an electrically conductive carbonaceous material.
- the electrodes of this invention comprise:
- electrically conductive material e.g., carbon black
- binder chosen to hold all particulate materials in contact with one another without degrading ionic conductivity
- Cathodes of this invention preferably comprise from about 50% to about 90% of electroactive material, about 5% to about 30% of the electrically conductive material, and the balance comprising binder.
- Anodes of this invention preferably comprise from about 50% to about 98% by weight of the electrically conductive material (e.g., a preferred graphite), with the balance comprising binder.
- Electrically conductive materials among those useful herein include carbon black, graphite, powdered nickel, metal particles, conductive polymers (e.g., characterized by a conjugated network of double bonds like polypyrrole and polyacetylene), and mixtures thereof.
- Binders useful herein preferably comprise a polymeric material and extractable plasticizer suitable for forming a bound porous composite.
- the electrode active material is mixed into a slurry with a polymeric binder compound, a solvent, a plasticizer, and optionally the electroconductive material.
- the active material slurry is appropriately agitated, and then thinly applied to a substrate via a doctor blade.
- the substrate can be a removable substrate or a functional substrate, such as a current collector ⁇ for example, a metallic grid or mesh layer) attached to one side of the electrode film.
- heat or radiation is applied to evaporate the solvent from the electrode film, leaving a solid residue.
- the electrode film is further consolidated, where heat and pressure are applied to the film to sinter and calendar it.
- the film may be air-dried at moderate temperature to yield self-supporting films of copolymer composition.
- the substrate is of a removable type it is removed from the electrode film, and further laminated to a current collector. With either type of substrate it may be necessary to extract the remaining plasticizer prior to incorporation into the battery cell.
- the batteries of the present invention comprise:
- the electrode active material of this invention may comprise the anode, the cathode, or both.
- the electrode active material comprises the cathode.
- the active material of the second, counter-electrode is any material compatible with the electrode active material of this invention.
- the anode may comprise any of a variety of compatible anodic materials well known in the art, including lithium, lithium alloys, such as alloys of lithium with aluminum, mercury, manganese, iron, zinc, and intercalation based anodes such as those employing carbon, tungsten oxides, and mixtures thereof.
- the anode comprises:
- the batteries of this invention also comprise a suitable electrolyte that provides a physical separation but allows transfer of ions between the cathode and anode.
- the electrolyte is preferably a material that exhibits high ionic conductivity, as well as having insular properties to prevent self-discharging during storage.
- the electrolyte can be either a liquid or a solid.
- a liquid electrolyte contains comprises a solvent and an alkali metal salt that together form an ionically conducting liquid. So called "solid electrolytes" contain in addition a matrix material that is used to separate the electrodes.
- LiH 2 PO 4 , Mg(OH) 2 , Fe 2 O 3 and Carbon Super P were wet ball mixed/milled in quantities sufficient to produce a commercial quantity of LiFe. 95 Mg 0 . 5 PO 4 .
- the mulled product was then pelletized. (5) The pellet was subjected to heating at 750 0 C for 4 hours.
- Step (6) The reaction product of Step (6) was then subjected to continuous vibration sieving.
- Example 2 10.0 kg of the composition produced in Example 2 was subjected to mechanofusion using an AMS-30F mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- Water cooling at 20 (l/min).
- the revolution speed was set at 2000 rpm and mechanofusion processing continued for 30 minutes. 8.21 kg of mechanof used powder was recovered.
- the starting composition had a bulk density of 0.519 g/ml and the finished product had a bulk density of 0.663 g/ml.
- the starting composition had a tap density of 1.099 g/ml and the finished product had a tap density of 1.356 g/ml.
- the starting composition had an average particle size (D50) 3.736 microns and the finished product had an average particle size (D50) of
- Example 2 10.0 kg of the composition produced in Example 2 was subjected to mechanofusion using an AMS-30F mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- Water cooling at 20 (l/min).
- the revolution speed was set at 1800 rpm and mechanofusion processing continued for 20 minutes. 9.20 kg of mechanofused powder was recovered.
- the starting composition had a bulk density of 0.502 g/ml and the finished product had a bulk density of 0.709 g/ml.
- the starting composition had a tap density of 1.035 g/ml and the finished product had a tap density of 1.416 g/ml.
