CA2972567C - Preparation method of battery composite material and precursor thereof - Google Patents
Preparation method of battery composite material and precursor thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/377—Phosphates of heavy metals of manganese
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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
- H01M4/04—Processes of manufacture in general
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
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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
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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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
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
A preparation method of battery composite material includes steps of providing a manganese-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water;
processing a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water to produce a first product; placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4; and processing a reaction of at least the first precursor, the lithium-contained compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce battery composite material.
Therefore, the preparation time is shortened, the energy consuming is reduced, the phase forming of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
processing a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water to produce a first product; placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4; and processing a reaction of at least the first precursor, the lithium-contained compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce battery composite material.
Therefore, the preparation time is shortened, the energy consuming is reduced, the phase forming of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
Description
PREPARATION ME IOD OF BATTERY COMPOSITE MATERIAL
AND PRECURSOR THEREOF
[0001]
FIELD OF THE INVENTION
AND PRECURSOR THEREOF
[0001]
FIELD OF THE INVENTION
[0002] The present invention relates to a preparation method, and more particularly to a preparation method of battery composite material and a precursor thereof BACKGROUND OF THE INVENTION
]0003] With the rapid development of global economy, the exhaustion of resources increases day by days. Recently, the concept of environmental protection becomes much more important. In order to overcome the problems of energy shortages and also focus on the sustainable management at the same time, looking for eco-friendly, clean and effective alternative energies has become an important development direction in the industry. Among varieties of alternative energies, the research and development of chemical battery is actively invested by related industries, such that the technology of battery preparation is improved, and the battery efficiency is enhanced. Furthermore, the chemical batteries are also widely used in our daily life, such as consuming electronics, medical equipment, electric bicycles, electric motorcycles, electric cars and electric buses.
[0004] In kinds of chemical batteries, lithium batteries are widely accepted in the market and become popular because of its characteristics of high energy density, no memory effect, long cycle life and non-pollution. In addition, the batteries applying lithium manganese phosphate (LiMnPO4) as the cathode material have higher energy density, higher charging and discharging capacity, stability and safety, and advantages of rich source of raw materials and lower price, so the lithium manganese phosphate has become a cathode material of lithium batteries with high potential in development.
100051 However, in the conventional preparation methods of lithium manganese phosphate, hydrothermal method and organic solution method are usually adopted, in which steps are more complicated. Furthermore, the preparation temperatures and the energy consumption are high in those methods, and the phase of manganese lithium phosphate is also unstable. In addition, the manganese lithium phosphate is often deemed as reactants of transition state.
100061 Therefore, there is a need of providing a preparation method of a battery composite material and a precursor thereof to solve the drawbacks in prior arts, simplify the steps of the preparation, reduce the energy consumption, and achieve the advantages of making the phase of manganese lithium phosphate stable.
SUMMARY OF THE INVENTION
100071 It is an object of the present invention to provide a preparation method of a battery composite material and a precursor thereof in order to solve the drawbacks of prior art.
100081 The present invention provides a preparation method of a battery composite material and a precursor thereof. Through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material. The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
100091 The present invention also provides a preparation method of a battery composite material and a precursor thereof By producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
[0010j In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by TI3PO4; (b) processing a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water to produce a first product; (c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(111)04)2(PO4)2(H20)4; and (d) processing a reaction of at least the first precursor, the lithium-contained compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material.
100111 In accordance with an aspect of the present invention, there is provided a preparation method of a precursor of a battery composite material. The preparation method of a precursor of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, phosphoric acid, and deionized water, wherein the chemical formula of the phosphoric acid is written by 1-131)04; (b) processing a
]0003] With the rapid development of global economy, the exhaustion of resources increases day by days. Recently, the concept of environmental protection becomes much more important. In order to overcome the problems of energy shortages and also focus on the sustainable management at the same time, looking for eco-friendly, clean and effective alternative energies has become an important development direction in the industry. Among varieties of alternative energies, the research and development of chemical battery is actively invested by related industries, such that the technology of battery preparation is improved, and the battery efficiency is enhanced. Furthermore, the chemical batteries are also widely used in our daily life, such as consuming electronics, medical equipment, electric bicycles, electric motorcycles, electric cars and electric buses.
[0004] In kinds of chemical batteries, lithium batteries are widely accepted in the market and become popular because of its characteristics of high energy density, no memory effect, long cycle life and non-pollution. In addition, the batteries applying lithium manganese phosphate (LiMnPO4) as the cathode material have higher energy density, higher charging and discharging capacity, stability and safety, and advantages of rich source of raw materials and lower price, so the lithium manganese phosphate has become a cathode material of lithium batteries with high potential in development.
100051 However, in the conventional preparation methods of lithium manganese phosphate, hydrothermal method and organic solution method are usually adopted, in which steps are more complicated. Furthermore, the preparation temperatures and the energy consumption are high in those methods, and the phase of manganese lithium phosphate is also unstable. In addition, the manganese lithium phosphate is often deemed as reactants of transition state.
100061 Therefore, there is a need of providing a preparation method of a battery composite material and a precursor thereof to solve the drawbacks in prior arts, simplify the steps of the preparation, reduce the energy consumption, and achieve the advantages of making the phase of manganese lithium phosphate stable.
SUMMARY OF THE INVENTION
100071 It is an object of the present invention to provide a preparation method of a battery composite material and a precursor thereof in order to solve the drawbacks of prior art.
100081 The present invention provides a preparation method of a battery composite material and a precursor thereof. Through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material. The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
100091 The present invention also provides a preparation method of a battery composite material and a precursor thereof By producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
[0010j In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by TI3PO4; (b) processing a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water to produce a first product; (c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(111)04)2(PO4)2(H20)4; and (d) processing a reaction of at least the first precursor, the lithium-contained compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material.
