WO2010051746A1 - Matériau actif de cathode, batterie secondaire lithium-ion et batterie rechargeable le comprenant - Google Patents

Matériau actif de cathode, batterie secondaire lithium-ion et batterie rechargeable le comprenant Download PDF

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WO2010051746A1
WO2010051746A1 PCT/CN2009/074769 CN2009074769W WO2010051746A1 WO 2010051746 A1 WO2010051746 A1 WO 2010051746A1 CN 2009074769 W CN2009074769 W CN 2009074769W WO 2010051746 A1 WO2010051746 A1 WO 2010051746A1
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active material
cathode active
cathode
lifepo
material according
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PCT/CN2009/074769
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English (en)
Inventor
Ye Tian
Tangli Cheng
Xiaobing Xi
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Byd Company Limited
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Priority claimed from US12/316,180 external-priority patent/US8057711B2/en
Priority claimed from US12/316,165 external-priority patent/US8062559B2/en
Priority claimed from CN2008101892388A external-priority patent/CN101478042B/zh
Priority claimed from CN200810189233A external-priority patent/CN101740749A/zh
Priority claimed from CN2008101892354A external-priority patent/CN101740750B/zh
Application filed by Byd Company Limited filed Critical Byd Company Limited
Publication of WO2010051746A1 publication Critical patent/WO2010051746A1/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
    • H01M4/58—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • H01M4/0402—Methods of deposition of the material
    • H01M4/0404—Methods of deposition of the material by coating on electrode collectors
    • 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
    • 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
    • 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 rechargeable batteries, more specifically, to a composite compound having a mixed crystalline structure that can be used as a cathode material for lithium secondary batteries.
  • Lithium secondary batteries are widely used in various devices such laptop computers, cameras, camcorders, PDAs, cell phones, iPods and other portable electronic devices. These batteries are also growing in popularity for defense, automotive and aerospace applications because of high energy density thereof.
  • a cathode material for lithium battery is disclosed in U.S. Pat. Application No. 2007/0207385A1 including a first compound and a second compound.
  • the first compound has a formula of A 3x Ml 2y (P ⁇ 4 ) 3 .
  • the second compound is at least one compound selected from the group consisting of SiC, BN and metal oxide having a formula of M2 a O b , coating on the first compound.
  • A is at least one element selected from the group consisting of Groups IA, HA and IIIA.
  • Each of the Ml and M2 is selected from at least one element from Groups HA, IIIA, IVA and VA and transition metal elements, respectively. More specifically, each of the Ml and M2 is at least one element selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Be, Mg, Ca, Sr, B, Al, Sn, Ga, In, Si and Ge. And the material of LiFePO 4 /ZnO/C, LiFeP0 4 /ZnA10 2 /C, LiFePO 4 /CuO/C and LiFePO 4 /ZnAlO/C are disclosed in the examples of the application.
  • the present invention needs to provide a cathode active material, which has a novel crystal structure that may enhance electrical properties of the battery significantly. Further, the present invention needs to provide a lithium ion secondary battery having a cathode made therefrom.
  • a cathode active material comprising a mixed crystal.
  • the mixed crystal may have: a first crystalline substance having at least one member with one of following general formulas Li x M' y (X0 4 ) z , LiM 5 XO 5 , LiM 5 XO 6 and LiM 5 X 2 O 7 in which 0 ⁇ x/z ⁇ l and 0 ⁇ y/z ⁇ l .l, the M 5 may be an element selected from a group consisting of Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, Nb and Zn, and the X may be an element selected from a group consisting of P, S, As, Mo and W; and a second crystalline substance having one or more members with a general formula of A a M b N c O d , in which A, M and N may be different metals selected from groups HA, IIIA, IVA, VA, IB, HB, IIIB, IVB,
  • a lithium ion secondary battery in which the battery may comprise a battery shell, electrodes and electrolyte with the electrodes and electrolyte being sealed within the battery shell, the electrodes having wounded or stacked cathode, anode and divider film.
  • the cathode may further comprise the cathode active material as described above.
  • the present invention for the first time, successfully provides a lithium metal intercalation compound with a mixed crystal.
  • the novel cathode material disclosed in the present invention significantly improves electrical properties of lithium batteries.