- the starting composition had an average particle size (D50) 3.794 microns and the finished product had an average particle size (D50) 3.006 microns.
- Example 2 10.0 kg of the composition produced in Example 2 was subjected to mechanofusion using an AMS-30F mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- Water cooling at 20 (l/min).
- the revolution speed was set at 1905 rpm and mechanofusion processing continued for 20 minutes,. 9,20 kg of mechanofused powder was recovered.
- the starting composition had a buik density of 0.503 g/ml and the finished product had a bulk density of 0.734 g/ml.
- the starting composition had a tap density of 1.049 g/ml and the finished product had a tap density of 1.446 g/mS.
- the starting composition had an average particle size (D50) 3.910 microns and the finished product had an average particle size (D50) 3.485 microns.
- Example 2 10.0 kg of the composition produced in Example 2 was subjected to mechanofusion using an AMS-30F mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- Water cooling at 20 (l/min).
- the revolution speed was set at 1900 rpm and mechanofusion processing continued for 20 minutes. 9.10 kg of mechanofused powder was recovered.
- the starting composition had a bulk density of 0.499 g/ml and the finished product had a bulk density of 0.714 g/ml.
- the starting composition had a tap density of 1.058 g/ml and the finished product had a tap density of 1.455 g/ml.
- the starting composition had an average particle size (D50) 4.005 microns and the finished product had an average particle size (D50) 3.199 microns.
- EXAMPLE 7 Mechanofusion processing of LiFe -95 Mg-OsPO 4
- Example 2 50Og of the composition produced in Example 2 was subjected to mechanofusion using an AMS-Lab mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- Water cooling at 2 (l/min).
- the revolution speed was set at 2655 rpm and mechanofusion processing continued for 30 minutes. 390.6 g of mechanofused powder was recovered.
- the starting composition had a bulk density of 0.519 g/ml and the finished product had a bulk density of 0.575 g/ml.
- the starting composition had a tap density of 0.937 g/ml and the finished product had a tap density of 1.137 g/ml.
- the starting composition had an average particle size (D50) 2.595 microns and the finished product had an average particle size (D50) 2.462 microns.
- Example 2 500 g of the composition produced in Example 2 was subjected to mechanofusion using an AMS-Lab mixer commercially available from Hosokawa Micron Corporation.
- the press head was set at SS/5mm.
- the revolution speed was set at 2098 rpm and mechanofusion processing continued for 20 minutes. 390.6 g of mechanofused powder was recovered.
- the starting composition had a bulk density of 0.519 g/ml and the finished, product had a bulk density of 0.654 g/ml.
- the starting composition had a tap density of 0.937 g/ml and the finished product had a tap density of 1.255 g/ml.
- the starting composition had an average particle size (D50) 2.595 microns and the finished product had an average particle size (D50) 2.350 microns.
- Example 1 The composition produced in Example 1 was subjected to mechanofusion using an AMS-30F mixer commercially available from Hosokawa Micron Corporation as described in Example 3-8..
- Figure 3 shows SEM imaging of the porous powder produced in
- Example 1 (200Ox) (no mechanofusion of AMS processing).
- Figure 4 shows (image) of the dense powder produced after AMS processing (500Ox).
- Table 1 shows the tap densities of various powder produced by the methodologies given in the Examples. It can be seen therefrom that the AMS (mechnofusion) processed powders give higher density powders. Table 1
- Electrode films were made according to the methodology described above.
- Figure 5 shows the SEM imaging of the rough/porous film produced with powder that had no AMS (mechanofusion) processing (100x).
- Figure 6 shows the SEM imaging of the smooth/dense film produced with powder that had AMS (mechanofusion) processing (15Ox).
- Figure 7 shows the SEM imaging of the rough/porous film produced with powder that had no AMS ⁇ mechanofusion) processing (1000x).
- Figure 8 shows the SEM imaging of the rough/porous film produced with powder that had AMS (mechanofusion) processing (1000x).
- Table 2 shows the characteristic of a film produced with powder that had no AMS (mechanofusion) processing prepared as in Example 1.
- Coin cells were produced using the films produce with the AMS processed powder according to known methodology.
- the capacity vs. voltage is shown in Figure 9 and the charge/discharge data for such cells is given in Table 3.
