US20120267580A1 - Electroactive agglomerated particles - Google Patents
Electroactive agglomerated particles Download PDFInfo
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- US20120267580A1 US20120267580A1 US13/470,344 US201213470344A US2012267580A1 US 20120267580 A1 US20120267580 A1 US 20120267580A1 US 201213470344 A US201213470344 A US 201213470344A US 2012267580 A1 US2012267580 A1 US 2012267580A1
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
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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
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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
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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
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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
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- Y10S977/777—Metallic powder or flake
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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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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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
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- Y10S977/779—Possessing nanosized particles, powders, flakes, or clusters other than simple atomic impurity doping
Definitions
- electroactive agglomerated particles which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, and processes of preparation thereof.
- LiFePO 4 agglomerated particles are known as are agglomerated particles of Li 4 Ti 5 O 12 .
- these agglomerated particles typically consist of only a single electroactive material ( FIG. 2 ).
- LiFePO 4 agglomerated particles usually consist of a uniform mixture of LiFePO 4 and carbon, while Li 4 Ti 5 O 12 agglomerated particles usually consist of a uniform mixture of Li 4 Ti 5 O 12 and a conductive additive.
- FIGS. 3 to 5 Examples of some other mixtures of two or more intercalation nanoparticles and optionally additives such as conductivity aids, are shown in FIGS. 3 to 5 , including LiFePO 4 coated onto LiNi x Co 1 ⁇ x O 2 ( FIG. 3 ), V 2 O 5 blends with LiFePO 4 ( FIG. 4 ), and physical mixtures of micron-sized LiFePO 4 and LiNi x Co 1 ⁇ x O 2 particles ( FIG. 5 ).
- electroactive agglomerated particles which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material.
- the agglomerated particles may further comprise metal nanoparticles or carbon particles.
- the agglomerated particles may each independently comprise a coating.
- agglomerates of nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, in combination with one or more binders are also provided herein.
- the agglomerates may further comprise metal nanoparticles or carbon particles.
- electroactive agglomerated particles which comprise a first electroactive material and nanoparticles of a second electroactive material, wherein the nanoparticles of the second electroactive material are embedded in the particles of the first electroactive material.
- a method for preparing the agglomerates of nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, in combination with one or more binders comprises mixing nanoparticles of a first electroactive material, nanoparticles of a second electroactive material, and one or more binders together. In certain embodiments, the method further comprises heating the agglomerates at an elevated temperature.
- FIG. 1 is a schematic drawing of an agglomerated particle comprising two types of nanoparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles).
- FIG. 2 is a schematic drawing of an agglomerated particle comprising a single type of nanoparticles.
- FIG. 3 is a schematic drawing of an electroactive particle of a first electroactive material, coated with a second electroactive material.
- FIG. 4 is a schematic drawing of a blend of two types of nanoparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles).
- FIG. 5 is a schematic drawing of a blend of two types of microparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles).
- FIG. 6 is a schematic drawing of an agglomerated particle of a first electroactive material (a clear circle) embedded with nanoparticles of a second electroactive material (shaded circles).
- FIG. 7 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated microparticles, which comprise LiFePO 4 nanoparticles (70% by weight) and LiMn 2 O 4 nanoparticles (30% by weight).
- FIG. 8 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated microparticles, which comprise LiFePO 4 nanoparticles (50% by weight) and Li(NiCoMn) 1/3 O 2 nanoparticles (50% by weight).
- FIG. 9 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated micoparticles, which comprise LiFePO 4 nanoparticles (80% by weight) and Li(NiCoMn) 1/3 O 2 nanoparticles (20% by weight).
- electroactive agglomerated particles which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, and processes of preparation thereof.
- electroactive agglomerated particles which comprise a first electroactive material and nanoparticles of a second electroactive material, wherein the nanoparticles of the second electroactive material are embedded in the particle of the first electroactive material.
- Electroactive agglomerated particles are useful in rechargeable lithium batteries.
- FIG. 1 shows an agglomerated particle of the present disclosure.
- the agglomerated particles comprise two or more different nanoparticles.
- electroactive agglomerated particles comprising two or more types of nanoparticles.
- the two or more types of nanoparticles each comprise different electroactive material.
- the first type is nanoparticles of a first type first electroactive material
- the second type is nanoparticles of a second electroactive material.
- the electroactive agglomerated particles are provided as microparticles to increase the particle flowability.
- the electroactive agglomerated particles have an average particle size ranging from about 0.1 to about 100 ⁇ m, from about 1 to about 50 ⁇ m, from about 1 to about 20 ⁇ m, from about 1 to about 15 ⁇ m, or from about 1 to about 5 ⁇ m.
- the electroactive agglomerated particles have an average surface area ranging from about 0.1 to about 100 m 2 /g, from about 1 to about 50 m 2 /g, from about 2 to about 20 m 2 /g, from about 5 to about 20 m 2 /g, or from about 10 to about 15 m 2 /g.
- the agglomerated particles have such particle size distribution that 10% of the electroactive agglomerated particles have a particle size of about 0.05 ⁇ m, about 0.1 ⁇ m, or about 1 ⁇ m; and 90% of the electroactive agglomerated particles have a particle size of about 500 ⁇ m, about 100 ⁇ m, about 50 ⁇ m, about 20 ⁇ m, about 15 ⁇ m, or about 5 ⁇ m.
- the particle size distribution is that 10% of the electroactive agglomerated particles have a particle size of 1 ⁇ m and 90% of the electroactive agglomerated particles have a particle size of 15 ⁇ m.
- each type of nanoparticles in the electroactive agglomerated particles independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm.
- each type of nanoparticles in the electroactive agglomerated particles may independently have various shapes, including, but not limited to, sphere, fibril, or platelet.
- V 2 O 5 fibrils can be mixed with LiFePO 4 spheres.
- the agglomerated particles can further comprise one or more additives, such as carbon.
- the agglomerated particles can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- the agglomerated particles can be subsequently coated to provide additional desired chemical and/or physical properties, such as chemical inertness (by coating with Al 2 O 3 or ZnO, for example) or electrical conductivity (by coating with, e.g., ionic conductors).
- the electroactive agglomerated particles provided herein comprise two types of nanoparticles, nanoparticles of a first electroactive material, and nanoparticles of a second electroactive material.
- the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO 4 , wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO 4 . In yet another embodiment, the first electroactive material is LiMnPO 4 . In yet another embodiment, the first electroactive material is LiVPO 4 .
- the first electroactive material is AM a 1 ⁇ x M b x PO 4 , wherein A is Li, Na, or a mixture thereof; M a is Fe, Co, Mn, or a mixture thereof; M b is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15.
- the first electroactive material is LiM a 1 ⁇ x M b x PO 4 .
- the first electroactive material is NaM a 1 ⁇ x M b x PO 4 .
- the second electroactive material is a metal oxide.
- the second electroactive material is selected from the group consisting of LiCoO 2 ; LiNiCoO 2 ; LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4; Li(NiMnCo) 1/3 O 2 ; Li(NiMn) 1/2 O 2 ; and LiV 2 O 5 .
- the second electroactive material is LiCoO 2 .
- the second electroactive material is LiNiCoO 2 .
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo) 1/3 O 2 . In yet another embodiment, the second electroactive material is Li(NiMn) 1/2 O 2 . In yet another embodiment, the second electroactive material is LiV 2 O 5 .
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1.