100111 In accordance with an aspect of the present invention, there is provided a preparation method of a precursor of a battery composite material. The preparation method of a precursor of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, phosphoric acid, and deionized water, wherein the chemical formula of the phosphoric acid is written by 1-131)04; (b) processing a
3 reaction of the manganese-contained compound, the phosphoric acid, and the deionized water to produce a first product; and (c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(1-1PO4)2(PO4)2(H20)4.
10012] In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of processing a reaction of a precursor, a lithium-contained compound, and deionized water, adding a carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the precursor is written by Mn5(HPO4)2(PO4)2(H20)4, and the chemical formula of the battery composite material is written by LiMnPO4.
[0013] In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, an iron-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by I-L3PO4; (b) processing a reaction of the manganese-contained compound, the iron-contained compound, the phosphoric acid, and a portion of the deionized water to produce a second product; (c) placing the second product at a first temperature for at least a first time period to produce a second precursor, wherein the chemical formula of the second precursor is written by (Mnx, Fe 1-x)s(IIP04)2(PO4)/ (H20)4, and wherein x is larger than 0.5 and less than or equal to I; and (d) processing a reaction of at least the second precursor, the lithium-contained compound, and another portion of the
10012] In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of processing a reaction of a precursor, a lithium-contained compound, and deionized water, adding a carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the precursor is written by Mn5(HPO4)2(PO4)2(H20)4, and the chemical formula of the battery composite material is written by LiMnPO4.
[0013] In accordance with an aspect of the present invention, there is provided a preparation method of a battery composite material. The preparation method of a battery composite material at least comprises steps of: (a) providing a manganese-contained compound, an iron-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by I-L3PO4; (b) processing a reaction of the manganese-contained compound, the iron-contained compound, the phosphoric acid, and a portion of the deionized water to produce a second product; (c) placing the second product at a first temperature for at least a first time period to produce a second precursor, wherein the chemical formula of the second precursor is written by (Mnx, Fe 1-x)s(IIP04)2(PO4)/ (H20)4, and wherein x is larger than 0.5 and less than or equal to I; and (d) processing a reaction of at least the second precursor, the lithium-contained compound, and another portion of the
4 deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the battery composite material is written by LiMn,Fe1_,PO4.
[0014] The above contents of the present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed description and accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 schematically illustrates the flow chart of a preparation method of a battery composite material according to an embodiment of the present invention;
[0016] FIG. 2 schematically illustrates a detailed flow chart of the preparation method of a battery composite material according to an embodiment of the present invention;
[0017] FIG. 3 schematically illustrates the flow chart of a preparation method of a battery composite material according to another embodiment of the present invention;
100181 FIG. 4A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to an embodiment of the present invention;
[0019] FIG. 413 schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to an embodiment of the present invention;
[0020] FIG. 5A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0021] FIG. 5B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0022] FIG. 6A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0023] FIG. 6B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0024] FIG. 7A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0025] FIG. 7B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[00261 FIG. 8A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0027] FIG. 813 schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0028] FIG. 9A schematically illustrates the X-ray diffraction analysis diagram of a battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0029] FIG. 9B schematically illustrates the SEM analysis diagram of a battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0030] FIG. 9C schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0031] FIG. 10A schematically illustrates the X-ray diffraction analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention:
[00321 FIG. 10B schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[00331 FIG. 11A schematically illustrates the X-ray diffraction analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0034] FIG. 11B schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0035] FIG. 12 schematically illustrates a charging and discharging characteristic diagram of a cell battery made of the battery composite material prepared by the preparation method of the battery composite material of the present invention; and [0036] FIG. 13 schematically illustrates a charging and discharging characteristic diagram of another cell battery made of the battery composite material prepared by the preparation method of the battery composite material of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0037] The present invention will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of preferred embodiments of this invention are presented herein for purpose of illustration and description only. It is not intended to be exhaustive or to be limited to the precise form disclosed.
[00381 Please refer to FIG. 1, which schematically illustrates the flow chart of a preparation method of a battery composite material according to an embodiment of the present invention. As shown in FIG.
1, the preparation method of a battery composite material of the present invention comprises steps as follows. Firstly, in a step S100, a manganese-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and cleionizeci water are provided, among which the chemical formula of the phosphoric acid is written by 1-131)04.
In some embodiments, the manganese-contained compound is manganese carbonate (MnCO3), manganese nitrate (Mn(NO3)2), manganese sulfate (MnSO4) or other compound containing manganese-ion. The lithium-contained compound is lithium carbonate (Li2CO3), lithium hydroxide (Li0H), lithium acetate (LiCH3C00) or other compound containing lithium-ion, but not limited herein. Furthermore, the carbon source is a carbohydrate, an organic compound, a polymer or a macromolecule material, but not limited thereto.
[00391 Next, in a step S200, a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water is processed to produce a first product. The step S200 further comprises a step of performing a grinding and dispersing action and a drying action to the first product. The grinding action can be implemented by a ball mill, and the drying action can be implemented by rolling dehydration or spray drying, but not limited herein. In addition, the drying method of rolling dehydration can perform drying action to the first product abundantly and rapidly, so that the productivity of the dried first product produced by rolling dehydration is high.
[0040] Then, in a step S300, the first product is placed at a first temperature for at least a first time period to produce a first precursor, and the chemical formula of the first precursor is written by Mn5(11PO4)2(PO4)2(I170)4. In some embodiments, the first temperature is larger than or equal to 60 C, and less than or equal to 100 C, which means 60 C the first temperature <100 C. The first time period is larger than or equal to 18 hours, that is to say, the first time period 18 hours.
100411 Lastly, in a step 8400, a reaction of at least the first precursor, the lithium-contained compound, and another portion of the &ionized water is processed, then the carbon source is added and then calcined to produce the battery composite material such as lithium manganese phosphate (LiMnPO4).