  • FIG. 1 shows a XRD pattern of a composite compound according to Example i
  • Fig. 2 shows a XRD pattern of a composite compound according to Example 2
  • Fig. 3 shows a XRD pattern of a composite compound according to Example 3.
  • Fig. 4 shows a XRD pattern of a composite compound according to Example 4.
  • Fig. 5 shows a XRD pattern of a composite compound according to Example 5; and Fig. 6 shows a XRD pattern of a composite compound according to Example
  • a mixed crystal can be referred to as a solid solution. It is a crystal containing a second constituent, which fits into and is distributed in the lattice of the host crystal.
  • IUPAC Compendium of Chemical Terminology 2nd is a crystal containing a second constituent, which fits into and is distributed in the lattice of the host crystal.
  • a cathode active material can be provided having a mixed crystal structure.
  • the mixed crystal structure may have: a first crystalline substance having one or more members with the general formulas Li x M' y (X0 4 ) z , LiM 5 XO 5 , LiM 5 XO 6 and LiM 5 X 2 O 7 , in which:
  • M 5 may be an element selected from the group of Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, Nb and Zn;
  • X may be an element selected from the group of P, S, As, Mo and W; and a second crystalline substance having one or more members with the general formula A a MbN c Od, in which:
  • A, M and N are different metals selected from groups HA, IIIA, IVA, VA, IB, HB, IIIB, IVB, VB, VIB, VIIB and VIII in the periodic table; and
  • the cathode active material may have electrical conductivity of about 0.01 to about 10 S/cm at about 25 0 C.
  • the mixed crystal structure can be formed by sintering two or more compounds, the intermediary mixture having oxygen vacancies or metallic crystalline structures. The two or more compounds do not exhibit any major chemical reactions when mixed together. However, upon sintering, a large number of crystalline defects can be formed, thereby altering the electronic states of the compounds creating a large number of oxygen vacancies. These oxygen vacancies provide the needed carriers, thus greatly enhancing the electrical conductivity of the mixed crystal.
  • the cathode active material can achieve electrical conductivity of about 0.1 to 2S/cm at about 25°C with a Simens per centimeter, which is larger than traditional lithium iron phosphate cathode active materials.
  • the first crystalline substance and the second crystalline substance may have a molar ratio of about 1 to 0.01-0.05.
  • the first crystalline substance can have a mixed crystalline structure with the general formula Li x M' y (X ⁇ 4 ) z including one or more members selected from the group consisting of LiFeO 4 , LiMnPO 4 and LiCoPO 4 etc.
  • single-crystalline structures including Li 3 Fe 2 (PO 4 ) S , LiTi 2 (PO 4 ) 3 , Li 3 V 2 (PO 4 ) 3 and Li 2 Na V 2 (PO 4 ) 3 may be incorporated.
  • the first crystalline substance can be LiTiPOs.
  • the first crystalline substance can include LiVMoO 6 and LiVWO 6 respectively.
  • the first crystalline substance can include LiVP 2 O 7 and LiFeAs 2 O 7 .
  • M' may include element Fe and one or more members selected form the group consisting of Mn, Co, Ni, Ti, Y, Mg, Ca and Zn, and the amount of Fe is from 90 % to 100 % by molar.
  • the first crystalline substance can include one or more members selected from LiFePO 4 , Li 0 99 Y 0 01 FePO 4 and LiR 1 Fe I-1 PO 4 , in which 0 ⁇ i ⁇ 0.1, R may be one or more members selected from elements Mn, Co, Ni, Ti, Mg, Ca and Zn.
  • the second crystalline substance can include one or more members selected from the group consisting of Bi 4 Ti 3 Oi 2 , CuNb 2 Oo, MnTaO 4 , FeWO 4 , ZnZrNb 2 Og, NiNb 2 O 6 , NiZrNb 2 O 8 , FeTiNb 2 O 8 , MnTiNb 2 O 8 , MgSnNb 2 O 8 , ZnTa 2 O 6 , Cu 0 S 5 Zn 0 1 5Nb 2 O 6 , YBa 3 Ti 2 O 8 5, Zr 0 75 Ti 0 75 Sn 0 5O 4 , HfTiO 4 and MgNb 2 O 6 .