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are 0.33.
- the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiFePO 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiMnPO 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiFePO 4 (type 1) and nanoparticles of V 2 O 5 (type 2).
- the agglomerated particles comprise from about 1 to about 99%, from about 30 to about 95%, from about 50 to about 90%, from about 60% to about 90%, or from about 80% to 90% by weight of the nanoparticles (type 1) of the first electroactive material; and from about 99 to about 1%, from about 70 to about 5%, from about 50 to about 10%, from about 40 to about 10%, or from about 20 to about 10% by weight of the nanoparticles (type 2) of the second electroactive material.
- the agglomerated particles comprise from about 50 to about 90% by weight of the nanoparticles of the first electroactive material and from about 50 to about 10% by weight of the nanoparticles of the second electroactive material.
- the agglomerated particles comprise from about 60 to about 90% by weight of the nanoparticles of the first electroactive material and from about 40 to about 10% by weight of the nanoparticles of the second electroactive material. In still another embodiment, the agglomerated particles comprise from about 80 to about 90% by weight of the nanoparticles of the first electroactive material and from about 20 to about 10% by weight of the nanoparticles of the second electroactive material.
- agglomerated particles can be used to make electrodes using conventional processing techniques, such as reverse roll coating or doctor blade coating.
- Another advantage is that one of the two electroactive materials can enhance the electrical or ionic conductivity of the other without reducing specific capacity.
- the agglomerated particles of LiFePO 4 and LiNiXo 1 ⁇ x O 2 nanoparticles the voltage behaviors of both the LiFePO 4 and LiNi x Co 1 ⁇ x O 2 materials are retained, so that the agglomerated particles behave as a superposition of the two.
- agglomerates comprising two or more types of nanoparticles, in combination with one or more binders.
- the two or more types of nanoparticles each comprise different electroactive material.
- the first type is nanoparticles of a first electroactive material
- the second type is nanoparticles of a second electroactive material.
- the agglomerates provided herein are microparticles.
- the agglomerates have an average particle size ranging from about 0.1 to about 100 ⁇ m, from about 1 to about 50 ⁇ m, from about 1 to about 20 ⁇ m, from about 1 to about 15 ⁇ m, or from about 1 to about 5 ⁇ m.
- agglomerates have an average surface area ranging from about 0.1 to about 100 m 2 /g, from about 1 to about 50 m 2 /g, from about 2 to about 20 m 2 /g, from about 5 to about 20 m 2 /g, or from about 10 to about 15 m 2 /g.
- the agglomerates have such particle size distribution that 10% of the agglomerates have a particle size of about 0.05 ⁇ m, about 0.1 ⁇ m, or about 1 ⁇ m; and 90% of the agglomerates have a particle size of about 500 ⁇ m, about 100 ⁇ m, about 50 ⁇ m, about 20 ⁇ m, about 15 ⁇ m, or about 5 ⁇ m. In certain embodiments, the particle size distribution is that 10% of the agglomerates have a particle size of 1 ⁇ m and 90% of the agglomerates have a particle size of 15 ⁇ m.
- each type of nanoparticles in the agglomerates independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm.
- each type of nanoparticles in the agglomerates may independently have various shapes, including, but not limited to, sphere, fibril, or platelet.
- the agglomerates can further comprise one or more additives, such as carbon.
- the agglomerates can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- the agglomerates provided herein comprise two types of nanoparticles, nanoparticles of a first electroactive material, and nanoparticles of a second electroactive material.
- the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO 4 , wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO 4 . In yet another embodiment, the first electroactive material is LiMnPO 4 . In yet another embodiment, the first electroactive material is LiVPO 4 .
- the first electroactive material is AM a 1 ⁇ x M b x PO 4 , wherein A is Li, Na, or a mixture thereof; M a is Fe, Co, Mn, or a mixture thereof; M b is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15.
- the first electroactive material is LiM a 1 ⁇ x M b x PO 4 .
- the first electroactive material is NaM a 1 ⁇ x M b x PO 4 .
- the second electroactive material is a metal oxide.
- the second electroactive material is selected from the group consisting of LiCoO 2 ; LiNiCoO 2 ; LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4; Li(NiMnCo) 1/3 O 2 ; Li(NiMn) 1/2 O 2 ; and LiV 2 O 5 .
- the second electroactive material is LiCoO 2 .
- the second electroactive material is LiNiCoO 2 .
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo) 1/3 O 2 . In yet another embodiment, the second electroactive material is Li(NiMn) 1/2 O 2 . In yet another embodiment, the second electroactive material is LiV 2 O 5 .
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1.
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are 0.33.
- the first electroactive material is LiFePO 4 .
- the second electroactive material is LiCoO 2 .
- the second electroactive material is LiNiCoO 2 .
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the second electroactive material is Li(NiMnCo) 1/3 O 2 . In yet another embodiment, the second electroactive material is Li(NiMn) 1/2 O 2 . In still another embodiment, the second electroactive material is LiV 2 O 5 .
- the agglomerates provided herein are microparticles comprising nanoparticles of LiFePO 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the agglomerates are microparticles comprising nanoparticles of LiMn 2 O 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x CO 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the agglomerates provided herein are microparticles comprising nanoparticles of LiFePO 4 (type 1) and nanoparticles of V 2 O 5 (type 2).
- the first electroactive material is a lithium compound. In certain embodiments, the first electroactive material is LiMPO 4 , wherein M is a transition metal. In certain embodiments, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In certain embodiments, the first electroactive material is LiFePO 4 . In certain embodiments, the first electroactive material is LiMnPO 4 . In certain embodiments, the first electroactive material is LiVPO 4 .
- the second electroactive material is a metal oxide. In certain embodiments, the second electroactive material is selected from the group consisting of LiCoO 2 , LiNiCoO 2 , Li(NiMnCo) 1/3 O 2 , Li(NiMn) 1/2 O 2 , and LiV 2 O 5 .
- the first electroactive material is LiFePO 4 .
- the second electroactive material is LiCoO 2 . In certain embodiments, the second electroactive material is LiNiCoO 2 . In certain embodiments, the second electroactive material is Li(NiMnCO) 1/3 O 2 . In certain embodiments, the second electroactive material is Li(NiMn) 1/2 O 2 . In certain embodiments, the second electroactive material is LiV 2 O 5 .
- Suitable binders for use in the agglomerates provided herein include, but are not limited to, coal tar, solid ionic conductors, asphalt pitch, and polymeric binders, such as polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and styrene butadiene rubber (SBR).
- PTFE polytetrafluoroethylene
- CMC carboxymethyl cellulose
- PVDF polyvinylidene fluoride
- PVA polyvinyl alcohol
- SBR styrene butadiene rubber
- the binder is selected from the group consisting of coal tar, solid ionic conductor, asphalt pitch, a polymeric binder, and mixtures thereof.
- the polymer binder is selected from the group consisting of polytetrafluoroethylene, carboxymethyl cellulose, polyvinylidene fluoride, polyvinyl alcohol, and styrene butadiene rubber.
- the binder is selected from the group consisting of a mixture of lithium nitride and lithium phosphate; a mixture of lithium phosphorus oxynitride and lithium phosphate; Li 1+x+y (Al, Ga) x (Ti, Ge) 2 ⁇ x Si y P 3 ⁇ y O 12 , where 0 ⁇ x ⁇ 1 and 0 ⁇ y ⁇ 1; Li x Si y M z O v N w , where 0.3 ⁇ x ⁇ 0.46, 0.05 ⁇ y ⁇ 0.15, 0.016 ⁇ z ⁇ 0.05, 0.42 ⁇ v ⁇ 0.05 ⁇ w ⁇ 0.029, and M is selected from the group consisting of Nb, Ta, and W.