[00421 In some embodiments, in the step 8400, a reaction of the first precursor, an iron-contained compound, the lithium-contained compound, and another portion of the deionized water can be processed, and the iron-contained compound is heptairon hexaphosphate (Fe7(PO4)6), iron(III) phosphate dihydrate (FePO4 = 2H20) or other compound containing iron-ion. Then, the carbon source is added and then calcined to produce the battery composite material such as lithium iron manganese phosphate, which is written by LiMn,Fe1_,PO4, and x is larger than 0.5 and less than or equal to 1.
100431 That is to say, in the preparation method of battery composite material and a precursor thereof of the present invention, through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material.
The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
Meanwhile, by producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
[0044] Please refer to FIG. 1 and FIG. 2. FIG. 2 schematically illustrates a detailed flow chart of the preparation method of a battery composite material according to an embodiment of the present invention.
As shown in FIG. I and FIG. 2, the detail of the step S400 of the preparation method of a battery composite material comprises steps as follows. In a step S401, a reaction of the first precursor, the lithium-contained compound and a portion of the deionized water is processed, and a dispersant is added. The dispersant can be a nonionic surfactant such as Triton X-100. Next, in a step S402, a grinding action is performed, and the carbon source is added to obtain a first precursor solution. The grinding action can be implemented by a ball mill, but not limited thereto. Then, in a step S403, a spray drying action and a thermal treatment is performed to the first precursor solution to produce the battery composite material such as lithium manganese phosphate (LiMnPO4).
[0045] In the step S403, the spray drying action can be performed by a rotary disk spray dryer, but not limited herein. In addition, the thermal treatment is performed to the spray-dried product at a temperature larger than 600 C for at least 5 hours, such as sintering to phase at 600 C for 5 hours, but not limited thereto.
[0046] Please refer to FIG. 3, which schematically illustrates the flow chart of a preparation method of a battery composite material according to another embodiment of the present invention. As shown in FIG. 3, the preparation method of a battery composite material of the present invention comprises steps as follows. Firstly, in a step S500, a manganese-contained compound, an iron-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water are provided, among which the chemical formula of the phosphoric acid is written by 1-13PO4. In some embodiments, the manganese-contained compound is manganese carbonate (MnCO3), manganese nitrate (Mn(NO3)2), manganese sulfate (MnSO4) or other compound containing manganese-ion. The iron-contained compound is iron(11) acetate (1'e(CI-13C001-1)2), iron(II) oxalate dihydrate (FeC204 =
21-120) or other compound containing iron-ion. The lithium-contained compound is lithium carbonate (Li2CO3), lithium hydroxide (Li0H), lithium acetate (LiCI-13C00) or other compound containing lithium-ion, but not limited herein. Furthermore, the carbon source is a carbohydrate, an organic compound, a polymer or a macromolecule material, but not limited thereto.
[0047] Next, in a step S600, a reaction of the manganese-contained compound, the iron-contained compound, the phosphoric acid, and a portion of the deionized water is processed to produce a second product.
The step S600 further comprises a step of performing a grinding and dispersing action and a drying action to the second product.
[0048] Then, in a step S700, the second product is placed at a first temperature for at least a first time period to produce a second precursor.
The chemical formula of the second precursor is written by (Mn,,Fel.,)5(HPO4)2(PO4)2(i-120)4, and 0.5<x 1. Furthermore, the first temperature 100'C, and the first time period'-' 18 hours.
[0049] Lastly, in a step S800, a reaction of at least the second precursor, the lithium-contained compound, and another portion of the deionized water is processed, then the carbon source is added so as to be calcined for producing the battery composite material. The chemical formula of the battery composite material is written by LiMnje1_xPO4.
100501 The following embodiments are presented herein for purpose of' illustration and description of the preparation method of' the battery composite material and the precursor thereof of the present disclosure.
10051] Embodiment 1 100521 Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (1-131'04) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a first product. Next, the first product is grinded and dispersed by the hall mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(HPO4)2(PO4)2(1420)4.
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 413.
[0053] Ilmbodiment 2 [0054] Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (143PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a first product. Next, the first product is grinded and dispersed by the ball mill, then dried through the rolling dehydration, and placed at the temperature of 60 C to 100 C for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(FIP04)2(PO4)2(1-120)4. The surface exterior is analyzed through SEM. and the SEM analysis diagram is shown as FIG. 413.
[0055] Embodiment 3 [0056] Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (i-131)04) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a First product. Next, the first product is grinded and dispersed by the ball mill, then dried through the spray drying method, and placed at the temperature of 60 C to 100 C for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(FIP04)2(PO4)7(1-1)0)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 4B.
100571 Embodiment 4 100581 Firstly, 894.9 grams of manganese nitrate (Mn(NO3)2), 575.61 grams of phosphoric acid (1131304) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction. Then, the PI-I value is adjusted to 7-8 by ammonia solution (NH4OH), and the solution is precipitated to produce a first product. Next, the first product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 5A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(1-1PO4)2(PO4)2(H20)4. The surface exterior is analyzed through SEM. and the SEM analysis diagram is shown as FIG. 5B.
[0059] Embodiment 5 [0060] Firstly, 754.9 grams of manganese sulfate (MnSO4), 575.61 grams of phosphoric acid (1131304) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction. Then, the Pfl value is adjusted to 7-8 by ammonia solution (NI140I1), and the solution is precipitated to produce a first product.
After filtering, the first product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to I00 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray ditThaction, and the analysis diagram is shown as FIG. 6A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(EIP04)2(PO4)-0120)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 6B.
[00611 Embodiment 6 [0062] Firstly, 402.3 grams of manganese carbonate (MnCO3), 260.9 grams of iron(II) acetate (Fe(CH3C0014)2), 571.61 grams of phosphoric acid (113PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a second product. Next, the second product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 7A. After comparing the diagram with JCPDS card, the compound is confirmed to be (Mn0.7,Fe0.3)5(HPO4)2(PO4)7(H20)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 713.
