CA2585594C - Cathode material for manufacturing a rechargeable battery - Google Patents
Cathode material for manufacturing a rechargeable battery Download PDFInfo
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- CA2585594C CA2585594C CA2585594A CA2585594A CA2585594C CA 2585594 C CA2585594 C CA 2585594C CA 2585594 A CA2585594 A CA 2585594A CA 2585594 A CA2585594 A CA 2585594A CA 2585594 C CA2585594 C CA 2585594C
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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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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- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A cathode material includes crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 µm. Each of the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
Description
1 ~
CATHODE IdATERIAL FOR I4ANUFACTURING A RECIiARGEASLE BATTERY
BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a cathode material for manufacturing a rechargeable battery, more particularly to a cathode material for manufacturing a rechargeable battery whichincludes crystalline nanometer-szzed primary particles and micrometer-sized secondary particles, each of the micrometer-sized secondary particles being composed of the crystalline nanometer-sized primary particles.xhis invention also relates to a cathode for a rechargeable battery including 'the cathode material, 2. Description of the Relat.ed Art Along with diversified development of electronic products, there is increasing need for portable power supplies. For example, electronic consumer products, medical devices, motorcycles, automobiles, and power tools and the like require a portable power supply for power source.
Fo=current portab].e powersupplies,rechargeable batteries are relatively popular. Since lithium rechargeable batteries have a high ratio of volume to capacity, pollution-free and recyclable charge/discharge properties, and no memory effect, it has a great development poten'tial in the future.
Additionally, a cathodernaterial used for manufacture of the cathode plays an important role in the performance 2 t , of the rechargeable battery. Among the known cathode materials, since lithium ferrous phosphate compounds and the related compounds having similar properties to LiFePO4 compounds, such as LiMPO9, in which M represents transition elements, e.g., manganese (Mn), cobalt (Co), and nickel (Ni), are environmentally benign, relatively stable and abundant, and have relatively good electrochemical properties, e.g., high specific capacity, good charge/discharge cycling performance, and good thermostability, they have been evaluated to be the cathode material with greatest development potential.
However, at present, there is a difference between practical and theoretical electrochemical properties of known LiFeP09 compounds and the related compounds. For example, the theoretical specific capacity of L9.k'eP09 compounds and the related compounds is about 170 mAh/g, whereas the LiFePO9 compounds disclosed in U.S. Patent No.
5, 910, 382 have a specific capacity of about 95 mAh/g, which is far below the theoretical specific capacity. In order to improve the capacity property of the LiFe?04 compounds, it has been proposed to add other elements to the LiFePO4 compounds having one of o1ivine and NASICON structures so as to increase the capacity propez'ty of the Li FePO4 compounds, see U.S.Patent Nos. 6, 716, 372 and6,815,122.However,since the elements used for substituting iron are not easily available, production cost is relatively high.
In addition, U.S. Patent No. 6,632,566 (hereinafter I. .
CATHODE IdATERIAL FOR I4ANUFACTURING A RECIiARGEASLE BATTERY
BACKGROUND OF THE INVENTION
1. Field of the Invention This invention relates to a cathode material for manufacturing a rechargeable battery, more particularly to a cathode material for manufacturing a rechargeable battery whichincludes crystalline nanometer-szzed primary particles and micrometer-sized secondary particles, each of the micrometer-sized secondary particles being composed of the crystalline nanometer-sized primary particles.xhis invention also relates to a cathode for a rechargeable battery including 'the cathode material, 2. Description of the Relat.ed Art Along with diversified development of electronic products, there is increasing need for portable power supplies. For example, electronic consumer products, medical devices, motorcycles, automobiles, and power tools and the like require a portable power supply for power source.
Fo=current portab].e powersupplies,rechargeable batteries are relatively popular. Since lithium rechargeable batteries have a high ratio of volume to capacity, pollution-free and recyclable charge/discharge properties, and no memory effect, it has a great development poten'tial in the future.
Additionally, a cathodernaterial used for manufacture of the cathode plays an important role in the performance 2 t , of the rechargeable battery. Among the known cathode materials, since lithium ferrous phosphate compounds and the related compounds having similar properties to LiFePO4 compounds, such as LiMPO9, in which M represents transition elements, e.g., manganese (Mn), cobalt (Co), and nickel (Ni), are environmentally benign, relatively stable and abundant, and have relatively good electrochemical properties, e.g., high specific capacity, good charge/discharge cycling performance, and good thermostability, they have been evaluated to be the cathode material with greatest development potential.
However, at present, there is a difference between practical and theoretical electrochemical properties of known LiFeP09 compounds and the related compounds. For example, the theoretical specific capacity of L9.k'eP09 compounds and the related compounds is about 170 mAh/g, whereas the LiFePO9 compounds disclosed in U.S. Patent No.
5, 910, 382 have a specific capacity of about 95 mAh/g, which is far below the theoretical specific capacity. In order to improve the capacity property of the LiFe?04 compounds, it has been proposed to add other elements to the LiFePO4 compounds having one of o1ivine and NASICON structures so as to increase the capacity propez'ty of the Li FePO4 compounds, see U.S.Patent Nos. 6, 716, 372 and6,815,122.However,since the elements used for substituting iron are not easily available, production cost is relatively high.
In addition, U.S. Patent No. 6,632,566 (hereinafter I. .
3 ~
referred to as the '566 patent) discloses increase in the specific surface of the Lir'eP09 compound powders in favor of diffusion of lithium ions in the powders, thereby enhancing capacity of a cathode material made f rom the LiFePO4 compound powcters. Pazticularly, the cathode material described in the '566 patent is produced by sintering the LiFePO4 compound powders at a suitable temperature in such a manner that, the cathode material thus formed is composed of separate single-phase crystalline particles having a grain size not larger than 10 ,u m. Although the capacity of the cathode material illustrated in the Examples of the '566 patent can be about 163 mAri/g, the LiFePO~ compound powders included in the cathode material have a relatively large particle size and uneven distribution. Thus, the cathode material of the 1566 patent cannot be used with aqueous binders and aqueous solvents when applied to manufacture of the cathode. Besides, since the chaxge/discharge rate of the battery with the cathode material of the '566 patent is about C/37, which is calculated based on data shown in the Examples of the '566 patent, such charge/discharge rate is too low for practical application and needs to be improved.
The applicant has proposed a method for making a lithium mixed metal compound, such as the lithium ferrous phosphate compounds having an olivine structure, in Canadian patent application No. 2, 522, 114 (hereinafter referred to as the '114 application) . The method disclosed in the '114 application includes preparing a reactant mixture that comprises ion sources of the lithium ferrous phosphate compounds, and exposing the reactant mixture to a non-oxidizing atmosphere in the presence of suspended carbon particles. The lithium ferrous phosphate compounds thus made are in powder form and have relatively small particle size and even distribution.