- the agglomerates provided herein are microparticles of nanoparticles of LiFePO 4 and nanoparticles of LiNi x Co 1 ⁇ x O 2 , in combination with a binder, such as coal tar.
- the agglomerates provided herein are microparticles of nanoparticles of LiMn 2 O 4 and nanoparticles of LiNi x Co 1 ⁇ x O 2 , in combination with a binder, such as coal tar.
- the agglomerates provided herein are microparticles of nanoparticles of LiFePO 4 and nanoparticles of V 2 O 5 , in combination with a binder, such as coal tar.
- the agglomerates comprise from about 30 to about 95% by weight of the nanoparticles (type 1) of the first electroactive material, from about 70 to about 5% by weight of the nanoparticles (type 2) of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s). In another embodiment, the agglomerates comprise from about 50 to about 90% by weight of the nanoparticles (type 1) of the first electroactive material, from about 50 to about 10% by weight of the nanoparticles (type 2) of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s).
- the agglomerates comprise from about 60 to about 90% by weight of the nanoparticles of the first electroactive material, from about 80 to about 90% by weight of the nanoparticles of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s). Nevertheless, the total amount of all the ingredients in the agglomerates should equal to 100%.
- electroactive agglomerated particles which comprise a first electroactive material and one or more types of nanoparticles of electroactive materials that differ from the first electroactive, wherein the nanoparticles are embedded in the particle of the first electroactive material.
- the embedded electroactive agglomerated particles are microparticles.
- the embedded electroactive agglomerated particles have an average particle size ranging from about 0.1 to about 100 ⁇ m, from about 1 to about 50 ⁇ m, from about 1 to about 20 ⁇ m, from about 1 to about 15 ⁇ m, or from about 1 to about 5 ⁇ m.
- the electroactive agglomerated particles have an average surface area ranging from about 0.1 to about 100 m 2 /g, from about 1 to about 50 m 2 /g, from about 2 to about 20 m 2 /g, from about 5 to about 20 m 2 /g, or from about 10 to about 15 m 2 /g.
- the embedded agglomerated particles have such particle size distribution that 10% of the embedded electroactive agglomerated particles have a particle size of about 0.05 ⁇ m, about 0.1 ⁇ m, or about 1 ⁇ m; and 90% of the embedded electroactive agglomerated particles have a particle size of about 500 ⁇ m, about 100 ⁇ m, about 50 ⁇ m, about 20 ⁇ m, about 15 ⁇ m, or about 5 ⁇ m.
- the particle size distribution is that 10% of the embedded electroactive agglomerated particles have a particle size of 1 ⁇ m and 90% of the embedded electroactive agglomerated particles have a particle size of 15 ⁇ m.
- each type of nanoparticles in the embedded electroactive agglomerated particles independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm.
- each type of nanoparticles in the embedded electroactive agglomerated particles may independently have various shapes, including, but not limited to, sphere, fibril, or platelet.
- the embedded agglomerated particles can further comprise one or more additives, such as carbon.
- the embedded agglomerated particles can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- the embedded agglomerated particles can be subsequently coated to provide additional desired chemical and/or physical properties, such as chemical inertness (by coating with Al 2 O 3 or ZnO, for example) or electrical conductivity (by coating with, e.g., ionic conductors).
- chemical inertness by coating with Al 2 O 3 or ZnO, for example
- electrical conductivity by coating with, e.g., ionic conductors.
- the embedded electroactive agglomerated particles provided herein comprise one type of nanoparticles, that is, nanoparticles of a second electroactive material.
- the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO 4 , wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO 4 . In yet another embodiment, the first electroactive material is LiMnPO 4 . In yet another embodiment, the first electroactive material is LiVPO 4 .
- the first electroactive material is AM a 1 ⁇ x M b x PO 4 , wherein A is Li, Na, or a mixture thereof; M a is Fe, Co, Mn, or a mixture thereof; M b is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15.
- the first electroactive material is LiM a 1 ⁇ x M b x PO 4 .
- the first electroactive material is NaM a 1 ⁇ x M b x PO 4 .
- the second electroactive material is a metal oxide.
- the second electroactive material is selected from the group consisting of LiCoO 2 , LiNiCoO 2 , LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4, Li(NiMnCo) 1/3 O 2 , Li(NiMn) 1/2 O 2 , and LiV 2 O 5 .
- the second electroactive material is LiCoO 2 .
- the second electroactive material is LiNiCoO 2 .
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo) 1/3 O 2 . In yet another embodiment, the second electroactive material is Li(NiMn) 1/2 O 2 . In yet another embodiment, the second electroactive material is LiV 2 O 5 .
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1.
- the second electroactive material is LiNi x Mn y Co 1 ⁇ x ⁇ y O 2 , wherein x and y are 0.33.
- the embedded electroactive agglomerated particles provided herein are microparticles comprising LiFePO 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the embedded electroactive agglomerated particles provided herein are microparticles comprising LiMnPO 4 (type 1) and nanoparticles of LiNi x Co 1 ⁇ x O 2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4.
- the second electroactive material is LiNi x Co 1 ⁇ x O 2 , wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- the embedded electroactive agglomerated particles provided herein are microparticles comprising LiFePO 4 (type 1) and nanoparticles of V 2 O 5 (type 2).
- the embedded agglomerated particles comprise from about 1 to about 99%, from about 30 to about 95%, from about 50 to about 90%, from about 60% to about 90%, or from about 80% to 90% by weight of the first electroactive material; and from about 99 to about 1%, from about 70 to about 5%, from about 50 to about 10%, from about 40 to about 10%, or from about 20 to about 10% by weight of the second electroactive material.
- the embedded agglomerated particles comprise from about 50 to about 90% by weight of the first electroactive material and from about 50 to about 10% by weight of the second electroactive material.
- the embedded agglomerated particles comprise from about 60 to about 90% by weight of the first electroactive material and from about 40 to about 10% by weight of the second electroactive material. In still another embodiment, the embedded agglomerated particles comprise from about 80 to about 90% by weight of the first electroactive material and from about 20 to about 10% by weight of the second electroactive material.
- a method for preparing the agglomerates which comprises mixing nanoparticles of a first electroactive material, nanoparticles of a second electroactive material, and one or more binders.
- the mixing step can be performed using any conventional methods known to an ordinary of skill in the art, including, but not limited to, ball mixing and cospraying, such as thermal spraying and ultrasonic spraying.
- ball mixing and cospraying such as thermal spraying and ultrasonic spraying.