[0063] Embodiment 7 100641 Firstly, 402.3 grams of manganese carbonate (Mn(703), 269.8 grams of iron(II) oxalate dihydrate (FeC204 = 21+0), 571.61 grams of phosphoric acid (1-13PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a second product. Next, the second product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as NG. 8A. After comparing the diagram with JCPDS card, the compound is confirmed to be (Mn0,7,Fe0.3)5(HPO4)2(PO4)2(H20)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 8B.
100651 Embodiment 8 100661 799.88 grams of the precursor, Mn5(11PO4)2(PO4)2(II,0)4, obtained in the above-mentioned embodiments, 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 9A. After comparing the diagram with JCPDS card, the compound is confirmed to he lithium manganese phosphate (LiMnPO4).
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 913.
[0067] Embodiment 9 10068] 799.88 grams of the precursor, Mns(I IP04)2( PO4)2(1120)4, obtained in the above-mentioned embodiments, 209.7 grams of lithium hydroxide (I ,i0I1), and 2 liters of dcionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 9A. After comparing the diagram with JCPDS card, the compound is confirmed to be lithium manganese phosphate (LiMnPO4).
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 9C.
100691 Embodiment 10 100701 559.92 grams of the precursor, Mn5(11PO4)2(PO4)2(H20)4, obtained in the above-mentioned embodiments, 226.23 grams of heptairon hexaphosphate (Fe7(PO4)6), 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 10A. After comparing the diagram with JCPDS card, the compound is continued to be lithium iron manganese phosphate (LiMn0,7Fe0.3PO4). The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 10B.
[0071] Embodiment 11 [0072] 559.92 grams of the precursor, Mn5(111304)2(1304)2(1120)4, obtained in the above-mentioned embodiments, 226.23 grams of iron(III) phosphate dihydrate (Fe1304 = 21-I,0), 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction.. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 11A. After comparing the diagram with JCPDS card, the compound is confirmed to be lithium iron manganese phosphate (LiMno,7Fe0.3PO4). The surface exterior is analyzed through SEM, and the SEM analysis diagrarn is shown as FIG. 11B.
[0073] Embodiment 12 [0074] The lithium manganese phosphate (LiMnPO4) obtained in the above-mentioned embodiments is mixed with carbon black (Super P) and binder (NVDF+NMP) as the proportion of 8.5:0.5:1, and the weight percentage concentration of the binder is 4%. For example, firstly, 0.5 grams of carbon black (Super P) and 25 grams of binder (NVDF:NMP=40:960) are mixed at 1200 rpm for 10 minutes. Then, 8.5 grams of lithium manganese phosphate (LiMnPO4) is added and mixed for another 10 minutes. Next, the dispersed slurry is coated with thickness of 0.3 mm on an aluminum substrate by a blade coater, and the coated pole piece is put into the oven, dried at 11 0 C for I hour and then taken out. Then, a round pole plate is made with lithium as the negative electrode, and a diameter of the round pole plate is 1.3 cm. Then, lithium hexafluorophosphate (LiPF6) with molarity as 1M, EC and EMC
are mixed as electrolyte, among which the volume ratio of EC and EMC
is 3:7. Lastly, the coated pole piece, the round pole plate and the electrolyte are made into a coin-cell battery. The electric characteristics of charging and discharging are tested and analyzed through a charging and discharging machine. The test and the analysis are performed at 0.1 coulombs for two cycles and 2 coulombs for two cycles. The charging and discharging characteristic diagram is shown as FIG. 12. The cutoff voltage of the coin-cell battery is 2 to 4.5 volts.
10075] Embodiment 13 100761 The lithium iron manganese phosphate (LiMn,Fe1_xPO4) obtained in the above-mentioned embodiments is mixed with carbon black (Super P) and binder (NVDF+NMP) as the proportion of 8.5:0.5:1, and the weight percentage concentration of the binder is 4%. For example, firstly, 0.5 grams of carbon black (Super P) and 25 grams of binder (NVDF:NMP=40:960) are mixed at 1200 rpm for 10 minutes.
Then, 8.5 grams of lithium iron manganese phosphate (LiMn,Fe1PO4) is added and mixed for another 10 minutes. Next, the dispersed slurry is coated with thickness of 0.3 mm on an aluminum substrate by a blade coater, and the coated pole piece is put into the oven, dried at 110 C for 1 hour and then taken out. Then, a round pole plate is made with lithium as the negative electrode, and a diameter of the round pole plate is 1.3 cm.
Then, lithium hexafluorophosphate (LiPF6) with molarity as 1M, EC and EMC are mixed as electrolyte, among which the volume ratio of EC and EMC is 3:7. Lastly, the coated pole piece, the round pole plate and the electrolyte are made into a coin-cell battery. The electric characteristics of charging and discharging are tested and analyzed through a charging and discharging machine. The test and the analysis are performed at 0.1 coulombs for two cycles and 2 coulombs for two cycles. The charging and discharging characteristic diagram is shown as FIG. 13. The cutoff voltage of the coin-cell battery is 2 to 4.5 volts.
100771 From the above description, the present invention provides a preparation method of battery composite material and a precursor thereof Through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material.
The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
Meanwhile, by producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
100781 While the invention has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention needs not be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.