  • the mixed crystal structure can further include carbon, which is about 1-5 % of the mixed crystal structure by weight. The carbon can further enhance the electrical conductivity of the mixed crystal.
  • a method of preparing a cathode active material for lithium secondary batteries comprising the following steps:
  • A, M and N are different metals selected from groups HA, IIIA, IVA, VA, IB, HB, IIIB, IVB, VB, VIB, VIIB and VIII in the periodic table; 0 ⁇ a ⁇ 6, 0 ⁇ b ⁇ 6, 0 ⁇ c ⁇ 6 and 0 ⁇ d ⁇ 12; a and b cannot both be O at the same time; and
  • the first material and the second material may have a molar ratio of about 1 to 0.01-0.05.
  • the second material can be formed by heating oxide compounds of A, M and N with a molar ratio of a : b : c at about 400 to 1000 0 C for about 8 to 15 hours.
  • the sintered product can be measured with a Rigaku D/MAX-2200/PC x-ray diffraction (XRD) instrument to acquire an XRD pattern thereof, which can subsequently be compared with known chemical standards provided by the system.
  • the oxide compound or oxygen-containing compound of A can be oxides of A and/or sintered products of oxides of A and other compounds, the oxides of A and other compounds include hydroxides of A, carbonates of A, and bicarbonates of A.
  • the oxide compound or oxygen-containing compound of M can be oxides of M and/or sintered products of oxides of M and other compounds, the oxides of M and other compounds include hydroxides of M, carbonates of M, and bicarbonates of M.
  • the oxide compound or oxygen-containing compound of N can be oxides of N and/or sintered products of oxides of N and other compounds, the oxides of N and other compounds include hydroxides of N, carbonates of N, and bicarbonates of N.
  • the first material may include one or more members selected from the group consisting of LiFePO 4 , LiMnPO 4 , LiCoPO 4 , Li 3 Fe 2 (PO 4 ) S , LiTi 2 (PO 4 ),, Li 3 V 2 (PO 4 ),, Li 2 NaV 2 (PO 4 ),, Li 0 99 Yo O iFePO 4 , LiR 1 Fe 1-1 PO 4 , LiTiPO 5 , LiVMoO 6 , LiVWO 6 , LiVP 2 O 7 and LiFeAs 2 O 7 in which 0 ⁇ i ⁇ 0.1, R is one or more members selected from elements Mn, Co, Ni, Ti, Mg, Ca and Zn.
  • the first material may include one or more members selected from LiFePO 4 , Li 0 99 Y 0 0 1 FePO 4 and LiR 1 Fe I-1 PO 4 .
  • the second material can include one or more members selected from the group consisting of Bi 4 Ti 3 Oi 2 , CuNb 2 O 6 , MnTaO 4 , FeWO 4 , ZnZrNb 2 O 8 , NiNb 2 O 6 , NiZrNb 2 O 8 , FeTiNb 2 O 8 , MnTiNb 2 O 8 , MgSnNb 2 O 8 , ZnTa 2 O 6 , Cu 0 85 Zn 0 I5 Nb 2 O 6 , YBa 3 Ti 2 O 8 5 , Zr 0 75 Ti 0 75 Sn 0 5 O 4 , HfTiO 4 and MgNb 2 O 6 .
  • the method may further comprise sintering a carbon additive into the two crystalline substances, the carbon additive capable of providing the mixed crystal with about 1-5 % of carbon by weight.
  • the carbon additive includes one or more members selected from the group consisting of carbon black, acetylene black, graphite, glucose, sucrose, citric acid, starch, dextrin, polyethylene glycol, and other organic and inorganic sources.
  • the examples are for illustration purpose rather than for limitation. A person skilled in the art can use equivalents thereof to achieve the same as described herein.
  • a heating rate of the sintering step ranges from 5 to 20 0 C per minute, a sintering temperature thereof from 500 to 800 0 C, and a sintering time thereof from 5 to 32 hours.
  • the sintering atmosphere is chose according the selected materials. For example, when the first or second material is easily oxidized, the sintering atmosphere may be inert atmosphere or reduction atmosphere; and when the first or second material is not easily oxidized, the sintering atmosphere may be any atmosphere.