SiAMARY OF THE INVENTION
The present invention was developed on the basis of the co-pending '114application.Theinventorof the present invention concezves a cathode material that includes crystalline nanometer-sized primary particles of a metal ~ compound having one of alivine and NASICON structures, and micrometer-sized secondary particles, each of the micrometer-sized secondary particles being composed of the crystalline nanometer-sized primary particles. The inventor of the present invention found that the cathode material including mzcrometer-sized secondary particles, each of which is composed of crystalline nanometer-sized primary particles of a metal compound, may be produced by modifying the method called for in the '114 application.
Therefore, according to one aspect of this invention, a cathode material includes crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 ,ctm. Each of I. õ
the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
According to another aspect.of thisinven.tion,a cathode for a rechargeable battery includes an electrode plate and 5 a coating of a cathode material coated on the electrode plate. The cathode material includes crystalline nanometer-sized primary particlesofa metalcompound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 g m. Each of the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of the preferred embodiments of this invention, with reference to the accompanying drawings, in which;
Fig. 1 shows a SEM photograph to illustrate surface morphology of micrometer-sized secondary particles included in the cathode material prepared according to Example D of the present invention;
Fig. 2 shows a SEM photograph to illu5trate surface morphology of nanometer-sized primary particles which compose each of the micrometer-sized secondary particles included in the cathode material prepared according to Example D of the present invention;
referred to as the '566 patent) discloses increase in the specific surface of the Lir'eP09 compound powders in favor of diffusion of lithium ions in the powders, thereby enhancing capacity of a cathode material made f rom the LiFePO4 compound powcters. Pazticularly, the cathode material described in the '566 patent is produced by sintering the LiFePO4 compound powders at a suitable temperature in such a manner that, the cathode material thus formed is composed of separate single-phase crystalline particles having a grain size not larger than 10 ,u m. Although the capacity of the cathode material illustrated in the Examples of the '566 patent can be about 163 mAri/g, the LiFePO~ compound powders included in the cathode material have a relatively large particle size and uneven distribution. Thus, the cathode material of the 1566 patent cannot be used with aqueous binders and aqueous solvents when applied to manufacture of the cathode. Besides, since the chaxge/discharge rate of the battery with the cathode material of the '566 patent is about C/37, which is calculated based on data shown in the Examples of the '566 patent, such charge/discharge rate is too low for practical application and needs to be improved.
The applicant has proposed a method for making a lithium mixed metal compound, such as the lithium ferrous phosphate compounds having an olivine structure, in Canadian patent application No. 2, 522, 114 (hereinafter referred to as the '114 application) . The method disclosed in the '114 application includes preparing a reactant mixture that comprises ion sources of the lithium ferrous phosphate compounds, and exposing the reactant mixture to a non-oxidizing atmosphere in the presence of suspended carbon particles. The lithium ferrous phosphate compounds thus made are in powder form and have relatively small particle size and even distribution.
SiAMARY OF THE INVENTION
The present invention was developed on the basis of the co-pending '114application.Theinventorof the present invention concezves a cathode material that includes crystalline nanometer-sized primary particles of a metal ~ compound having one of alivine and NASICON structures, and micrometer-sized secondary particles, each of the micrometer-sized secondary particles being composed of the crystalline nanometer-sized primary particles. The inventor of the present invention found that the cathode material including mzcrometer-sized secondary particles, each of which is composed of crystalline nanometer-sized primary particles of a metal compound, may be produced by modifying the method called for in the '114 application.
Therefore, according to one aspect of this invention, a cathode material includes crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 ,ctm. Each of I. õ
the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
According to another aspect.of thisinven.tion,a cathode for a rechargeable battery includes an electrode plate and 5 a coating of a cathode material coated on the electrode plate. The cathode material includes crystalline nanometer-sized primary particlesofa metalcompound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 g m. Each of the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
BRIEF DESCRIPTION OF THE DRAWINGS
Other features and advantages of the present invention will become apparent in the following detailed description of the preferred embodiments of this invention, with reference to the accompanying drawings, in which;
Fig. 1 shows a SEM photograph to illustrate surface morphology of micrometer-sized secondary particles included in the cathode material prepared according to Example D of the present invention;
Fig. 2 shows a SEM photograph to illu5trate surface morphology of nanometer-sized primary particles which compose each of the micrometer-sized secondary particles included in the cathode material prepared according to Example D of the present invention;
Fig. 3 shows a particle-size analytical plot to illustrate particle-size distribution of the cathode material prepared according to Example D of the present invention;
Fig. 4 shows a SEM photograph to illustrate surface morphology of micrometer-sized secondary particles included in the cathode materi.al prepared according to Example H of the present invention;
Fig. 5 shows a specific capacity versus cycle number plot of a cathode coated with a coating of a cathode material obtained from Example F of the present invention;
Eig. 6 is a voltage versus specific capacity plot for a cathode coated with a coating of a cathode material obtained from Example G of this invention;
Fig. 7 is a voltage versus specific capacity plot for a cathode coatedwith a coating of a cathodematerial obtained from Example H of this invention;
Fig. 8 is a voltage versus capacity plot for a cathode rechargeable battery with a cathode coated with a coating of a cathode material obtained from Example F of this invention at different charge/discharge rates;
Fig. 9 is a voltage versus capacity plot for cathode rechargeable batteries, each of which has a cathode coated with a coating of a mixture of a cathode material obtained from Example F of this invention and one of various binders;
and Fig. 10 is a schematic sectional view to illustrate structure of a cathode for a rechargeable battery according to this invention.
DETAILED DESCRIPTION OF THE PREFERRED II+BODIIMENTS
The preferred embodiment of a cathode materialaccording to this invention includes crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 ,u m. Each of 10 the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
Preferably, each of the micrometer-sized secondary particles is formed by sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles. More preferably, the cathode material of this invention further includes a carbonaceouscomponent.
Most preferably, the cathode material of this invention fuxther includes carbon particles adhered to the surfaces of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondary particles. In addition, the cathode material of this invention is preferred to have a BET specific surface area ranging from 5 to 100 m2/g.
Preferably, the metal compound has a formula of A3xM2y (P04) 3, in which A represents at least one first metal element selected from the group consisting of Groups IA, IIA and IIIA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and ITIA,, transition elements, and mixtures thereof; and 0<xi5l.2, 0<y,<,,1, 6.