[0014] The above contents of the present invention will become more readily apparent to those ordinarily skilled in the art after reviewing the following detailed description and accompanying drawings, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 schematically illustrates the flow chart of a preparation method of a battery composite material according to an embodiment of the present invention;
[0016] FIG. 2 schematically illustrates a detailed flow chart of the preparation method of a battery composite material according to an embodiment of the present invention;
[0017] FIG. 3 schematically illustrates the flow chart of a preparation method of a battery composite material according to another embodiment of the present invention;
100181 FIG. 4A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to an embodiment of the present invention;
[0019] FIG. 413 schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to an embodiment of the present invention;
[0020] FIG. 5A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0021] FIG. 5B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0022] FIG. 6A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0023] FIG. 6B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0024] FIG. 7A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0025] FIG. 7B schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[00261 FIG. 8A schematically illustrates the X-ray diffraction analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0027] FIG. 813 schematically illustrates the SEM analysis diagram of a precursor prepared by the preparation method according to another embodiment of the present invention;
[0028] FIG. 9A schematically illustrates the X-ray diffraction analysis diagram of a battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0029] FIG. 9B schematically illustrates the SEM analysis diagram of a battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0030] FIG. 9C schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0031] FIG. 10A schematically illustrates the X-ray diffraction analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention:
[00321 FIG. 10B schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[00331 FIG. 11A schematically illustrates the X-ray diffraction analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0034] FIG. 11B schematically illustrates the SEM analysis diagram of another battery composite material prepared by the preparation method of the battery composite material of the present invention;
[0035] FIG. 12 schematically illustrates a charging and discharging characteristic diagram of a cell battery made of the battery composite material prepared by the preparation method of the battery composite material of the present invention; and [0036] FIG. 13 schematically illustrates a charging and discharging characteristic diagram of another cell battery made of the battery composite material prepared by the preparation method of the battery composite material of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0037] The present invention will now be described more specifically with reference to the following embodiments. It is to be noted that the following descriptions of preferred embodiments of this invention are presented herein for purpose of illustration and description only. It is not intended to be exhaustive or to be limited to the precise form disclosed.
[00381 Please refer to FIG. 1, which schematically illustrates the flow chart of a preparation method of a battery composite material according to an embodiment of the present invention. As shown in FIG.
1, the preparation method of a battery composite material of the present invention comprises steps as follows. Firstly, in a step S100, a manganese-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and cleionizeci water are provided, among which the chemical formula of the phosphoric acid is written by 1-131)04.
In some embodiments, the manganese-contained compound is manganese carbonate (MnCO3), manganese nitrate (Mn(NO3)2), manganese sulfate (MnSO4) or other compound containing manganese-ion. The lithium-contained compound is lithium carbonate (Li2CO3), lithium hydroxide (Li0H), lithium acetate (LiCH3C00) or other compound containing lithium-ion, but not limited herein. Furthermore, the carbon source is a carbohydrate, an organic compound, a polymer or a macromolecule material, but not limited thereto.
[00391 Next, in a step S200, a reaction of the manganese-contained compound, the phosphoric acid, and a portion of the deionized water is processed to produce a first product. The step S200 further comprises a step of performing a grinding and dispersing action and a drying action to the first product. The grinding action can be implemented by a ball mill, and the drying action can be implemented by rolling dehydration or spray drying, but not limited herein. In addition, the drying method of rolling dehydration can perform drying action to the first product abundantly and rapidly, so that the productivity of the dried first product produced by rolling dehydration is high.
[0040] Then, in a step S300, the first product is placed at a first temperature for at least a first time period to produce a first precursor, and the chemical formula of the first precursor is written by Mn5(11PO4)2(PO4)2(I170)4. In some embodiments, the first temperature is larger than or equal to 60 C, and less than or equal to 100 C, which means 60 C the first temperature <100 C. The first time period is larger than or equal to 18 hours, that is to say, the first time period 18 hours.
100411 Lastly, in a step 8400, a reaction of at least the first precursor, the lithium-contained compound, and another portion of the &ionized water is processed, then the carbon source is added and then calcined to produce the battery composite material such as lithium manganese phosphate (LiMnPO4).
[00421 In some embodiments, in the step 8400, a reaction of the first precursor, an iron-contained compound, the lithium-contained compound, and another portion of the deionized water can be processed, and the iron-contained compound is heptairon hexaphosphate (Fe7(PO4)6), iron(III) phosphate dihydrate (FePO4 = 2H20) or other compound containing iron-ion. Then, the carbon source is added and then calcined to produce the battery composite material such as lithium iron manganese phosphate, which is written by LiMn,Fe1_,PO4, and x is larger than 0.5 and less than or equal to 1.
100431 That is to say, in the preparation method of battery composite material and a precursor thereof of the present invention, through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material.
The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
Meanwhile, by producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
[0044] Please refer to FIG. 1 and FIG. 2. FIG. 2 schematically illustrates a detailed flow chart of the preparation method of a battery composite material according to an embodiment of the present invention.
As shown in FIG. I and FIG. 2, the detail of the step S400 of the preparation method of a battery composite material comprises steps as follows. In a step S401, a reaction of the first precursor, the lithium-contained compound and a portion of the deionized water is processed, and a dispersant is added. The dispersant can be a nonionic surfactant such as Triton X-100. Next, in a step S402, a grinding action is performed, and the carbon source is added to obtain a first precursor solution. The grinding action can be implemented by a ball mill, but not limited thereto. Then, in a step S403, a spray drying action and a thermal treatment is performed to the first precursor solution to produce the battery composite material such as lithium manganese phosphate (LiMnPO4).
[0045] In the step S403, the spray drying action can be performed by a rotary disk spray dryer, but not limited herein. In addition, the thermal treatment is performed to the spray-dried product at a temperature larger than 600 C for at least 5 hours, such as sintering to phase at 600 C for 5 hours, but not limited thereto.