  • a lithium ion secondary battery having a battery shell, electrodes and electrolyte, the electrodes and electrolyte being sealed within the battery shell, the electrodes having wounded or stacked cathode, anode and divider film, the cathode further including the cathode active materials described above.
  • the cathode may include cathode components such as the cathode active materials described above with adhesives.
  • the adhesives can be hydrophobic or hydrophilic binding additives without any specific binder ratio restrictions.
  • the hydrophilic to hydrophobic adhesive binder can have weight ratios of about 0.3 : 1 to about 1 : 1.
  • the adhesive can be solid, aqueous or as an emulsion.
  • the concentration can be adjusted accordingly based on methods of preparing the cathode, anode and the slurry viscosity and coating.
  • the hydrophilic adhesive solution has a concentration of about 0.5 to 4 weight percent while the hydrophobic latex binder has a concentration of about 10 to 80 weight percent.
  • Hydrophobic adhesives can include PTFE, styrene butadiene rubber, or mixtures thereof.
  • Hydrophilic adhesives can include HPMC, CMC, hydroxyethyl cellulose, polyvinyl alcohol, or mixtures thereof.
  • the binder content can be about 0.01 to 8 % by weight of the total cathode active material.
  • conductive agents may be incorporated or added in the cathode active material, the conductive agents include, but without limitation, graphite, carbon fiber, carbon black, metal powders and fibers as well as any suitable material understood by one skilled in the art.
  • the conductive agent can be about
  • the method of preparing the cathode includes using solvents to dissolve the cathode active material and mixing with adhesives and conductive agents to form a cathode slurry.
  • the cathode slurry can be applied onto cathode collectors, dried, rolled or compressed, and sliced into pieces to produce the cathode. In one example, the slurry can be dried at about 100 to 150 0 C for about 2 to 10 hours.
  • the cathode collectors include aluminum foil, copper foil, nickel-plated steel or punched stainless steel.
  • the types of solvent to use include N-methyl pyrrolidone (NMP), dimethylformamide (DMF), diethyl formamide (DEF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), water, alcohol and mixtures thereof.
  • NMP N-methyl pyrrolidone
  • DMF dimethylformamide
  • DEF diethyl formamide
  • DMSO dimethyl sulfoxide
  • THF tetrahydrofuran
  • water alcohol and mixtures thereof.
  • the amount of solvent to use can be adjusted accordingly to provide the proper slurry coating and viscosity. In one instance, the amount of solvent can be about 40 to 90 % by weight of the cathode active material.
  • the method of preparing the cathode and types of solvents, adhesives, conductive agents and cathode collectors can also incorporate other techniques understood by one skilled in the art.
  • the lithium secondary battery includes a battery shell, electrodes and electrolyte, the electrodes and electrolyte capable of being sealed within the battery shell.
  • the electrodes may include wounded or stacked cathode, anode and divider film with the cathode utilizing the cathode active material of the presently disclosed embodiments.
  • the divider film can be situated between the cathode and anode for preventing electrical shortcuts and for maintaining the electrolytic solution.
  • the divider film can include any membrane including, but without limitation, micro-porous membrane polyolefin, polyethylene fibers, ultra-fine glass fibers and fiber paper.
  • the anode can incorporate any anode active materials and known methods of forming such materials as known in the arts.
  • the anode active material can be provided in slurry form and coated onto anode collectors similar to the cathode collectors above.
  • the anode active material may include carbon additives such as non-carbon graphite, graphite, and polymers having undergone high-temperature carbon oxidation.
  • the carbon additive can also include pyrolytic coal, coke, organic polymer sintered materials and activated carbons.
  • the organic polymer sintered materials include phenolic resin, epoxy resin, and carbonized products obtained by sintering.
  • Adhesives can utilize traditional adhesives for lithium secondary batteries including polyvinyl alcohol, PTFE, carboxymethyl cellulose (CMC), hydroxymethyl cellulose (HMC), and styrene butadiene rubber (SBR).
  • the adhesive binder can be about 0.5 to 8 weight percent of the total anode active material.
  • the anode active material can further include conductive agents, the conductive agent capable of increasing electrical conductivity and reducing internal resistance of the battery.
  • the conductive agent may include, but without limitation to, carbon black, nickel powder and copper powder etc. Other conductive agents known by one skilled in the art may also be utilized and can be about 0.1 to 12 weight percent of the anode active material.