More preferably, the at least one first metal element is selected from the group consista.ng of Li, Na, K, Be, Mg, 8, Al, andmi.xtures thereof, and the at least one second metal element is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, X, Zr, Nb, Mo, Be, Mg, Ca, Sr, B, Al, Ge, Sn, Ga, and mixtures thereof.
The abovementioned cathode material according to this invention may be manufactured by a method involving formation of particulate precursors of the metal compound followed by crystallization of the metal compound of the particulate precursors to form the crystalline nanometer-sized primary particles and sintering of the crystalline nanometer-sized primary particles.
l'articulazly,the methodincludes:preparing a reactant solution including the metal compound, the metal compound having a formula of A3xM2y(PO4)3i in which A xepresents at least one first metal element selected from the group consisting of Groups IA, IIA and I IIA, and mixtures thereof, M represents at least one second meta], element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof, and 0<x =1.2, OEy _-:S1.6;
drying the reactantsolution to form particulate precursors of the metal compound; and heating the particulate precursors under a non-oxidizing atmosphere in the presence 9 ' of suspended carbon particles so as to crystallize the metal compound of each of the particulate precursors to form the crystalline nanometer-sized primary particles and so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles to form each of the micrometer-sized secondary particles.
Drying operation of the reactant solution may be conducted through dehydration, ultrasonic spray-drying, spray-drying, freeze-drying, vacuum-drying, filtering, or spray pyrolysis techniques.
Heating operation of the particulate precursors is preferably conducted at a temperature ranging from 400 to 900 C for 6 to 48 hours.
Alternatively, the abovementioned cathode material according to this invention may be manufactured by a method involving heating of particulate precursors to form the crystalline nanometer-sized primary particles, subsequently granulating the crystalline nanometer-sized primary particles to form the micrometer-sized secondary particles, and followed by sintering of the crystalline nanomater-sized primary particles of each of the micrometer-sized secondary particles.
Particularly, the alternative method includes:
preparing a reactantsolutionincluding the metal compound, the metal compound having a formula of A3xM2y (POy) 3, in which A represents at least one first metal element selected from the group consisting of Groups IA, I IA and IIxA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof; and 0<x ~1.2, 5 0<y='S 1. 6; drying the reactant solution to form particulate precursors of the metal compound; heating the particulate precursoxs in the presence of suspended carbon particles so as to crystallize the metal compound of each of the particulate precursors to form the crystalline 10 nanometer-sized primary particles; granulating the crystalline nanometer-sized primary particles into micrometer-sized secondary particles; and heating the granulated micrometer-sized secondary particles under a non-oxidizing atmosphere in the presence of suspended carbon particles so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondaryparticles.
Preferably, the heating operation of the particulate precursors is conducted at a temperatvre ranging from 550 'G to 600 C for 2 to 24 hours. Preferably, heating operation of the granulated micrometer-sized secondary particles is conducted at a temperature ranging from 400 to 900'C for 6 to 48 hours.
In addition, during manufacture of the preferred embodiment of the cathode material of this invention according to the abovementioned methods, a carbonaceous I. ,.
component is optionally added into the reactant solution prior to the drying operation of the reactant solution_ The carbonaCeous component is one of an organic acid selected from the group consisting of citric acid, oxalic acid, tartaric acid, lactic acid, terephthalic acid, ethylenediaminetetraacetic acid, and acetic acid; a carbohydrate selected from the group consisting of sucrose, lactose, glucose, andoligose; and carbon powders madefrom a material selected from the group consisting of acetylene carbon black, carbon black, mesophase carbon micro beads (MCMS), supper P and graphite.
Referring to P'ig. 10, the preferred embodiment of a cathode for a rechargeable battery according to this invention includes an electrode plate 1, and a coating 2 of the abovementioned cathode material of this invention coated on the electrode plate 1.
Preferably, the cathode material further includes an aqueous binder, in addition to an aqueous solvent. More preferably, the aqueous binder is styrene-butadiene rubber (SHR). More preferably, the aqueous solvent is deionized wat(ar.
Alternatively, the cathode material may further include a non-aqueous binder. Preferably, the non-aqueous binder is po].yvinylidene fluoride (PVDF). Preferably, the non-aqueous solvent is N-methyl-pyrrolidone (NMP).
Preferably, the cathode material may further include a thickener. More pref erably, the thickener is carboxymethyl r cellulose (CMC).
In addition, the preferred embodiment of the cathode thus made may be combined with an anode and an electrolyte to form the rechargeable battery.
Example Analytical Eauipment 1. Scanning Electron Microscope (SEM): Hitachi model S-3500V.
2. Paxticle size distribution analyzer: Horiba, LA-910.
3. Charge/discharge cycle tester: Maccor Series 4000 and 3200 Automated Test Systems (Maccor Inc., Tulsa, Oklahoma, U.S.A) 4. Accelerated surface and porosimetry system: ASAP 2010 (Micromeritics, U.S.A.) Example A
0.2 mole of ferric nitrate (Fe(NO3)3) was added into 200 ml of deionized watex. After Fe(N03)3 was completely dissolved in the deionized water, 0.2 moles of phosphoric acid and 100 ml of 2N lithium hydroxide (LiOH) solution were added in sequence, so as to form a mixture having a stoichiometric ratio 1- 1: 1 of Fe3+: T~i+: POq3+. 100 znl of 0.252 g oxalic acid solution was added to the mixture having Fe3+, Li+, and PO93+ ions. The reactant solution thus formed was dried to form particulate precursors of LiFePO4-based metal compound.
Alext, the particulate precursors were placed in an aluminumoxide cx'ueible.The crucible together with charcoal was placed in a tubul.ar furnace which was heated at 700 C for 12 hours in the presence of an argon carrier gas flowing into the furnace. Carbon particles formed from the charcoal were suspended in the argon carrier gas and were mixed with the micro-particulate precursors, thereby crystallizing the metal compound of each of the particulate precursors to form the crystalline nanometer-szzed primary particles and causing sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles to form each of the micrometer-sized secondary particles. A cathode material having one of olivine and NASIC4N structures and including micrometer-sized secondary particles having a particle size ranging from 1 to 50 g m was obtained. Particularly, each of the micrometer-sized secondary particles is composed of crystalline nanometer-sized primary particles of the LiFePOg-based metal compound that have a particle size ranging from 10 to 500 nm and that have carbon particles adhered to surfaces thereof, and is formed by sintering of contacted portions of the surfaces of adjacent ones of the crystalline nanometer-sized primary particles.
Example B
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles, was prepared in a manner similar to that of Example A, except that 0.2 mole of Fe (NO3) 3 was replaced with 0.2 mole of ferric chloride (FeC13) Example C
In this example, the powdered cathode material incJ.udes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example A, except that 0. 2 mole of Fe (N03) 3 was replaced with 0.2 mole of iron (Fe) powders.