[0046] Please refer to FIG. 3, which schematically illustrates the flow chart of a preparation method of a battery composite material according to another embodiment of the present invention. As shown in FIG. 3, the preparation method of a battery composite material of the present invention comprises steps as follows. Firstly, in a step S500, a manganese-contained compound, an iron-contained compound, phosphoric acid, a lithium-contained compound, a carbon source, and deionized water are provided, among which the chemical formula of the phosphoric acid is written by 1-13PO4. In some embodiments, the manganese-contained compound is manganese carbonate (MnCO3), manganese nitrate (Mn(NO3)2), manganese sulfate (MnSO4) or other compound containing manganese-ion. The iron-contained compound is iron(11) acetate (1'e(CI-13C001-1)2), iron(II) oxalate dihydrate (FeC204 =
21-120) or other compound containing iron-ion. The lithium-contained compound is lithium carbonate (Li2CO3), lithium hydroxide (Li0H), lithium acetate (LiCI-13C00) or other compound containing lithium-ion, but not limited herein. Furthermore, the carbon source is a carbohydrate, an organic compound, a polymer or a macromolecule material, but not limited thereto.
[0047] Next, in a step S600, a reaction of the manganese-contained compound, the iron-contained compound, the phosphoric acid, and a portion of the deionized water is processed to produce a second product.
The step S600 further comprises a step of performing a grinding and dispersing action and a drying action to the second product.
[0048] Then, in a step S700, the second product is placed at a first temperature for at least a first time period to produce a second precursor.
The chemical formula of the second precursor is written by (Mn,,Fel.,)5(HPO4)2(PO4)2(i-120)4, and 0.5<x 1. Furthermore, the first temperature 100'C, and the first time period'-' 18 hours.
[0049] Lastly, in a step S800, a reaction of at least the second precursor, the lithium-contained compound, and another portion of the deionized water is processed, then the carbon source is added so as to be calcined for producing the battery composite material. The chemical formula of the battery composite material is written by LiMnje1_xPO4.
100501 The following embodiments are presented herein for purpose of' illustration and description of the preparation method of' the battery composite material and the precursor thereof of the present disclosure.
10051] Embodiment 1 100521 Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (1-131'04) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a first product. Next, the first product is grinded and dispersed by the hall mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(HPO4)2(PO4)2(1420)4.
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 413.
[0053] Ilmbodiment 2 [0054] Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (143PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a first product. Next, the first product is grinded and dispersed by the ball mill, then dried through the rolling dehydration, and placed at the temperature of 60 C to 100 C for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(FIP04)2(PO4)2(1-120)4. The surface exterior is analyzed through SEM. and the SEM analysis diagram is shown as FIG. 413.
[0055] Embodiment 3 [0056] Firstly, 574.7 grams of manganese carbonate (MnCO3), 575.61 grams of phosphoric acid (i-131)04) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a First product. Next, the first product is grinded and dispersed by the ball mill, then dried through the spray drying method, and placed at the temperature of 60 C to 100 C for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 4A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(FIP04)2(PO4)7(1-1)0)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 4B.
100571 Embodiment 4 100581 Firstly, 894.9 grams of manganese nitrate (Mn(NO3)2), 575.61 grams of phosphoric acid (1131304) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction. Then, the PI-I value is adjusted to 7-8 by ammonia solution (NH4OH), and the solution is precipitated to produce a first product. Next, the first product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 5A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(1-1PO4)2(PO4)2(H20)4. The surface exterior is analyzed through SEM. and the SEM analysis diagram is shown as FIG. 5B.
[0059] Embodiment 5 [0060] Firstly, 754.9 grams of manganese sulfate (MnSO4), 575.61 grams of phosphoric acid (1131304) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction. Then, the Pfl value is adjusted to 7-8 by ammonia solution (NI140I1), and the solution is precipitated to produce a first product.
After filtering, the first product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to I00 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray ditThaction, and the analysis diagram is shown as FIG. 6A. After comparing the diagram with JCPDS card, the compound is confirmed to be Mn5(EIP04)2(PO4)-0120)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 6B.
[00611 Embodiment 6 [0062] Firstly, 402.3 grams of manganese carbonate (MnCO3), 260.9 grams of iron(II) acetate (Fe(CH3C0014)2), 571.61 grams of phosphoric acid (113PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a second product. Next, the second product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 7A. After comparing the diagram with JCPDS card, the compound is confirmed to be (Mn0.7,Fe0.3)5(HPO4)2(PO4)7(H20)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 713.
[0063] Embodiment 7 100641 Firstly, 402.3 grams of manganese carbonate (Mn(703), 269.8 grams of iron(II) oxalate dihydrate (FeC204 = 21+0), 571.61 grams of phosphoric acid (1-13PO4) with weight percentage concentration equal to 85.1%, and 2 liters of deionized water are provided to process a reaction in order to produce a second product. Next, the second product is grinded and dispersed by the ball mill, and then placed at the temperature of 60 C to 100 C to dry for at least 18 hours to produce the precursor by the process of a low-temperature phase method. The precursor is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as NG. 8A. After comparing the diagram with JCPDS card, the compound is confirmed to be (Mn0,7,Fe0.3)5(HPO4)2(PO4)2(H20)4. The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 8B.
100651 Embodiment 8 100661 799.88 grams of the precursor, Mn5(11PO4)2(PO4)2(II,0)4, obtained in the above-mentioned embodiments, 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 9A. After comparing the diagram with JCPDS card, the compound is confirmed to he lithium manganese phosphate (LiMnPO4).
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 913.
[0067] Embodiment 9 10068] 799.88 grams of the precursor, Mns(I IP04)2( PO4)2(1120)4, obtained in the above-mentioned embodiments, 209.7 grams of lithium hydroxide (I ,i0I1), and 2 liters of dcionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 9A. After comparing the diagram with JCPDS card, the compound is confirmed to be lithium manganese phosphate (LiMnPO4).
The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 9C.
100691 Embodiment 10 100701 559.92 grams of the precursor, Mn5(11PO4)2(PO4)2(H20)4, obtained in the above-mentioned embodiments, 226.23 grams of heptairon hexaphosphate (Fe7(PO4)6), 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 10A. After comparing the diagram with JCPDS card, the compound is continued to be lithium iron manganese phosphate (LiMn0,7Fe0.3PO4). The surface exterior is analyzed through SEM, and the SEM analysis diagram is shown as FIG. 10B.