  • the method of preparing the anode may include: using solvents to dissolve the anode active material and mixing with adhesives and conductive agents to form anode slurry.
  • the anode slurry can be applied onto the anode collectors similar to that of the cathode slurry described above, dried, rolled or compressed, and sliced into pieces to produce the anode.
  • the slurry can be dried at about 100 to 150 0 C for about 2 to 10 hours.
  • the types of solvent for dissolving the anode active material include N-methyl pyrrolidone (NMP), dimethylformamide (DMF), diethyl formamide (DEF), dimethyl sulfoxide (DMSO), tetrahydrofuran (THF), water, alcohol and mixtures thereof.
  • NMP N-methyl pyrrolidone
  • DMF dimethylformamide
  • DEF diethyl formamide
  • DMSO dimethyl sulfoxide
  • THF tetrahydrofuran
  • water alcohol and mixtures thereof.
  • the amount and concentration of solvents to use can be adjusted accordingly to provide the proper slurry coating and viscosity.
  • the amount of anode slurry applied to the anode collector can be about 40 to 90 weight percent of the anode active material.
  • the electrolyte for the lithium secondary battery can be a non-aqueous electrolyte, which can be formed by dissolving lithium salt in a non-aqueous solvent.
  • the lithium salt electrolyte can include one or more members selected from lithium hexafluorophosphate (LiPF 6 ), lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluoroarsenate (LiAsF 6 ), lithium hexafluorosilicate (LiSiF 6 ), lithium tetraphenylborate (LiB(C 6 H 5 ) 4 ), lithium chloride (LiCl), lithium bromide (LiBr), lithium aluminum tetrachloride (LiAlCl 4 ), LiC(S ⁇ 2 CF 3 ) 3 , LiCH 3 SO 3 , and LiN(SO 2 CFs) 2 .
  • the non-aqueous solvent can be chain ester and ester ring mixed solution, the chain ester being one or more members of dimethyl carbonate (DMC), diethyl carbonate (DEC), ethylmethyl carbonate (EMC), methylpropyl carbonate (MPC), dimethylpropyl carbonate (DPC) and other fluoride or sulfur-containing unsaturated key chain organic esters, with the ester ring being one or more members of ethylene carbonate (EC), propylene carbonate (PC), vinylene carbonate (VC), gamma-butyrolactone ( ⁇ -BL), sodium fluoride and other lactone-containing or unsaturated organic ester rings.
  • the lithium salt electrolyte has a concentration of about 0.1 to 2 mole per liter.
  • the presently disclosed lithium secondary batteries can be provided by processes known by one skilled in the art.
  • the preparation method may include winding or stacking cathode, anode and divider films into the battery core, and placing the battery core into the battery shell, adding the electrolyte, and sealing the battery accordingly.
  • the winding, stacking and sealing of the batteries can utilize traditional techniques as understood by one skilled in the art.
  • other known steps of manufacturing the lithium secondary battery can be incorporated.
  • EXAMPLE 1 Firstly, Mix MnCO 3 , TiO 2 and Nb 2 Os with a molar ratio of 1 : 1 : 1, grind the mixture in a ball mill for 5 hours, heat in a nitrogen atmosphere at 10 0 C per minute to 500 0 C and continue sintering the product for 10 hours. With a Rigaku D/MAX-2200/PC, an XRD pattern is obtained on the resulting product. In comparison with the standard XRD pattern for MnTiNb 2 Og, it is determined that the sintered product is MnTiNb 2 Os.
  • the LiFePO 4 can be prepared by mixing lithium carbonate, ferrous oxalate, and ammonium dihydrogen phosphate in a Li : Fe : P molar ratio of 1 : 1 : 1.
  • the LiFePO 4 can be prepared by other lithium, iron and phosphate sources or by a third party.
  • the LiFePO 4 can be prepared by mixing lithium oxalate, iron oxide and diammonium hydrogen phosphate in a Li : Fe : P molar ratio of 0.95 : 1 : 1, which can be added to the ZnTa 2 Oo at a diammonium hydrogen phosphate to ZnTa 2 Oo molar ratio of 1 : 0.03 (taking into account the phosphorous components in the mixture).
  • the LiFePO 4 can be prepared by other lithium, iron and phosphate sources or by a third party.