Example D
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example C, except that 100 ml of 0. 252g oxal ic acid solution was replaced wi'th 100 ml of 0.42 g citric acid solution.
Example E
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example D, except that 0.1 g of glucose was added to the reactant solution after the addition of the citric acid solution.
Example F
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example 0, except that 0.1 g of sucrose was added to the reactant solution after the addition of the citric acid solution.
5 Example G
zn this example, the powdered cathode material inclvdes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that 10 of Example D, except that 0.2 mole of the iron powders were replaced with a mixture of 0.196 mole of iron powders, 0. 002 mole of magnesiumchloride (MgC12) , and 0. 002 mo1.e of aluminum chloride (AlC13). The powdered cathode mate.rial includes micrometer-sized secondary particles, each of which is 15 composed of nanometer-sized primary particles of LiFeo.98Mgo.oiAlo.aiPO4 adhered with carbon particles.
Example H
In this2xample,the powdered cathode materiaJ.includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner sinilar to that of Example b, except that the reactant solution was dried to from particulate precursors. The particulate precursors were placed in the aluminum oxide crucible, and the crucible was then placed in the tubular furnace for conducting crystallization of the LiFePO,-based metal compound of the particulate precursors to form crystalline nanometer-sized primary particJ.es. The tubular furnace was heated to 600 C at a rate of 5 C /min and was maintained at this temperature for 4 hours. The tubular furnace was then cooled to room temperature. The crystalline nanometer-sized primary particles were mixed with and dispersed in 2 wt% of polyvinylene alcohol solution (in a solid-to-liquid ratio of 40:60) in a ball mill for three hours of granulation process to form a slurry. The slurry was spray-dried to form micrometer-sized secondary particles. The micrometer-s%zed secondary_particJ.es were then placed in the aluminum oxide crucible in which charcoal was placed.
The crucible was heated at 800 C for 8 hours in the presence of a nitrogen carrier gas flowing into the furnace. Carbon particles formed from the charcoal were suspended in the nitrogen carrier gas and were mixed with the micrometer-sized secondary particles so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondary particles. The furnace was then cooled to room temperature. A powdered cathode material having one of olivine and NASICON
structures and including micrometer-sized secondary particles having a particle size ranging from 1 to 50 u m was obtained. Particularly, each of the micrometer-sized secondary particles is composed of crystalline nanometer-sized primary particles of the LiFeF04--based metal compound that have a particle size ranging from 10 to 500 nm and that have carbon particles adhered to surfaces thereof, and is formed by sintering of contacted portions of the surfaces of adjacent ones of the crystalline nanometer-sized primary particles.
Results of Evaluation Tests Diameter analysis Figs. 1 and 2 show SEM photographs of the powdered cathode material obtained from Example 0 under observation using a scanning electron microscope at magnifzcation ratios of 5000 times and 10000 times, respectively. From the results shown in Figs. 1 and 2, the powdered cathode material obtained from Example D includes the micrometer-sized secondary particles having a particle size larger than 10gm, each of which is composed of the crystalline nanometer-sized primary particles having a particle size ranging from 50 to 100 nm.
Subsequently, 10 g of the powdered cathode material obtained from Example D was placed in the particle size distribution analyzer to evaluate particle size distribution of the mzcrometer-si.zed secondary particles.
From results shown in Fig. 3, 10%, 20%, 30%, 50%, 80%, and 90% of cumulative volumetric diameters of the powdered cathode material of Example D are respectively at about 33.7,um, 27.6,um, 23.8ttm, 18.3gm, ll;um and 7.0,um. From the value of 50% of cumulative volumetric diameter, it is inferred that the particles included in the cathode material are micro-scale. In addition, since only one peak is shown in the plot of Fig. 3, this indicates that particle size distribution of the micrometer-sized secondary particles of Example D is uniform.
Fig. 4 shows a SEM photograph of the powdered cathode material obtained from Example H under observation using a scanning electron microscope at a magnification ratio of 5000 times. From the result shown in Fig. 4, whxch is similar to that of Fig. 1, the powdered cathode material obtained from Example H includes the micrometer-sized secondary particles having a particle size larger than 10 ,C m, each of which is composed of the crystalline nanometer-sized primary particles havzng a particle size ranging from 50 to 100 nm.
Specific surface area analysis The BET (Brunauer-Emmett-Teller) specific surface area of the powdered cathode matexial of Example E at 77K was calculated from nitrogen isothermal absorption/ desorption curve, and has a value of 38.42 m2/g. Similarly, the value of the BET specific surface area of the powdered cathode material of Example H is about 39 m2/g. The conventional cathode material described in the '566 patent in the background part has a BET specific surfaee area of about 2. 5 m2/g. Apparently, the cathode material of this invention has a much higher BET specific surface area.
Char e/discharge test The powdered cathode material obtained f rom respective Examples F, G and H was evenly mixed with carbon black and I
polyvinylidene fluoride in a weight ratio of 83:10:7 to form a slurry mixture. The slurry mixture was then coated on an aluminum foil and was dx'ied to produce a cathode specimen.
The cathode specimen was combined with lithium metal to form a 2032 type button rechargeable battery.
Charge/discharge tests were performed on the button rechargeable battery thus formed with a Maccor Series 4000 Automated Test System (Maccor Inc., Tulsa, Oklahoma, U.S.A.).
The applied charge/discharge voltage ranged from 2.8 v to 4. 0 v, and the charge/discharge rate was set to 0. 2C. Results of the chaxge/discharge test are shown in Figs. 5, 6 and 7.
From the result shown in Fig. 5, the initial specific capacity of the cathode made from the powdered cathode material of Example F can reach 152 mAh/g, and such specific capacity can be maintained at 100% after ten charge/discharge cycles. From the result shown in Fig. 6, the initial specific capacity of the charge curve of the cathode made from the powdered cathode material of Example G can reach 167 mAh/g, which approximates the theoretical specific capacity of lithium ferrous phosphate compounds, i.e., 170 mAh/g. In addita.on, from the result shown in Fig.
7, the specific capacity of the charge curve of the cathode made from the powdered cathode material of Example H can reach 162 mAh/g.
Charege/discharge test of a whole battery The powdered cathode material obtained from Example F was mixed with different solvents and binders and then coated on electrode plates to form batteries. Each of the batteries was tested at different charge/discharge rates to evaluate the electrical property.
5 Battery 1 The powdered cathode material obtained from Example E'was mixed with polyvinylidenefluoride and carbon powders in a weight ratio of 85:12:3 in N-methyl-pyrroJ.idone (NMP) solvent to form a mixture having a viscosity of 4000 mPa. s.