[0071] Embodiment 11 [0072] 559.92 grams of the precursor, Mn5(111304)2(1304)2(1120)4, obtained in the above-mentioned embodiments, 226.23 grams of iron(III) phosphate dihydrate (Fe1304 = 21-I,0), 184.7 grams of lithium carbonate (Li2CO3), and 2 liters of deionized water are provided to process a reaction.. Next, after dispersing and grinding, carbon source is added to obtain precursor solution. Then, the precursor solution is dried by the spray drying method, and sintered to phase at 600 C for 5 hours to produce the battery composite material. The battery composite material is analyzed in manner of X-ray diffraction, and the analysis diagram is shown as FIG. 11A. After comparing the diagram with JCPDS card, the compound is confirmed to be lithium iron manganese phosphate (LiMno,7Fe0.3PO4). The surface exterior is analyzed through SEM, and the SEM analysis diagrarn is shown as FIG. 11B.
[0073] Embodiment 12 [0074] The lithium manganese phosphate (LiMnPO4) obtained in the above-mentioned embodiments is mixed with carbon black (Super P) and binder (NVDF+NMP) as the proportion of 8.5:0.5:1, and the weight percentage concentration of the binder is 4%. For example, firstly, 0.5 grams of carbon black (Super P) and 25 grams of binder (NVDF:NMP=40:960) are mixed at 1200 rpm for 10 minutes. Then, 8.5 grams of lithium manganese phosphate (LiMnPO4) is added and mixed for another 10 minutes. Next, the dispersed slurry is coated with thickness of 0.3 mm on an aluminum substrate by a blade coater, and the coated pole piece is put into the oven, dried at 11 0 C for I hour and then taken out. Then, a round pole plate is made with lithium as the negative electrode, and a diameter of the round pole plate is 1.3 cm. Then, lithium hexafluorophosphate (LiPF6) with molarity as 1M, EC and EMC
are mixed as electrolyte, among which the volume ratio of EC and EMC
is 3:7. Lastly, the coated pole piece, the round pole plate and the electrolyte are made into a coin-cell battery. The electric characteristics of charging and discharging are tested and analyzed through a charging and discharging machine. The test and the analysis are performed at 0.1 coulombs for two cycles and 2 coulombs for two cycles. The charging and discharging characteristic diagram is shown as FIG. 12. The cutoff voltage of the coin-cell battery is 2 to 4.5 volts.
10075] Embodiment 13 100761 The lithium iron manganese phosphate (LiMn,Fe1_xPO4) obtained in the above-mentioned embodiments is mixed with carbon black (Super P) and binder (NVDF+NMP) as the proportion of 8.5:0.5:1, and the weight percentage concentration of the binder is 4%. For example, firstly, 0.5 grams of carbon black (Super P) and 25 grams of binder (NVDF:NMP=40:960) are mixed at 1200 rpm for 10 minutes.
Then, 8.5 grams of lithium iron manganese phosphate (LiMn,Fe1PO4) is added and mixed for another 10 minutes. Next, the dispersed slurry is coated with thickness of 0.3 mm on an aluminum substrate by a blade coater, and the coated pole piece is put into the oven, dried at 110 C for 1 hour and then taken out. Then, a round pole plate is made with lithium as the negative electrode, and a diameter of the round pole plate is 1.3 cm.
Then, lithium hexafluorophosphate (LiPF6) with molarity as 1M, EC and EMC are mixed as electrolyte, among which the volume ratio of EC and EMC is 3:7. Lastly, the coated pole piece, the round pole plate and the electrolyte are made into a coin-cell battery. The electric characteristics of charging and discharging are tested and analyzed through a charging and discharging machine. The test and the analysis are performed at 0.1 coulombs for two cycles and 2 coulombs for two cycles. The charging and discharging characteristic diagram is shown as FIG. 13. The cutoff voltage of the coin-cell battery is 2 to 4.5 volts.
100771 From the above description, the present invention provides a preparation method of battery composite material and a precursor thereof Through simple aqueous solution method, the precursor is produced by reacting in acidic environment to prepare the battery composite material.
The steps of the preparation method are less complicated, such that the preparation time is reduced, and the preparation effectiveness is enhanced.
Meanwhile, by producing the precursor at low temperature within a short time period in the process of a low-temperature phase method, the energy consumption is reduced, the phase of the precursor is more stable, and the advantages of reducing the cost of preparation and enhancing the quality of products are achieved.
100781 While the invention has been described in terms of what is presently considered to be the most practical and preferred embodiments, it is to be understood that the invention needs not be limited to the disclosed embodiment. On the contrary, it is intended to cover various modifications and similar arrangements included within the spirit and scope of the appended claims which are to be accorded with the broadest interpretation so as to encompass all such modifications and similar structures.
Claims (12)
1. A preparation method of a battery composite material, at least comprising steps of:
(a) providing a manganese-containing compound, phosphoric acid, a lithium-containing compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the phosphoric acid, and a portion of the deionized water to produce a first product;
(c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours; and (d) processing a reaction of at least the first precursor, the lithium-containing compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein step (c) does not comprise any stirring action.
(a) providing a manganese-containing compound, phosphoric acid, a lithium-containing compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the phosphoric acid, and a portion of the deionized water to produce a first product;
(c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours; and (d) processing a reaction of at least the first precursor, the lithium-containing compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein step (c) does not comprise any stirring action.
2. The preparation method according to claim 1, wherein the manganese-containing compound is manganese carbonate, manganese nitrate or manganese sulfate, and the lithium-containing compound is lithium carbonate, lithium hydroxide or lithium acetate.
3. The preparation method according to claim 1, wherein the chemical formula of the battery composite material is written by LiMnPO4.
4. The preparation method according to claim 1, wherein the step (d) is processing a reaction of the first precursor, an iron-containing compound, the lithium-containing compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the battery composite material is written by LiMn x Fe1-x PO4, and wherein x is larger than 0.5 and less than 1.