- the production method will depend on the nature of the nanoparticles employed.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, and coal tar are prepared by mixing LiFePO 4 and metal oxide nanoparticles together; contacting the nanoparticle mixture with a coal tar fume, and ball mixing the nanoparticle mixture.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black are prepared by mixing LiFePO 4 and metal oxide nanoparticles together, contacting the nanoparticle mixture with a coal tar fume and carbon black, and ball mixing the nanoparticle mixture.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, metal nanoparticles (such as Al, Ti, or Cr), and coal tar are prepared by mixing LiFePO 4 nanoparticles, metal oxide nanoparticles, and metal nanoparticles together, contacting the nanoparticle mixture with coal tar fume, and ball mixing the nanoparticle mixture.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, and coal tar are prepared by air-injecting LiFePO 4 nanoparticles, metal oxide nanoparticles, and coal tar, independently and simultaneously, from three tubes into a flowing bed.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black are prepared by air-injecting LiFePO 4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black, independently and simultaneously, from four tubes into a flowing bed.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, metal nanoparticles (such as Al, Ti, or Cr), and coal tar are prepared by air-injecting LiFePO 4 nanoparticles, metal oxide nanoparticles, metal nanoparticles, and coal tar, independently and simultaneously, from four tubes into a flowing bed.
- a method for preparing the electroactive agglomerated particles which comprises heating the agglomerates prepared as described herein to an elevated temperature.
- the elevated temperature is ranging from about 200 to about 1000° C., from about 250 to about 750° C., from about 300 to about 700° C., or from about 400 to about 600° C.
- Negative and positive electrodes were coated onto an Al foil and Cu foil, respectively, using a small doctor blade coater, and then calendared to designed thickness. Then the electrodes were silted to designed width and dried in a vacuum oven at high temperature. Once the electrodes were dried, all subsequently cell fabrication steps were carried out inside a drying room at a Dew point of about ⁇ 35° C. The electrodes were tabbed first and then wound into jellyrolls. The jellyrolls were then inserted into an 18650 can and an EC based electrolyte would be put into the cell under vacuum. The cells were crimped for sealing after electrolyte filling. The cell was then be aged and formed.
- the cell was tested one week after the formation.
- the cell capacities and voltage profiles at ⁇ 1 C and ⁇ 5 C (or ⁇ 10 C for the Mn mixed particle) were measured by the following procedure: i) the cell was charged to 3.9V at 0.6 A for 2.5 hours; ii) the cell then rested for several minutes; iii) the cell was discharged to 2.2 V at 1 C rate; iv) the cell rested for another several minutes; v) the cell was then charged to 3.9V at 0.6 A; vi) the cell rested for several minutes; and vii) the cell was discharged to 2.2 V at ⁇ 5 C or ⁇ 10 C depending on the mixed particles.
- the microsized agglomerates of LiFePO 4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black were prepared by mixing LiFePO 4 and metal oxide nanoparticles together, contacting the nanoparticle mixture with a coal tar fume and carbon black, and ball mixing the nanoparticle mixture.
- the metal oxide particles used herein are LiMn 2 O 4 and Li(NiCoMn) 1/3 O 2 nanoparticles.
- Fe 2 O 3 is mixed with Li 2 CO 3 and (NH 4 ) 2 HPO 4 in the presence of carbon.
- To the mixture is then added nanoparticles of a second electroactive material and then thoroughly mixed again.
- the resulting mixture is heated under N 2 at an elevated temperature from about 700 to about 850° C. to yield microsized agglomerates, each of which comprises LiFePO 4 nanoparticles and the metal oxide nanoparticles.
- Fe 2 O 3 particles are mixed with LiH 2 PO 4 and Mg(OH) 2 particles in the presence of carbon.
- To the mixture is then added nanoparticles of a second electroactive material and then thoroughly mixed again.
- the resulting mixture is heated under N 2 at an elevated temperature from about 700 to about 850° C. to yield microsized agglomerates, each of which comprises LiFe 1 ⁇ x Mg x PO 4 nanoparticles and the metal oxide nanoparticles.
- LiFePO 4 is prepared via a sol-gel synthesis from Fe(NO 3 ) 3 .9H 2 O, lithium acetate dehydrate, and phosphoric acid (85%). The iron nitrate and lithium acetate are combined with phosphoric acid (85%) in a stoichiometric ratio of 1:1:1. Distilled water is then added until all the constituents are completely dissolved. Nanoparticles of a second electroactive material, such as a metal oxide, are added. The pH of the mixture is adjusted to 8.5 to 9.5 using NH 4 OH to form a sol. The sol is then heated on a hot plate with stirring to form a gel. The sample is then fired to 500° C.
- a second electroactive material such as a metal oxide
- the mixture is then ground using a planetary ball mill in a solvent, such as ethanol and acetone.
- a solvent such as ethanol and acetone.
- the grinding solvent is then evaporated under nitrogen and the resulting powder is thoroughly mixed and fired to about 600° C. to yield embedded microsized particles which each comprise LiFePO 4 and the metal oxide nanoparticles.
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Abstract
Provided herein are electroactive agglomerated particles, which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive materials, and processes of preparation thereof.
Description
- This application is a continuation of U.S. application Ser. No. 11/872,713, filed Oct. 16, 2007, which claims the benefit of U.S. Provisional Application Nos. 60/859,541, filed Nov. 17, 2006; and 60/945,914, filed Jun. 23, 2007. The disclosures of these applications are incorporated by reference herein in their entirety.
- Provided herein are electroactive agglomerated particles, which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, and processes of preparation thereof.
- Agglomerated nanoparticles are currently used in batteries. For example, LiFePO4 agglomerated particles are known as are agglomerated particles of Li4Ti5O12. However, these agglomerated particles typically consist of only a single electroactive material (
FIG. 2 ). For example, LiFePO4 agglomerated particles usually consist of a uniform mixture of LiFePO4 and carbon, while Li4Ti5O12 agglomerated particles usually consist of a uniform mixture of Li4Ti5O12 and a conductive additive. - Examples of some other mixtures of two or more intercalation nanoparticles and optionally additives such as conductivity aids, are shown in
FIGS. 3 to 5 , including LiFePO4 coated onto LiNixCo1−xO2 (FIG. 3 ), V2O5 blends with LiFePO4 (FIG. 4 ), and physical mixtures of micron-sized LiFePO4 and LiNixCo1−xO2 particles (FIG. 5 ). - Provided herein are electroactive agglomerated particles, which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material. The agglomerated particles may further comprise metal nanoparticles or carbon particles. In addition, the agglomerated particles may each independently comprise a coating.
- Also provided herein are agglomerates of nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, in combination with one or more binders. The agglomerates may further comprise metal nanoparticles or carbon particles.
- Further provided herein are electroactive agglomerated particles, which comprise a first electroactive material and nanoparticles of a second electroactive material, wherein the nanoparticles of the second electroactive material are embedded in the particles of the first electroactive material.
- Provided herein is a method for preparing the agglomerates of nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, in combination with one or more binders. The method comprises mixing nanoparticles of a first electroactive material, nanoparticles of a second electroactive material, and one or more binders together. In certain embodiments, the method further comprises heating the agglomerates at an elevated temperature.