10 Then, the mixture was coated on an aluminum electrode plate and dried at 100 C. The dried aluminum electrode plate has a thickness of 132 um, and the powdered cathode material coated on the aluminum electrode plate was not peeled therefrom. The electrode plate was then cut and assembled 15 with a carbon anode and an electrolyte solution containing 1 mol/l of LiPF6 in 5 g of ethylene carbonate/diethyl carbonate (EC/DEC) to form a prismatic battery.
Chaxge/discharge tests were performed on the prismatic battery at various charge/dischargerates,i.e.,0.2C,0.5C, 20 1C, 2C, 3C and SC, using a Maccor Series 4000 Automated Test System (Maccor Inc. , Tulsa, Oklahoma, U. S.A. ). _Tn Fig.
8, curves 1, 2, 3, 4,5 and 6 respectively correspond to voltage to capacity relationship of the battery 1 at charge/discharge rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C.
Fzom the results shown in Fig. 8, it is noted that the battery 1 can be efficiently charged and discharged at different charge/discharge rates. Particularly, the capacity of discharge at a charge/discharge rate of SCis approximately 87% of that of discharge at a charge/discharge rate of 0.2C.
The results shown in Fig. 8 demonstrate that the powdered cathode material of this invention can be easily coated on and adhered to the electrode plate so as to achieve high charge/discharge rates.
Battery 2 The powdered cathode material obtained from Example F was mixed with styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), and carbon powders in a weight ratio of 95:1.5:0.5:3 in deionized water to form a mixture having a viscosity of 4000 mPa . s. Then, themixture was coated on an aluminum electrode plate and dried at 80 'C . The dried aluminum electrode plate has a thickness of 200 gm, and the powdered cathode material coated on the aluminum electrode plate was not peeled therefrom. The electrode plate was then cut and assembled with a carbon anode and an electrolyte solution containing 1 mol/]. of LiPF6in 5 g ofethylene carbonate/diethyl.carbonate(EC/DEC) to form a 18650 battery. Charge/discharge tests were performed on the 18650 battery at various charge/discharge rates, i. e. , 0. 5C, 1C, 2C, 5C and 8C, using a Maccor Series 3200,Automated Test System (Maccor Inc., Tulsa, Oklahoma, U.S.A.). In Fig. 9, curves 1, 2, 3, 4,and 5 respectively correspond to voltage to capacity relationship of the battery 2 at charge/discharge rates of 0.5C, 1C, 2C, 5C, and 8C. From the results shown in Fig. 9, it is noted that 22 ' the battery 2 can be efficiently charged and discharged at different charge/discharge rates. Particularly, the capacity of discharge at a charge/discharge rate of 8C is approximately 90% of that of di.scharge at a charge/discharge rate of 0.5C.
In view of the foregoing, compared with the conventional cathode material, the cathode material.of this invention, which includes micrometer-sized secondary particles having a particle size ranging from 1 to 50 gm, each of which is composed of crystalline nanometer-sized primary particles of a metal compound, has an improved specific surface area and capacity.
In addition, the cathode material of this invention is compatible with various binders, particularly aqueous binders, and aqueous solvents, particularly deionized water, and canbe easily coated on and firmly adhered to the electrode plate.
while the present invention has been described in connection with what is considered the most practical and preferred embodiments, itisunderstood that this invention is not limxted to the disclosed embodiments but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation and equivalent arrangements.
Fig. 4 shows a SEM photograph to illustrate surface morphology of micrometer-sized secondary particles included in the cathode materi.al prepared according to Example H of the present invention;
Fig. 5 shows a specific capacity versus cycle number plot of a cathode coated with a coating of a cathode material obtained from Example F of the present invention;
Eig. 6 is a voltage versus specific capacity plot for a cathode coated with a coating of a cathode material obtained from Example G of this invention;
Fig. 7 is a voltage versus specific capacity plot for a cathode coatedwith a coating of a cathodematerial obtained from Example H of this invention;
Fig. 8 is a voltage versus capacity plot for a cathode rechargeable battery with a cathode coated with a coating of a cathode material obtained from Example F of this invention at different charge/discharge rates;
Fig. 9 is a voltage versus capacity plot for cathode rechargeable batteries, each of which has a cathode coated with a coating of a mixture of a cathode material obtained from Example F of this invention and one of various binders;
and Fig. 10 is a schematic sectional view to illustrate structure of a cathode for a rechargeable battery according to this invention.
DETAILED DESCRIPTION OF THE PREFERRED II+BODIIMENTS
The preferred embodiment of a cathode materialaccording to this invention includes crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 ,u m. Each of 10 the micrometer-sized secondary particles is composed of the crystalline nanometer-sized primary particles.
Preferably, each of the micrometer-sized secondary particles is formed by sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles. More preferably, the cathode material of this invention further includes a carbonaceouscomponent.
Most preferably, the cathode material of this invention fuxther includes carbon particles adhered to the surfaces of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondary particles. In addition, the cathode material of this invention is preferred to have a BET specific surface area ranging from 5 to 100 m2/g.
Preferably, the metal compound has a formula of A3xM2y (P04) 3, in which A represents at least one first metal element selected from the group consisting of Groups IA, IIA and IIIA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and ITIA,, transition elements, and mixtures thereof; and 0<xi5l.2, 0<y,<,,1, 6.
More preferably, the at least one first metal element is selected from the group consista.ng of Li, Na, K, Be, Mg, 8, Al, andmi.xtures thereof, and the at least one second metal element is selected from the group consisting of Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, X, Zr, Nb, Mo, Be, Mg, Ca, Sr, B, Al, Ge, Sn, Ga, and mixtures thereof.
The abovementioned cathode material according to this invention may be manufactured by a method involving formation of particulate precursors of the metal compound followed by crystallization of the metal compound of the particulate precursors to form the crystalline nanometer-sized primary particles and sintering of the crystalline nanometer-sized primary particles.
l'articulazly,the methodincludes:preparing a reactant solution including the metal compound, the metal compound having a formula of A3xM2y(PO4)3i in which A xepresents at least one first metal element selected from the group consisting of Groups IA, IIA and I IIA, and mixtures thereof, M represents at least one second meta], element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof, and 0<x =1.2, OEy _-:S1.6;
drying the reactantsolution to form particulate precursors of the metal compound; and heating the particulate precursors under a non-oxidizing atmosphere in the presence 9 ' of suspended carbon particles so as to crystallize the metal compound of each of the particulate precursors to form the crystalline nanometer-sized primary particles and so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles to form each of the micrometer-sized secondary particles.