  • the LiFePO 4 can be prepared by mixing lithium hydroxide, ferrous carbonate and phosphoric acid in a Li : Fe : P molar ratio of 1.05 : 1 :1.05, which can be added to the YBa 3 Ti 2 Og 5 at a phosphoric acid to YBa 3 Ti 2 Og S molar ratio of 1 : 0.02 (taking into account the phosphorous components in the mixture).
  • the LiFePO 4 can be prepared by other lithium, iron and phosphate sources or by a third party.
  • EXAMPLE 4 Mix CuO, ZnO and Nb 2 O 5 with a molar ratio of 0.85 : 0.15 : 1, grind the mixture in a ball mill for 5 hours, heat in a nitrogen atmosphere at a heating rate of 7 0 C per minute to 1000 0 C and continue sintering the product for 15 hours. With the Rigaku D/MAX-2200/PC, an XRD pattern can be carried out on the resulting product. And it is determined that the sintered product is Cuo 85 Zn 0 15 Nb 2 Oo in comparison with the standard XRD pattern of Cuo 85 Zn 0 15 Nb 2 Oo.
  • Example 1 The remaining steps incorporate those used in Example 1 , with the difference being that the Cuo 85Zn 0 15Nb 2 Oo substitutes the MnTiNb 2 Os to provide a LiFePO 4 / Cuo 85Zn 0 15Nb 2 Oo / C mixed crystal cathode active material.
  • the remaining steps are the same as those used in Example 1, with the difference being that the Zr 0 7S Ti 0 7S Sn 0 S O 4 substitutes the MnTiNb 2 Og to provide a LiFePO 4 / Zr 0 75 Ti 0 75 Sn 0 5 O 4 / C mixed crystal cathode active material.
  • the remaining steps are the same as those used in Example 1, with the difference being that the ZnAlO 2 substitutes the MnTiNb 2 Og to provide a LiFePO 4 / ZnAlO 2 / C mixed crystal cathode active material.
  • LiMn 0 02 Fe 0 98 PO 4 a mixture Li 2 CO 3 , FeC 2 O 4 -2H 2 O, NH 4 H 2 PO 4 and MnCO 3 in a molar ratio to the stoichiometry of LiMn 0 02 Fe 0 9 sPO 4 . Grind the mixture in a ball mill with ethanol for 5 hours, remove and dry at room temperature.
  • LiMg 0 03 Fe 0 97 PO 4 a mixture Li 2 CO 3 , FeC 2 O 4 -2H 2 O, NH 4 H 2 PO 4 and MgO in a molar ratio to the stoichiometry of LiMg 0 03 Fe 0 97 PO 4 . Grind the mixture in a ball mill with ethanol for 5 hours, remove and dry at room temperature.
  • LiZn 0 07 Fe 0 93 PO 4 a mixture Li 2 CO 3 , FeC 2 O 4 -2H 2 O, NH 4 H 2 PO 4 and ZnCO 3 in a molar ratio to the stoichiometry Of LiZn 0 07 Fe 0 93 PO 4 . Grind the mixture in a ball mill with ethanol for 5 hours, remove and dry at room temperature.
  • Example B of U.S. Patent Application No. 2007/0207385 provides a cathode material with LiFePO 4 to ZnAlO 2 with a molar ratio of 1 : 0.04 and carbon additive to provide a total carbon content of 5 % by weight in the final product.
  • the ZnAlO 2 and carbon additive are coated on the exterior surfaces of the LiFePO 4 to provide a cathode active material having LiFePO 4 / ZnAlO 2 / C.
  • the cathode active materials of the present embodiments can achieve electrical conductivity up to 1.8 S / cm measured by a Siemens per Centimeter.
  • the cathode active material of Comparative example Rl obtained by known publication having ZnAlO 2 and carbon additives coated on the surfaces of LiFePO 4 , achieves electrical conductivity of 2.6 x 10 "6 S / cm while the cathode active material of Example A7, having similar composition to that of Comparative example Rl but provides by the presently disclosed method, achieves electrical conductivity of 0.5 S / cm, the latter being 19,000 times more electrically conductive.