-
FIG. 1 is a schematic drawing of an agglomerated particle comprising two types of nanoparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles). -
FIG. 2 is a schematic drawing of an agglomerated particle comprising a single type of nanoparticles. -
FIG. 3 is a schematic drawing of an electroactive particle of a first electroactive material, coated with a second electroactive material. -
FIG. 4 is a schematic drawing of a blend of two types of nanoparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles). -
FIG. 5 is a schematic drawing of a blend of two types of microparticles, e.g., nanoparticles of a first electroactive material (shaded circles) and nanoparticles of a second electroactive material (clear circles). -
FIG. 6 is a schematic drawing of an agglomerated particle of a first electroactive material (a clear circle) embedded with nanoparticles of a second electroactive material (shaded circles). -
FIG. 7 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated microparticles, which comprise LiFePO4 nanoparticles (70% by weight) and LiMn2O4 nanoparticles (30% by weight). -
FIG. 8 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated microparticles, which comprise LiFePO4 nanoparticles (50% by weight) and Li(NiCoMn)1/3O2 nanoparticles (50% by weight). -
FIG. 9 is a discharge curve of a lithium ion cell with a cathode comprising agglomerated micoparticles, which comprise LiFePO4 nanoparticles (80% by weight) and Li(NiCoMn)1/3O2 nanoparticles (20% by weight). - Provided herein are electroactive agglomerated particles, which comprise nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, and processes of preparation thereof. Also provided herein are electroactive agglomerated particles, which comprise a first electroactive material and nanoparticles of a second electroactive material, wherein the nanoparticles of the second electroactive material are embedded in the particle of the first electroactive material.
- Electroactive agglomerated particles are useful in rechargeable lithium batteries.
FIG. 1 shows an agglomerated particle of the present disclosure. The agglomerated particles comprise two or more different nanoparticles. - In one embodiment, provided herein are electroactive agglomerated particles comprising two or more types of nanoparticles. In one embodiment, the two or more types of nanoparticles each comprise different electroactive material. In another embodiment, the first type is nanoparticles of a first type first electroactive material, and the second type is nanoparticles of a second electroactive material.
- In another embodiment, the electroactive agglomerated particles are provided as microparticles to increase the particle flowability. In certain embodiments, the electroactive agglomerated particles have an average particle size ranging from about 0.1 to about 100 μm, from about 1 to about 50 μm, from about 1 to about 20 μm, from about 1 to about 15 μm, or from about 1 to about 5 μm. In certain embodiments, the electroactive agglomerated particles have an average surface area ranging from about 0.1 to about 100 m2/g, from about 1 to about 50 m2/g, from about 2 to about 20 m2/g, from about 5 to about 20 m2/g, or from about 10 to about 15 m2/g. In certain embodiments, the agglomerated particles have such particle size distribution that 10% of the electroactive agglomerated particles have a particle size of about 0.05 μm, about 0.1 μm, or about 1 μm; and 90% of the electroactive agglomerated particles have a particle size of about 500 μm, about 100 μm, about 50 μm, about 20 μm, about 15 μm, or about 5 μm. In certain embodiments, the particle size distribution is that 10% of the electroactive agglomerated particles have a particle size of 1 μm and 90% of the electroactive agglomerated particles have a particle size of 15 μm.
- In certain embodiments, each type of nanoparticles in the electroactive agglomerated particles independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm. Furthermore, each type of nanoparticles in the electroactive agglomerated particles may independently have various shapes, including, but not limited to, sphere, fibril, or platelet. For example, V2O5 fibrils can be mixed with LiFePO4 spheres.
- The agglomerated particles can further comprise one or more additives, such as carbon. Alternatively, the agglomerated particles can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- The agglomerated particles can be subsequently coated to provide additional desired chemical and/or physical properties, such as chemical inertness (by coating with Al2O3 or ZnO, for example) or electrical conductivity (by coating with, e.g., ionic conductors).
- In one embodiment, the electroactive agglomerated particles provided herein comprise two types of nanoparticles, nanoparticles of a first electroactive material, and nanoparticles of a second electroactive material.
- In one embodiment, the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO4, wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO4. In yet another embodiment, the first electroactive material is LiMnPO4. In yet another embodiment, the first electroactive material is LiVPO4. In yet another embodiment, the first electroactive material is AMa 1−xMb xPO4, wherein A is Li, Na, or a mixture thereof; Ma is Fe, Co, Mn, or a mixture thereof; Mb is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15. In yet another embodiment, the first electroactive material is LiMa 1−xMb xPO4. In still another embodiment, the first electroactive material is NaMa 1−xMb xPO4.
- In another embodiment, the second electroactive material is a metal oxide. In another embodiment, the second electroactive material is selected from the group consisting of LiCoO2; LiNiCoO2; LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4; Li(NiMnCo)1/3O2; Li(NiMn)1/2O2; and LiV2O5. In yet another embodiment, the second electroactive material is LiCoO2. In yet another embodiment, the second electroactive material is LiNiCoO2. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo)1/3O2. In yet another embodiment, the second electroactive material is Li(NiMn)1/2O2. In yet another embodiment, the second electroactive material is LiV2O5. In yet another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1. In still another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are 0.33.
- In one embodiment, the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiFePO4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In yet another embodiment, the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiMnPO4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In still another embodiment, the electroactive agglomerated particles provided herein are microparticles comprising nanoparticles of LiFePO4 (type 1) and nanoparticles of V2O5 (type 2).
- In one embodiment, the agglomerated particles comprise from about 1 to about 99%, from about 30 to about 95%, from about 50 to about 90%, from about 60% to about 90%, or from about 80% to 90% by weight of the nanoparticles (type 1) of the first electroactive material; and from about 99 to about 1%, from about 70 to about 5%, from about 50 to about 10%, from about 40 to about 10%, or from about 20 to about 10% by weight of the nanoparticles (type 2) of the second electroactive material. In another embodiment, the agglomerated particles comprise from about 50 to about 90% by weight of the nanoparticles of the first electroactive material and from about 50 to about 10% by weight of the nanoparticles of the second electroactive material. In yet another embodiment, the agglomerated particles comprise from about 60 to about 90% by weight of the nanoparticles of the first electroactive material and from about 40 to about 10% by weight of the nanoparticles of the second electroactive material. In still another embodiment, the agglomerated particles comprise from about 80 to about 90% by weight of the nanoparticles of the first electroactive material and from about 20 to about 10% by weight of the nanoparticles of the second electroactive material.
- One of the advantages of the agglomerated particles is that these electroactive particles can be used to make electrodes using conventional processing techniques, such as reverse roll coating or doctor blade coating.
- Another advantage is that one of the two electroactive materials can enhance the electrical or ionic conductivity of the other without reducing specific capacity. For example, with the agglomerated particles of LiFePO4 and LiNiXo1−xO2 nanoparticles, the voltage behaviors of both the LiFePO4 and LiNixCo1−xO2 materials are retained, so that the agglomerated particles behave as a superposition of the two.
- Also provided herein are agglomerates comprising two or more types of nanoparticles, in combination with one or more binders. In one embodiment, the two or more types of nanoparticles each comprise different electroactive material. In another embodiment, the first type is nanoparticles of a first electroactive material, and the second type is nanoparticles of a second electroactive material.
- In one embodiment, the agglomerates provided herein are microparticles. In certain embodiments, the agglomerates have an average particle size ranging from about 0.1 to about 100 μm, from about 1 to about 50 μm, from about 1 to about 20 μm, from about 1 to about 15 μm, or from about 1 to about 5 μm. In certain embodiments, agglomerates have an average surface area ranging from about 0.1 to about 100 m2/g, from about 1 to about 50 m2/g, from about 2 to about 20 m2/g, from about 5 to about 20 m2/g, or from about 10 to about 15 m2/g. In certain embodiments, the agglomerates have such particle size distribution that 10% of the agglomerates have a particle size of about 0.05 μm, about 0.1 μm, or about 1 μm; and 90% of the agglomerates have a particle size of about 500 μm, about 100 μm, about 50 μm, about 20 μm, about 15 μm, or about 5 μm. In certain embodiments, the particle size distribution is that 10% of the agglomerates have a particle size of 1 μm and 90% of the agglomerates have a particle size of 15 μm.