Drying operation of the reactant solution may be conducted through dehydration, ultrasonic spray-drying, spray-drying, freeze-drying, vacuum-drying, filtering, or spray pyrolysis techniques.
Heating operation of the particulate precursors is preferably conducted at a temperature ranging from 400 to 900 C for 6 to 48 hours.
Alternatively, the abovementioned cathode material according to this invention may be manufactured by a method involving heating of particulate precursors to form the crystalline nanometer-sized primary particles, subsequently granulating the crystalline nanometer-sized primary particles to form the micrometer-sized secondary particles, and followed by sintering of the crystalline nanomater-sized primary particles of each of the micrometer-sized secondary particles.
Particularly, the alternative method includes:
preparing a reactantsolutionincluding the metal compound, the metal compound having a formula of A3xM2y (POy) 3, in which A represents at least one first metal element selected from the group consisting of Groups IA, I IA and IIxA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof; and 0<x ~1.2, 5 0<y='S 1. 6; drying the reactant solution to form particulate precursors of the metal compound; heating the particulate precursoxs in the presence of suspended carbon particles so as to crystallize the metal compound of each of the particulate precursors to form the crystalline 10 nanometer-sized primary particles; granulating the crystalline nanometer-sized primary particles into micrometer-sized secondary particles; and heating the granulated micrometer-sized secondary particles under a non-oxidizing atmosphere in the presence of suspended carbon particles so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondaryparticles.
Preferably, the heating operation of the particulate precursors is conducted at a temperatvre ranging from 550 'G to 600 C for 2 to 24 hours. Preferably, heating operation of the granulated micrometer-sized secondary particles is conducted at a temperature ranging from 400 to 900'C for 6 to 48 hours.
In addition, during manufacture of the preferred embodiment of the cathode material of this invention according to the abovementioned methods, a carbonaceous I. ,.
component is optionally added into the reactant solution prior to the drying operation of the reactant solution_ The carbonaCeous component is one of an organic acid selected from the group consisting of citric acid, oxalic acid, tartaric acid, lactic acid, terephthalic acid, ethylenediaminetetraacetic acid, and acetic acid; a carbohydrate selected from the group consisting of sucrose, lactose, glucose, andoligose; and carbon powders madefrom a material selected from the group consisting of acetylene carbon black, carbon black, mesophase carbon micro beads (MCMS), supper P and graphite.
Referring to P'ig. 10, the preferred embodiment of a cathode for a rechargeable battery according to this invention includes an electrode plate 1, and a coating 2 of the abovementioned cathode material of this invention coated on the electrode plate 1.
Preferably, the cathode material further includes an aqueous binder, in addition to an aqueous solvent. More preferably, the aqueous binder is styrene-butadiene rubber (SHR). More preferably, the aqueous solvent is deionized wat(ar.
Alternatively, the cathode material may further include a non-aqueous binder. Preferably, the non-aqueous binder is po].yvinylidene fluoride (PVDF). Preferably, the non-aqueous solvent is N-methyl-pyrrolidone (NMP).
Preferably, the cathode material may further include a thickener. More pref erably, the thickener is carboxymethyl r cellulose (CMC).
In addition, the preferred embodiment of the cathode thus made may be combined with an anode and an electrolyte to form the rechargeable battery.
Example Analytical Eauipment 1. Scanning Electron Microscope (SEM): Hitachi model S-3500V.
2. Paxticle size distribution analyzer: Horiba, LA-910.
3. Charge/discharge cycle tester: Maccor Series 4000 and 3200 Automated Test Systems (Maccor Inc., Tulsa, Oklahoma, U.S.A) 4. Accelerated surface and porosimetry system: ASAP 2010 (Micromeritics, U.S.A.) Example A
0.2 mole of ferric nitrate (Fe(NO3)3) was added into 200 ml of deionized watex. After Fe(N03)3 was completely dissolved in the deionized water, 0.2 moles of phosphoric acid and 100 ml of 2N lithium hydroxide (LiOH) solution were added in sequence, so as to form a mixture having a stoichiometric ratio 1- 1: 1 of Fe3+: T~i+: POq3+. 100 znl of 0.252 g oxalic acid solution was added to the mixture having Fe3+, Li+, and PO93+ ions. The reactant solution thus formed was dried to form particulate precursors of LiFePO4-based metal compound.
Alext, the particulate precursors were placed in an aluminumoxide cx'ueible.The crucible together with charcoal was placed in a tubul.ar furnace which was heated at 700 C for 12 hours in the presence of an argon carrier gas flowing into the furnace. Carbon particles formed from the charcoal were suspended in the argon carrier gas and were mixed with the micro-particulate precursors, thereby crystallizing the metal compound of each of the particulate precursors to form the crystalline nanometer-szzed primary particles and causing sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles to form each of the micrometer-sized secondary particles. A cathode material having one of olivine and NASIC4N structures and including micrometer-sized secondary particles having a particle size ranging from 1 to 50 g m was obtained. Particularly, each of the micrometer-sized secondary particles is composed of crystalline nanometer-sized primary particles of the LiFePOg-based metal compound that have a particle size ranging from 10 to 500 nm and that have carbon particles adhered to surfaces thereof, and is formed by sintering of contacted portions of the surfaces of adjacent ones of the crystalline nanometer-sized primary particles.
Example B
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles, was prepared in a manner similar to that of Example A, except that 0.2 mole of Fe (NO3) 3 was replaced with 0.2 mole of ferric chloride (FeC13) Example C
In this example, the powdered cathode material incJ.udes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example A, except that 0. 2 mole of Fe (N03) 3 was replaced with 0.2 mole of iron (Fe) powders.
Example D
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example C, except that 100 ml of 0. 252g oxal ic acid solution was replaced wi'th 100 ml of 0.42 g citric acid solution.
Example E
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example D, except that 0.1 g of glucose was added to the reactant solution after the addition of the citric acid solution.
Example F
In this example, the powdered cathode material includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that of Example 0, except that 0.1 g of sucrose was added to the reactant solution after the addition of the citric acid solution.
5 Example G
zn this example, the powdered cathode material inclvdes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner similar to that 10 of Example D, except that 0.2 mole of the iron powders were replaced with a mixture of 0.196 mole of iron powders, 0. 002 mole of magnesiumchloride (MgC12) , and 0. 002 mo1.e of aluminum chloride (AlC13). The powdered cathode mate.rial includes micrometer-sized secondary particles, each of which is 15 composed of nanometer-sized primary particles of LiFeo.98Mgo.oiAlo.aiPO4 adhered with carbon particles.