Abstract
Description
Claims
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Cited By (5)
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JP2010073520A (en) * | 2008-09-19 | 2010-04-02 | Hitachi Ltd | Lithium ion secondary battery |
JP2011216233A (en) * | 2010-03-31 | 2011-10-27 | Sumitomo Osaka Cement Co Ltd | Electrode material and film |
JP2012524017A (en) * | 2009-04-16 | 2012-10-11 | ヴァレンス テクノロジー インコーポレーテッド | Method for producing active material used in secondary electrochemical cell |
WO2014117394A1 (en) * | 2013-02-01 | 2014-08-07 | Valence Technology, Inc. | Method of making active materials for use in secondary electrochemical cells |
WO2014184533A1 (en) | 2013-05-14 | 2014-11-20 | Faradion Limited | Metal-containing compounds |
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JP5153189B2 (en) * | 2007-03-30 | 2013-02-27 | 三井造船株式会社 | Method for producing lithium ion secondary battery positive electrode material |
US20090148377A1 (en) * | 2007-12-11 | 2009-06-11 | Moshage Ralph E | Process For Producing Electrode Active Material For Lithium Ion Cell |
JP5604216B2 (en) * | 2010-08-09 | 2014-10-08 | 日本化学工業株式会社 | Method for producing lithium vanadium phosphate carbon composite |
JP5604217B2 (en) * | 2010-08-09 | 2014-10-08 | 日本化学工業株式会社 | Method for producing lithium vanadium phosphate carbon composite |
JP5612392B2 (en) * | 2010-08-09 | 2014-10-22 | 日本化学工業株式会社 | Method for producing lithium vanadium phosphate carbon composite |
JP5811695B2 (en) * | 2011-08-30 | 2015-11-11 | 日亜化学工業株式会社 | Olivine-type lithium transition metal oxide and method for producing the same |
JP6271865B2 (en) * | 2013-05-24 | 2018-01-31 | 日本ケミコン株式会社 | Method for manufacturing electrode material for power storage device |
JP6197202B2 (en) * | 2014-05-23 | 2017-09-20 | 住友大阪セメント株式会社 | Electrode material and membrane |
JP6341512B2 (en) * | 2014-12-15 | 2018-06-13 | 株式会社三井E&Sホールディングス | Method for producing electrode material for lithium ion secondary battery |
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US20020197534A1 (en) * | 2001-06-08 | 2002-12-26 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, process for production thereof, and lithium secondary battery |
US20060194112A1 (en) * | 2003-04-03 | 2006-08-31 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
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US6528033B1 (en) * | 2000-01-18 | 2003-03-04 | Valence Technology, Inc. | Method of making lithium-containing materials |
JP4061586B2 (en) * | 2003-04-11 | 2008-03-19 | ソニー株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
JP4999292B2 (en) * | 2004-07-21 | 2012-08-15 | 三洋電機株式会社 | Non-aqueous electrolyte battery |
JP4819342B2 (en) * | 2004-11-08 | 2011-11-24 | エレクセル株式会社 | Positive electrode for lithium battery and lithium battery using the same |
CA2506104A1 (en) * | 2005-05-06 | 2006-11-06 | Michel Gauthier | Surface modified redox compounds and composite electrode obtain from them |
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US20020197534A1 (en) * | 2001-06-08 | 2002-12-26 | Mitsui Mining Co., Ltd. | Anode material for lithium secondary battery, process for production thereof, and lithium secondary battery |
US20060194112A1 (en) * | 2003-04-03 | 2006-08-31 | Jeremy Barker | Electrodes Comprising Mixed Active Particles |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010073520A (en) * | 2008-09-19 | 2010-04-02 | Hitachi Ltd | Lithium ion secondary battery |
JP2012524017A (en) * | 2009-04-16 | 2012-10-11 | ヴァレンス テクノロジー インコーポレーテッド | Method for producing active material used in secondary electrochemical cell |
JP2011216233A (en) * | 2010-03-31 | 2011-10-27 | Sumitomo Osaka Cement Co Ltd | Electrode material and film |
WO2014117394A1 (en) * | 2013-02-01 | 2014-08-07 | Valence Technology, Inc. | Method of making active materials for use in secondary electrochemical cells |
WO2014184533A1 (en) | 2013-05-14 | 2014-11-20 | Faradion Limited | Metal-containing compounds |
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