- In certain embodiments, each type of nanoparticles in the agglomerates independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm. Furthermore, each type of nanoparticles in the agglomerates may independently have various shapes, including, but not limited to, sphere, fibril, or platelet.
- The agglomerates can further comprise one or more additives, such as carbon. Alternatively, the agglomerates can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- In one embodiment, the agglomerates provided herein comprise two types of nanoparticles, nanoparticles of a first electroactive material, and nanoparticles of a second electroactive material.
- In one embodiment, the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO4, wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO4. In yet another embodiment, the first electroactive material is LiMnPO4. In yet another embodiment, the first electroactive material is LiVPO4. In yet another embodiment, the first electroactive material is AMa 1−xMb xPO4, wherein A is Li, Na, or a mixture thereof; Ma is Fe, Co, Mn, or a mixture thereof; Mb is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15. In yet another embodiment, the first electroactive material is LiMa 1−xMb xPO4. In still another embodiment, the first electroactive material is NaMa 1−xMb xPO4.
- In another embodiment, the second electroactive material is a metal oxide. In another embodiment, the second electroactive material is selected from the group consisting of LiCoO2; LiNiCoO2; LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4; Li(NiMnCo)1/3O2; Li(NiMn)1/2O2; and LiV2O5. In yet another embodiment, the second electroactive material is LiCoO2. In yet another embodiment, the second electroactive material is LiNiCoO2. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo)1/3O2. In yet another embodiment, the second electroactive material is Li(NiMn)1/2O2. In yet another embodiment, the second electroactive material is LiV2O5. In yet another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1. In still another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are 0.33.
- In one embodiment, the first electroactive material is LiFePO4. In another embodiment, the second electroactive material is LiCoO2. In yet another embodiment, the second electroactive material is LiNiCoO2. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo)1/3O2. In yet another embodiment, the second electroactive material is Li(NiMn)1/2O2. In still another embodiment, the second electroactive material is LiV2O5.
- In one embodiment, the agglomerates provided herein are microparticles comprising nanoparticles of LiFePO4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In yet another embodiment, the agglomerates are microparticles comprising nanoparticles of LiMn2O4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCO1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In still another embodiment, the agglomerates provided herein are microparticles comprising nanoparticles of LiFePO4 (type 1) and nanoparticles of V2O5 (type 2).
- In certain embodiments, the first electroactive material is a lithium compound. In certain embodiments, the first electroactive material is LiMPO4, wherein M is a transition metal. In certain embodiments, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In certain embodiments, the first electroactive material is LiFePO4. In certain embodiments, the first electroactive material is LiMnPO4. In certain embodiments, the first electroactive material is LiVPO4.
- In certain embodiments, the second electroactive material is a metal oxide. In certain embodiments, the second electroactive material is selected from the group consisting of LiCoO2, LiNiCoO2, Li(NiMnCo)1/3O2, Li(NiMn)1/2O2, and LiV2O5. In certain embodiments, the first electroactive material is LiFePO4. In certain embodiments, the second electroactive material is LiCoO2. In certain embodiments, the second electroactive material is LiNiCoO2. In certain embodiments, the second electroactive material is Li(NiMnCO)1/3O2. In certain embodiments, the second electroactive material is Li(NiMn)1/2O2. In certain embodiments, the second electroactive material is LiV2O5.
- Suitable binders for use in the agglomerates provided herein include, but are not limited to, coal tar, solid ionic conductors, asphalt pitch, and polymeric binders, such as polytetrafluoroethylene (PTFE), carboxymethyl cellulose (CMC), polyvinylidene fluoride (PVDF), polyvinyl alcohol (PVA), and styrene butadiene rubber (SBR).
- Suitable solid ionic conductors include, but are not limited to, Li3PO4; Li3PO4Li1+x+y(Al, Ga)x(Ti, Ge)2−xSiyP3−yO12, where 0≦x≦1 and 0≦y≦1; LiaNbbTacOdNe, where 0.1≦a≦2.5, 0≦b≦1, 0≦c≦1, b+c=1, 0.1≦d≦5, and 0≦e≦2; LixSiyMzOvNw, where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z≦0.05, 0.42≦v≦0.05, 0≦w≦0.029, and M is selected from the group consisting of Nb, Ta, and W; mixtures of lithium phosphorus oxynitride and Li3PO4.
- In one embodiment, the binder is selected from the group consisting of coal tar, solid ionic conductor, asphalt pitch, a polymeric binder, and mixtures thereof. In another embodiment, the polymer binder is selected from the group consisting of polytetrafluoroethylene, carboxymethyl cellulose, polyvinylidene fluoride, polyvinyl alcohol, and styrene butadiene rubber. In yet another embodiment, the binder is selected from the group consisting of a mixture of lithium nitride and lithium phosphate; a mixture of lithium phosphorus oxynitride and lithium phosphate; Li1+x+y(Al, Ga)x(Ti, Ge)2−xSiyP3−yO12, where 0≦x≦1 and 0≦y≦1; LixSiyMzOvNw, where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z≦0.05, 0.42≦v≦0.05≦w≦0.029, and M is selected from the group consisting of Nb, Ta, and W.
- In one embodiment, the agglomerates provided herein are microparticles of nanoparticles of LiFePO4 and nanoparticles of LiNixCo1−xO2, in combination with a binder, such as coal tar.
- In another embodiment, the agglomerates provided herein are microparticles of nanoparticles of LiMn2O4 and nanoparticles of LiNixCo1−xO2, in combination with a binder, such as coal tar.
- In still another embodiment, the agglomerates provided herein are microparticles of nanoparticles of LiFePO4 and nanoparticles of V2O5, in combination with a binder, such as coal tar.
- In one embodiment, the agglomerates comprise from about 30 to about 95% by weight of the nanoparticles (type 1) of the first electroactive material, from about 70 to about 5% by weight of the nanoparticles (type 2) of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s). In another embodiment, the agglomerates comprise from about 50 to about 90% by weight of the nanoparticles (type 1) of the first electroactive material, from about 50 to about 10% by weight of the nanoparticles (type 2) of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s). In yet another embodiment, the agglomerates comprise from about 60 to about 90% by weight of the nanoparticles of the first electroactive material, from about 80 to about 90% by weight of the nanoparticles of the second electroactive material, and from about 0.1 to about 5% by weight of the binder(s). Nevertheless, the total amount of all the ingredients in the agglomerates should equal to 100%.
- Further provided herein are electroactive agglomerated particles, which comprise a first electroactive material and one or more types of nanoparticles of electroactive materials that differ from the first electroactive, wherein the nanoparticles are embedded in the particle of the first electroactive material.
- In one embodiment, the embedded electroactive agglomerated particles are microparticles. In certain embodiments, the embedded electroactive agglomerated particles have an average particle size ranging from about 0.1 to about 100 μm, from about 1 to about 50 μm, from about 1 to about 20 μm, from about 1 to about 15 μm, or from about 1 to about 5 μm. In certain embodiments, the electroactive agglomerated particles have an average surface area ranging from about 0.1 to about 100 m2/g, from about 1 to about 50 m2/g, from about 2 to about 20 m2/g, from about 5 to about 20 m2/g, or from about 10 to about 15 m2/g. In certain embodiments, the embedded agglomerated particles have such particle size distribution that 10% of the embedded electroactive agglomerated particles have a particle size of about 0.05 μm, about 0.1 μm, or about 1 μm; and 90% of the embedded electroactive agglomerated particles have a particle size of about 500 μm, about 100 μm, about 50 μm, about 20 μm, about 15 μm, or about 5 μm. In certain embodiments, the particle size distribution is that 10% of the embedded electroactive agglomerated particles have a particle size of 1 μm and 90% of the embedded electroactive agglomerated particles have a particle size of 15 μm.