Example H
In this2xample,the powdered cathode materiaJ.includes micrometer-sized secondary particles, each of which is composed of nanometer-sized primary particles adhered with carbon particles, was prepared in a manner sinilar to that of Example b, except that the reactant solution was dried to from particulate precursors. The particulate precursors were placed in the aluminum oxide crucible, and the crucible was then placed in the tubular furnace for conducting crystallization of the LiFePO,-based metal compound of the particulate precursors to form crystalline nanometer-sized primary particJ.es. The tubular furnace was heated to 600 C at a rate of 5 C /min and was maintained at this temperature for 4 hours. The tubular furnace was then cooled to room temperature. The crystalline nanometer-sized primary particles were mixed with and dispersed in 2 wt% of polyvinylene alcohol solution (in a solid-to-liquid ratio of 40:60) in a ball mill for three hours of granulation process to form a slurry. The slurry was spray-dried to form micrometer-sized secondary particles. The micrometer-s%zed secondary_particJ.es were then placed in the aluminum oxide crucible in which charcoal was placed.
The crucible was heated at 800 C for 8 hours in the presence of a nitrogen carrier gas flowing into the furnace. Carbon particles formed from the charcoal were suspended in the nitrogen carrier gas and were mixed with the micrometer-sized secondary particles so as to cause sintering of contacted portions of surfaces of adjacent ones of the crystalline nanometer-sized primary particles of each of the micrometer-sized secondary particles. The furnace was then cooled to room temperature. A powdered cathode material having one of olivine and NASICON
structures and including micrometer-sized secondary particles having a particle size ranging from 1 to 50 u m was obtained. Particularly, each of the micrometer-sized secondary particles is composed of crystalline nanometer-sized primary particles of the LiFeF04--based metal compound that have a particle size ranging from 10 to 500 nm and that have carbon particles adhered to surfaces thereof, and is formed by sintering of contacted portions of the surfaces of adjacent ones of the crystalline nanometer-sized primary particles.
Results of Evaluation Tests Diameter analysis Figs. 1 and 2 show SEM photographs of the powdered cathode material obtained from Example 0 under observation using a scanning electron microscope at magnifzcation ratios of 5000 times and 10000 times, respectively. From the results shown in Figs. 1 and 2, the powdered cathode material obtained from Example D includes the micrometer-sized secondary particles having a particle size larger than 10gm, each of which is composed of the crystalline nanometer-sized primary particles having a particle size ranging from 50 to 100 nm.
Subsequently, 10 g of the powdered cathode material obtained from Example D was placed in the particle size distribution analyzer to evaluate particle size distribution of the mzcrometer-si.zed secondary particles.
From results shown in Fig. 3, 10%, 20%, 30%, 50%, 80%, and 90% of cumulative volumetric diameters of the powdered cathode material of Example D are respectively at about 33.7,um, 27.6,um, 23.8ttm, 18.3gm, ll;um and 7.0,um. From the value of 50% of cumulative volumetric diameter, it is inferred that the particles included in the cathode material are micro-scale. In addition, since only one peak is shown in the plot of Fig. 3, this indicates that particle size distribution of the micrometer-sized secondary particles of Example D is uniform.
Fig. 4 shows a SEM photograph of the powdered cathode material obtained from Example H under observation using a scanning electron microscope at a magnification ratio of 5000 times. From the result shown in Fig. 4, whxch is similar to that of Fig. 1, the powdered cathode material obtained from Example H includes the micrometer-sized secondary particles having a particle size larger than 10 ,C m, each of which is composed of the crystalline nanometer-sized primary particles havzng a particle size ranging from 50 to 100 nm.
Specific surface area analysis The BET (Brunauer-Emmett-Teller) specific surface area of the powdered cathode matexial of Example E at 77K was calculated from nitrogen isothermal absorption/ desorption curve, and has a value of 38.42 m2/g. Similarly, the value of the BET specific surface area of the powdered cathode material of Example H is about 39 m2/g. The conventional cathode material described in the '566 patent in the background part has a BET specific surfaee area of about 2. 5 m2/g. Apparently, the cathode material of this invention has a much higher BET specific surface area.
Char e/discharge test The powdered cathode material obtained f rom respective Examples F, G and H was evenly mixed with carbon black and I
polyvinylidene fluoride in a weight ratio of 83:10:7 to form a slurry mixture. The slurry mixture was then coated on an aluminum foil and was dx'ied to produce a cathode specimen.
The cathode specimen was combined with lithium metal to form a 2032 type button rechargeable battery.
Charge/discharge tests were performed on the button rechargeable battery thus formed with a Maccor Series 4000 Automated Test System (Maccor Inc., Tulsa, Oklahoma, U.S.A.).
The applied charge/discharge voltage ranged from 2.8 v to 4. 0 v, and the charge/discharge rate was set to 0. 2C. Results of the chaxge/discharge test are shown in Figs. 5, 6 and 7.
From the result shown in Fig. 5, the initial specific capacity of the cathode made from the powdered cathode material of Example F can reach 152 mAh/g, and such specific capacity can be maintained at 100% after ten charge/discharge cycles. From the result shown in Fig. 6, the initial specific capacity of the charge curve of the cathode made from the powdered cathode material of Example G can reach 167 mAh/g, which approximates the theoretical specific capacity of lithium ferrous phosphate compounds, i.e., 170 mAh/g. In addita.on, from the result shown in Fig.
7, the specific capacity of the charge curve of the cathode made from the powdered cathode material of Example H can reach 162 mAh/g.
Charege/discharge test of a whole battery The powdered cathode material obtained from Example F was mixed with different solvents and binders and then coated on electrode plates to form batteries. Each of the batteries was tested at different charge/discharge rates to evaluate the electrical property.
5 Battery 1 The powdered cathode material obtained from Example E'was mixed with polyvinylidenefluoride and carbon powders in a weight ratio of 85:12:3 in N-methyl-pyrroJ.idone (NMP) solvent to form a mixture having a viscosity of 4000 mPa. s.
10 Then, the mixture was coated on an aluminum electrode plate and dried at 100 C. The dried aluminum electrode plate has a thickness of 132 um, and the powdered cathode material coated on the aluminum electrode plate was not peeled therefrom. The electrode plate was then cut and assembled 15 with a carbon anode and an electrolyte solution containing 1 mol/l of LiPF6 in 5 g of ethylene carbonate/diethyl carbonate (EC/DEC) to form a prismatic battery.
Chaxge/discharge tests were performed on the prismatic battery at various charge/dischargerates,i.e.,0.2C,0.5C, 20 1C, 2C, 3C and SC, using a Maccor Series 4000 Automated Test System (Maccor Inc. , Tulsa, Oklahoma, U. S.A. ). _Tn Fig.