  • NMP N-methylpyrrolidone
  • PVDF polyvinylidene fluoride
  • NMP N-methylpyrrolidone
  • each of batteries Al -Al 5 and ACl Separately place each of batteries Al -Al 5 and ACl on the testing cabinet.
  • Using a current of 0.5 C discharge the battery from 3.8 V to 2.5 V and record the discharge capacity as the battery's initial discharge capacity.
  • the following equation is used to calculate the battery's specific discharge capacity.
  • the test results for batteries Al -Al 5 and ACl are shown in Table 2.
  • Capacity maintenance rate (Discharge capacity after n th cycle / initial discharge capacity ) x 100 %
  • the cathode active materials according to Examples 1-15 of the presently disclosed invention are able to achieve better electrical performance than Comparative example Rl .
  • the cathode active materials of batteries Al -Al 5 are able to achieve specific discharge capacity of at least 123 mAh/g at 0.5 C and maintain greater than 95 % discharge capacity after 500 cycles.
  • the cathode active material of Comparative example Rl achieved specific discharge capacity of 112 mAh/g and maintained 90.12 % discharge capacity after 500 cycles while cathode active material of Example 7, having similar composition to that of Comparative example Rl but provided by the presently disclosed method, achieved specific discharge capacity of 126 mAh/g and maintained 96.44 % discharge capacity after 500 cycles. Accordingly, the cathode active materials for lithium secondary batteries and methods of manufacturing the same according to the presently disclosed embodiments are able to provide superior electrical performance, e.g., higher electrical conductivity, discharge capacity and discharge capacity maintenance or retention rate.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention porte sur un composé de lithium composite qui présente une structure cristalline mixte, le cristal mixte présentant une première substance cristalline contenant un ou plusieurs éléments ayant les formules générales suivantes LixM'y(XO4)z, LiM'XO5, LiM'XO6, et LiM'X2O7, dans lesquelles M' est un élément choisi dans un groupe constitué par Na, Mn, Fe, Co, Ni, Ti, V, Y, Mg, Ca, Nb et Zn; X est un élément choisi dans un groupe constitué par P, S, As, Mo et W, et une seconde substance cristalline contenant un ou plusieurs éléments ayant une formule générale AaMbNcOd. En outre, l'invention porte sur une batterie secondaire lithium-ion et sur une batterie rechargeable ayant une cathode comportant ce composé de lithium composite.
PCT/CN2009/074769 2008-11-05 2009-11-03 Matériau actif de cathode, batterie secondaire lithium-ion et batterie rechargeable le comprenant WO2010051746A1 (fr)

Applications Claiming Priority (14)

Application Number Priority Date Filing Date Title
CN200810173652.X 2008-11-05
CN200810173652 2008-11-05
CN200810175243.3 2008-11-06
CN200810175243 2008-11-06
US12/316,165 2008-12-09
US12/316,180 US8057711B2 (en) 2008-02-29 2008-12-09 Composite compound with mixed crystalline structure
US12/316,180 2008-12-09
US12/316,165 US8062559B2 (en) 2008-02-29 2008-12-09 Composite compound with mixed crystalline structure
CN2008101892388A CN101478042B (zh) 2008-11-05 2008-12-26 一种正极活性物质以及正极和电池
CN200810189235.4 2008-12-26
CN200810189233.5 2008-12-26
CN200810189233A CN101740749A (zh) 2008-11-06 2008-12-26 正极活性物质的制备方法及正极活性物质以及正极和电池
CN2008101892354A CN101740750B (zh) 2008-11-05 2008-12-26 正极活性物质的制备方法及正极活性物质以及正极和电池
CN200810189238.8 2008-12-26

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JP2021082537A (ja) * 2019-11-21 2021-05-27 パナソニックＩｐマネジメント株式会社 マグネシウムイオン二次電池、マグネシウムイオン二次電池用正極活物質及びマグネシウムイオン二次電池用正極

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CN106025254B (zh) * 2016-06-24 2019-03-29 常熟理工学院 一种镍锰酸锂正极材料的表面包覆改性方法
CN108773839B (zh) * 2018-06-14 2019-11-22 方嘉城 一种高压实磷酸铁锂的制备方法
CN109065877B (zh) * 2018-10-09 2021-11-12 湖南雅城新材料有限公司 一种纳米级磷酸铁的制备方法

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