- In certain embodiments, each type of nanoparticles in the embedded electroactive agglomerated particles independently has an average particle size ranging from about 1 to about 500 nm, from about 1 to about 200 nm, or from about 2 to about 100 nm. Furthermore, each type of nanoparticles in the embedded electroactive agglomerated particles may independently have various shapes, including, but not limited to, sphere, fibril, or platelet.
- The embedded agglomerated particles can further comprise one or more additives, such as carbon. Alternatively, the embedded agglomerated particles can further comprise metals (such as Al, Ti, or Cr), or metal oxides, such as aluminum oxide or zirconium oxide.
- The embedded agglomerated particles can be subsequently coated to provide additional desired chemical and/or physical properties, such as chemical inertness (by coating with Al2O3 or ZnO, for example) or electrical conductivity (by coating with, e.g., ionic conductors).
- In one embodiment, the embedded electroactive agglomerated particles provided herein comprise one type of nanoparticles, that is, nanoparticles of a second electroactive material.
- In one embodiment, the first electroactive material is a lithium compound. In another embodiment, the first electroactive material is a lithium phosphate compound. In yet another embodiment, the first electroactive material is LiMPO4, wherein M is a transition metal. In yet another embodiment, M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni. In yet another embodiment, the first electroactive material is LiFePO4. In yet another embodiment, the first electroactive material is LiMnPO4. In yet another embodiment, the first electroactive material is LiVPO4. In yet another embodiment, the first electroactive material is AMa 1−xMb xPO4, wherein A is Li, Na, or a mixture thereof; Ma is Fe, Co, Mn, or a mixture thereof; Mb is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.99, from about 0.01 to about 0.5, from about 0.01 to about 0.30, or from about 0.01 to about 0.15. In yet another embodiment, the first electroactive material is LiMa 1−xMb xPO4. In still another embodiment, the first electroactive material is NaMa 1−xMb xPO4.
- In another embodiment, the second electroactive material is a metal oxide. In another embodiment, the second electroactive material is selected from the group consisting of LiCoO2, LiNiCoO2, LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4, Li(NiMnCo)1/3O2, Li(NiMn)1/2O2, and LiV2O5. In yet another embodiment, the second electroactive material is LiCoO2. In yet another embodiment, the second electroactive material is LiNiCoO2. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In yet another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3. In yet another embodiment, the second electroactive material is Li(NiMnCo)1/3O2. In yet another embodiment, the second electroactive material is Li(NiMn)1/2O2. In yet another embodiment, the second electroactive material is LiV2O5. In yet another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are each independently ranging from 0 to about 0.95, from about 0.01 to about 0.9, from about 0.05 to about 0.80, from about 0.1 to about 0.5, or from 0.2 to about 0.4, and x+y is less than 1. In still another embodiment, the second electroactive material is LiNixMnyCo1−x−yO2, wherein x and y are 0.33.
- In one embodiment, the embedded electroactive agglomerated particles provided herein are microparticles comprising LiFePO4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In yet another embodiment, the embedded electroactive agglomerated particles provided herein are microparticles comprising LiMnPO4 (type 1) and nanoparticles of LiNixCo1−xO2 (type 2), wherein x is no less than 0 and no greater than 1, from about 0.05 to about 0.95, from about 0.1 to about 0.90, from about 0.2 to about 0.5, or from about 0.2 to about 0.4. In another embodiment, the second electroactive material is LiNixCo1−xO2, wherein x is from about 0.2 to about 0.5, from about 0.2 to about 0.4, or about 0.3.
- In still another embodiment, the embedded electroactive agglomerated particles provided herein are microparticles comprising LiFePO4 (type 1) and nanoparticles of V2O5 (type 2).
- In one embodiment, the embedded agglomerated particles comprise from about 1 to about 99%, from about 30 to about 95%, from about 50 to about 90%, from about 60% to about 90%, or from about 80% to 90% by weight of the first electroactive material; and from about 99 to about 1%, from about 70 to about 5%, from about 50 to about 10%, from about 40 to about 10%, or from about 20 to about 10% by weight of the second electroactive material. In another embodiment, the embedded agglomerated particles comprise from about 50 to about 90% by weight of the first electroactive material and from about 50 to about 10% by weight of the second electroactive material. In yet another embodiment, the embedded agglomerated particles comprise from about 60 to about 90% by weight of the first electroactive material and from about 40 to about 10% by weight of the second electroactive material. In still another embodiment, the embedded agglomerated particles comprise from about 80 to about 90% by weight of the first electroactive material and from about 20 to about 10% by weight of the second electroactive material.
- Provided herein is a method for preparing the agglomerates provided herein, which comprises mixing nanoparticles of a first electroactive material, nanoparticles of a second electroactive material, and one or more binders.
- The mixing step can be performed using any conventional methods known to an ordinary of skill in the art, including, but not limited to, ball mixing and cospraying, such as thermal spraying and ultrasonic spraying. The production method will depend on the nature of the nanoparticles employed.
- In one embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, and coal tar are prepared by mixing LiFePO4 and metal oxide nanoparticles together; contacting the nanoparticle mixture with a coal tar fume, and ball mixing the nanoparticle mixture.
- In another embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black are prepared by mixing LiFePO4 and metal oxide nanoparticles together, contacting the nanoparticle mixture with a coal tar fume and carbon black, and ball mixing the nanoparticle mixture.
- In yet another embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, metal nanoparticles (such as Al, Ti, or Cr), and coal tar are prepared by mixing LiFePO4 nanoparticles, metal oxide nanoparticles, and metal nanoparticles together, contacting the nanoparticle mixture with coal tar fume, and ball mixing the nanoparticle mixture.
- In yet another embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, and coal tar are prepared by air-injecting LiFePO4 nanoparticles, metal oxide nanoparticles, and coal tar, independently and simultaneously, from three tubes into a flowing bed.
- In yet another embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black are prepared by air-injecting LiFePO4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black, independently and simultaneously, from four tubes into a flowing bed.
- In still another embodiment, the microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, metal nanoparticles (such as Al, Ti, or Cr), and coal tar are prepared by air-injecting LiFePO4 nanoparticles, metal oxide nanoparticles, metal nanoparticles, and coal tar, independently and simultaneously, from four tubes into a flowing bed.
- Provided herein is a method for preparing the electroactive agglomerated particles provided herein, which comprises heating the agglomerates prepared as described herein to an elevated temperature. In one embodiment, the elevated temperature is ranging from about 200 to about 1000° C., from about 250 to about 750° C., from about 300 to about 700° C., or from about 400 to about 600° C.
- Electrode and Cell Fabrication
- Negative and positive electrodes were coated onto an Al foil and Cu foil, respectively, using a small doctor blade coater, and then calendared to designed thickness. Then the electrodes were silted to designed width and dried in a vacuum oven at high temperature. Once the electrodes were dried, all subsequently cell fabrication steps were carried out inside a drying room at a Dew point of about −35° C. The electrodes were tabbed first and then wound into jellyrolls. The jellyrolls were then inserted into an 18650 can and an EC based electrolyte would be put into the cell under vacuum. The cells were crimped for sealing after electrolyte filling. The cell was then be aged and formed.