8, curves 1, 2, 3, 4,5 and 6 respectively correspond to voltage to capacity relationship of the battery 1 at charge/discharge rates of 0.2C, 0.5C, 1C, 2C, 3C and 5C.
Fzom the results shown in Fig. 8, it is noted that the battery 1 can be efficiently charged and discharged at different charge/discharge rates. Particularly, the capacity of discharge at a charge/discharge rate of SCis approximately 87% of that of discharge at a charge/discharge rate of 0.2C.
The results shown in Fig. 8 demonstrate that the powdered cathode material of this invention can be easily coated on and adhered to the electrode plate so as to achieve high charge/discharge rates.
Battery 2 The powdered cathode material obtained from Example F was mixed with styrene-butadiene rubber (SBR), carboxymethyl cellulose (CMC), and carbon powders in a weight ratio of 95:1.5:0.5:3 in deionized water to form a mixture having a viscosity of 4000 mPa . s. Then, themixture was coated on an aluminum electrode plate and dried at 80 'C . The dried aluminum electrode plate has a thickness of 200 gm, and the powdered cathode material coated on the aluminum electrode plate was not peeled therefrom. The electrode plate was then cut and assembled with a carbon anode and an electrolyte solution containing 1 mol/]. of LiPF6in 5 g ofethylene carbonate/diethyl.carbonate(EC/DEC) to form a 18650 battery. Charge/discharge tests were performed on the 18650 battery at various charge/discharge rates, i. e. , 0. 5C, 1C, 2C, 5C and 8C, using a Maccor Series 3200,Automated Test System (Maccor Inc., Tulsa, Oklahoma, U.S.A.). In Fig. 9, curves 1, 2, 3, 4,and 5 respectively correspond to voltage to capacity relationship of the battery 2 at charge/discharge rates of 0.5C, 1C, 2C, 5C, and 8C. From the results shown in Fig. 9, it is noted that 22 ' the battery 2 can be efficiently charged and discharged at different charge/discharge rates. Particularly, the capacity of discharge at a charge/discharge rate of 8C is approximately 90% of that of di.scharge at a charge/discharge rate of 0.5C.
In view of the foregoing, compared with the conventional cathode material, the cathode material.of this invention, which includes micrometer-sized secondary particles having a particle size ranging from 1 to 50 gm, each of which is composed of crystalline nanometer-sized primary particles of a metal compound, has an improved specific surface area and capacity.
In addition, the cathode material of this invention is compatible with various binders, particularly aqueous binders, and aqueous solvents, particularly deionized water, and canbe easily coated on and firmly adhered to the electrode plate.
while the present invention has been described in connection with what is considered the most practical and preferred embodiments, itisunderstood that this invention is not limxted to the disclosed embodiments but is intended to cover various arrangements included within the spirit and scope of the broadest interpretation and equivalent arrangements.
Claims (14)
1. A cathode material, comprising crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 µm, each of said micrometer-sized secondary particles being composed of parts of said crystalline nanometer-sized primary particles, and parts of said crystalline nanometer-sized primary particles being individually present in the cathode material, wherein said crystalline nanometer-sized primary particles have carbon particles adhered to surfaces thereof, and said metal compound has a formula of A3x M2y(PO4)3, in which A represents at least one first metal element selected from the group consisting of Groups IA, IIA and IIIA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof; and 0 < x <= 1.2, 0 < y <= 1.6.
2. The cathode material of claim 1, wherein said cathode material has a BET specific surface area ranging from 5 to 100 m2/g.
3. The cathode material of claim 1, further comprising a carbonaceous component.
4. The cathode material of claim 1, wherein the at least one first metal element is selected from the group consisting of Li, Na, K, Be, Mg, B, Al, and mixtures thereof, and the at least one second metal element is 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, Ge, Sn, Ga, and mixtures thereof.
5. A cathode for a rechargeable battery, comprising an electrode plate and a coating of a cathode material coated on said electrode plate, wherein said cathode material comprises crystalline nanometer-sized primary particles of a metal compound having one of olivine and NASICON structures and a particle size ranging from 10 to 500 nm, and micrometer-sized secondary particles having a particle size ranging from 1 to 50 µm, each of said micrometer-sized secondary particles being composed of parts of said crystalline nanometer-sized primary particles, and parts of said crystalline nanometer-sized primary particles being individually present in the cathode material, wherein said crystalline nanometer-sized primary particles have carbon particles adhered to surfaces thereof, and said metal compound has a formula of A3x M2y(PO4)3, in which A represents at least one first metal element selected from the group consisting of Groups IA, IIA and IIIA, and mixtures thereof; M represents at least one second metal element selected from the group consisting of Groups IIA and IIIA, transition elements, and mixtures thereof; and 0 < x <= 1.2, 0 < y <= 1.6.
6. The cathode of claim 5, wherein said cathode material further comprises a carbonaceous component.
7. The cathode of claim 5, wherein the at least one first metal element is selected from the group consisting of Li, Na, K, Be, Mg, B, Al, and mixtures thereof, and the at least one second metal element is 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, Ge, Sn, Ga, and mixtures thereof.
8. The cathode of claim 5, wherein said cathode material has a BET
specific surface area ranging from 5 to 100 m2/g.
specific surface area ranging from 5 to 100 m2/g.
9. The cathode of claim 5, wherein said cathode material further comprises an aqueous binder.
10. The cathode of claim 9, wherein said aqueous binder is styrene-butadiene rubber (SBR).
11. The cathode of claim 5, wherein said cathode material further includes a thickener.
12. The cathode of claim 11, wherein said thickener is carboxymethyl cellulose (CMC).
13. The cathode of claim 5, wherein said cathode material further comprises a non-aqueous binder.
14. The cathode of claim 13, wherein said non-aqueous binder is selected from the group consisting of polyvinylidene fluoride (PVDF) and N-methyl-pyrrolidone (NMP).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100749646A CN100563047C (en) | 2006-04-25 | 2006-04-25 | Composite material suitable for manufacturing anode of secondary battery and battery manufactured by composite material |
| CN200610074964.6 | 2006-04-25 |
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| CA2585594A1 CA2585594A1 (en) | 2007-10-25 |
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| JP (1) | JP5039423B2 (en) |
| KR (1) | KR100809570B1 (en) |
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| CN100563047C (en) | 2009-11-25 |
| JP2007294461A (en) | 2007-11-08 |
| CA2585594A1 (en) | 2007-10-25 |
| JP5039423B2 (en) | 2012-10-03 |
| KR20070105266A (en) | 2007-10-30 |
| KR100809570B1 (en) | 2008-03-04 |
| EP1850409A1 (en) | 2007-10-31 |
| HK1109679A1 (en) | 2008-06-13 |
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