- The cell was tested one week after the formation. The cell capacities and voltage profiles at ˜1 C and ˜5 C (or ˜10 C for the Mn mixed particle) were measured by the following procedure: i) the cell was charged to 3.9V at 0.6 A for 2.5 hours; ii) the cell then rested for several minutes; iii) the cell was discharged to 2.2 V at 1 C rate; iv) the cell rested for another several minutes; v) the cell was then charged to 3.9V at 0.6 A; vi) the cell rested for several minutes; and vii) the cell was discharged to 2.2 V at ˜5 C or ˜10 C depending on the mixed particles.
- The microsized agglomerates of LiFePO4 nanoparticles, metal oxide nanoparticles, coal tar, and carbon black were prepared by mixing LiFePO4 and metal oxide nanoparticles together, contacting the nanoparticle mixture with a coal tar fume and carbon black, and ball mixing the nanoparticle mixture. The metal oxide particles used herein are LiMn2O4 and Li(NiCoMn)1/3O2 nanoparticles.
- Fe2O3 is mixed with Li2CO3 and (NH4)2HPO4 in the presence of carbon. To the mixture is then added nanoparticles of a second electroactive material and then thoroughly mixed again. The resulting mixture is heated under N2 at an elevated temperature from about 700 to about 850° C. to yield microsized agglomerates, each of which comprises LiFePO4 nanoparticles and the metal oxide nanoparticles.
- Fe2O3 particles are mixed with LiH2PO4 and Mg(OH)2 particles in the presence of carbon. To the mixture is then added nanoparticles of a second electroactive material and then thoroughly mixed again. The resulting mixture is heated under N2 at an elevated temperature from about 700 to about 850° C. to yield microsized agglomerates, each of which comprises LiFe1−xMgxPO4 nanoparticles and the metal oxide nanoparticles.
- LiFePO4 is prepared via a sol-gel synthesis from Fe(NO3)3.9H2O, lithium acetate dehydrate, and phosphoric acid (85%). The iron nitrate and lithium acetate are combined with phosphoric acid (85%) in a stoichiometric ratio of 1:1:1. Distilled water is then added until all the constituents are completely dissolved. Nanoparticles of a second electroactive material, such as a metal oxide, are added. The pH of the mixture is adjusted to 8.5 to 9.5 using NH4OH to form a sol. The sol is then heated on a hot plate with stirring to form a gel. The sample is then fired to 500° C. The mixture is then ground using a planetary ball mill in a solvent, such as ethanol and acetone. The grinding solvent is then evaporated under nitrogen and the resulting powder is thoroughly mixed and fired to about 600° C. to yield embedded microsized particles which each comprise LiFePO4 and the metal oxide nanoparticles.
- The examples set forth above are provided to give those of ordinary skill in the art with a complete disclosure and description of how to make and use the claimed embodiments, and are not intended to limit the scope of what is disclosed herein. Modifications that are obvious to persons of skill in the art are intended to be within the scope of the following claims. All publications, patents, and patent applications cited in this specification are incorporated herein by reference as if each such a publication, patent or patent application were specifically and individually indicated to be incorporated herein by reference.
Claims (18)
1. Electroactive agglomerated particles comprising nanoparticles of a first electroactive material and nanoparticles of a second electroactive material, wherein the agglomerated particles have an average particle size ranging from about 0.1 μm to about 100 μm.
2. The agglomerated particles of claim 1 , wherein the first electroactive material is LiMPO4, wherein M is a transition metal selected from the group consisting of Ti, V, Cr, Mn, Fe, Co, and Ni.
3. The agglomerated particles of claim 1 , wherein the first electroactive material is selected from the group consisting of LiFePO4, LiMnPO4, LiVPO4, and mixtures thereof.
4. The agglomerated particles of claim 1 , wherein the first electroactive material is AMa 1−xMb xPO4, wherein A is Li, Na, or a mixture thereof; Ma is Fe, Co, Mn, or a mixture thereof; Mb is Mg, Ca, Zn, Ni, Co, Cu, Al, B, Cr, Nb, or a mixture thereof; and x is from about 0.01 to about 0.30.
5. The agglomerated particles of claim 1 , wherein the second electroactive material is a metal oxide selected from the group consisting of LiCoO2, LiNiCoO2, Li(NiMnCo)1/3O2, Li(NiMn)1/2O2, LiNixCo1−xO2, and LiV2O5.
6. The agglomerated particles of claim 1 , comprising from about 30 to about 95% by weight of the nanoparticles of the first electroactive material and from about 70 to about 5% by weight of the nanoparticles of the second electroactive material.
7. The agglomerated particles of claim 1 , wherein the nanoparticles of the first electroactive material have an average particle size ranging from about 1 to about 500 nm.
8. The agglomerated particles of claim 1 , wherein the nanoparticles of the second electroactive material have an average particle size ranging from about 1 to about 500 nm.
9. The agglomerated particles of claim 1 further comprising one or more additives.
10. The agglomerated particles of claim 9 , wherein the additive is carbon.
11. The agglomerated particles of claim 1 , further comprising a metal or metal oxide.
12. The agglomerated particles of claim 11 , wherein the metal is Al, Ti, or Cr.
13. The agglomerates particles of claim 1 , further one or more binders.
14. The agglomerates of claim 13 , wherein the binder is selected from the group consisting of coal tar, solid ionic conductor, asphalt pitch, a polymeric binder, and mixtures thereof.
15. The agglomerates of claim 14 , wherein the polymer binder is selected from the group consisting of polytetrafluoroethylene, carboxymethyl cellulose, polyvinylidene fluoride, polyvinyl alcohol, and styrene butadiene rubber.
16. The agglomerates of claim 13 , wherein the binder is selected from the group consisting of a mixture of lithium nitride and lithium phosphate; a mixture of lithium phosphorus oxynitride and lithium phosphate; Li1+x+y(Al, Ga) x(Ti, Ge)2−xSiyP3−yO12, where 0≦x≦1 and 0≦y≦1; LixSiyMzOvNw, where 0.3≦x≦0.46, 0.05≦y≦0.15, 0.016≦z≦0.05, 0.42≦v≦0.05, 0≦w≦0.029, and M is selected from the group consisting of Nb, Ta, and W.
17. The agglomerates of claim 13 , comprising from about 30 to about 95% by weight of the nanoparticles of the first electroactive material, from about 70 to about 5% by weight of the nanoparticles of the second electroactive material, and from about 0.1 to about 5% by weight of the binders.
18. Embedded agglomerated particles comprising a first electroactive material and one or more types of nanoparticles of electroactive materials that are different from the first electroactive material, wherein the nanoparticles are embedded in the particle of the first electroactive material.
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US13/470,344 US20120267580A1 (en) | 2006-11-17 | 2012-05-13 | Electroactive agglomerated particles |
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US85954106P | 2006-11-17 | 2006-11-17 | |
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US11/872,713 US8197719B2 (en) | 2006-11-17 | 2007-10-16 | Electroactive agglomerated particles |
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US8197719B2 (en) | 2012-06-12 |
US20080116423A1 (en) | 2008-05-22 |
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