5. The preparation method according to claim 4, wherein the iron-containing compound is heptairon hexaphosphate, the chemical formula of which is written by Fe7(PO4)6, or the iron-containing compound is iron(III) phosphate dehydrate, the chemical formula of which is written by FePO4 .cndot. 2H2O.
6. The preparation method according to claim 1, wherein the step (b) further comprises a step (b1): performing a grinding and dispersing action and a drying action to the first product.
7. The preparation method according to claim 6, wherein the grinding and dispersing action is implemented by a ball mill.
8. The preparation method according to claim 6, wherein the drying action is implemented by rolling dehydration or spray drying.
9. The preparation method according to claim 1, wherein the step (d) further comprises steps of:
(d1) processing a reaction of the first precursor, the lithium-containing compound, and a portion of the deionized water, and adding a dispersant;
(d2) performing a grinding action, and adding the carbon source to obtain a first precursor solution; and (d3) performing a spray drying action and a thermal treatment to the first precursor solution to produce the battery composite material.
(d1) processing a reaction of the first precursor, the lithium-containing compound, and a portion of the deionized water, and adding a dispersant;
(d2) performing a grinding action, and adding the carbon source to obtain a first precursor solution; and (d3) performing a spray drying action and a thermal treatment to the first precursor solution to produce the battery composite material.
10. The preparation method according to claim 9, wherein the thermal treatment is performed at a temperature larger than 600°C for at least 5 hours.
11. A preparation method of a precursor of a battery composite material, at least comprising steps of:
(a) providing a manganese-containing compound, phosphoric acid, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the phosphoric acid, and the deionized water to produce a first product; and (c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours, wherein step (c) does not comprise any stirring action.
(a) providing a manganese-containing compound, phosphoric acid, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the phosphoric acid, and the deionized water to produce a first product; and (c) placing the first product at a first temperature for at least a first time period to produce a first precursor, wherein the chemical formula of the first precursor is written by Mn5(HPO4)2(PO4)2(H2O)4, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours, wherein step (c) does not comprise any stirring action.
12. A preparation method of a battery composite material, at least comprising steps of:
(a) providing a manganese-containing compound, an iron-containing compound, phosphoric acid, a lithium-containing compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the iron-containing compound, the phosphoric acid, and a portion of the deionized water to produce a second product;
(c) placing the second product at a first temperature for at least a first time period to produce a second precursor, wherein the chemical formula of the second precursor is written by (Mn x,Fe1-x)5(HPO4)2(PO4)2(H2O)4, and wherein x is larger than 0.5 and less than 1, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours; and (d) processing a reaction of at least the second precursor, the lithium-containing compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the battery composite material is written by LiMn x Fe1-x PO4, wherein step (c) does not comprise any stirring action.
(a) providing a manganese-containing compound, an iron-containing compound, phosphoric acid, a lithium-containing compound, a carbon source, and deionized water, wherein the chemical formula of the phosphoric acid is written by H3PO4;
(b) processing a reaction of the manganese-containing compound, the iron-containing compound, the phosphoric acid, and a portion of the deionized water to produce a second product;
(c) placing the second product at a first temperature for at least a first time period to produce a second precursor, wherein the chemical formula of the second precursor is written by (Mn x,Fe1-x)5(HPO4)2(PO4)2(H2O)4, and wherein x is larger than 0.5 and less than 1, wherein the first temperature is larger than or equal to 60°C and less than or equal to 100°C, and wherein the first time period is larger than or equal to 18 hours; and (d) processing a reaction of at least the second precursor, the lithium-containing compound, and another portion of the deionized water, adding the carbon source, and then calcining to produce the battery composite material, wherein the chemical formula of the battery composite material is written by LiMn x Fe1-x PO4, wherein step (c) does not comprise any stirring action.
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| US62/101,054 | 2015-01-08 | ||
| PCT/CN2016/070382 WO2016110261A1 (en) | 2015-01-08 | 2016-01-07 | Method for preparing battery composite material and precursor thereof |
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| CN115806282B (en) * | 2022-11-22 | 2024-05-10 | 贵州雅友新材料有限公司 | Flaky lithium iron manganese phosphate and synthesis method and application thereof |
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| CN101891177A (en) * | 2010-07-05 | 2010-11-24 | 华中农业大学 | A kind of preparation method of manganese phosphate material |
| WO2014032588A1 (en) * | 2012-08-28 | 2014-03-06 | 台湾立凯电能科技股份有限公司 | Method of producing battery composite material and its precursor |
| CN103000898A (en) * | 2012-12-11 | 2013-03-27 | 中国电子科技集团公司第十八研究所 | Preparation method for carbon compounded lithium ferromanganese phosphate used for lithium ion battery |
| WO2014098937A1 (en) * | 2012-12-21 | 2014-06-26 | Dow Global Technologies Llc | Lmfp cathode materials with improved electrochemical performance |
| JP6239095B2 (en) * | 2013-05-08 | 2017-11-29 | 台湾立凱電能科技股▲ふん▼有限公司 | Battery composite material and method for producing precursor thereof |
| WO2014180334A1 (en) * | 2013-05-08 | 2014-11-13 | 台湾立凯电能科技股份有限公司 | Method for preparing battery composite material and the precursor thereof |
| CN103413943B (en) | 2013-08-14 | 2015-06-17 | 湖北万润新能源科技发展有限公司 | Lithium manganese phosphate positive electrode material and preparation method thereof |
| JP5846453B2 (en) * | 2013-09-11 | 2016-01-20 | 株式会社デンソー | Method for producing positive electrode active material |
| CN103985868A (en) * | 2014-05-28 | 2014-08-13 | 天津大学 | Lithium iron phosphate lithium/carbon composite positive electrode material and synthesis method for lithium ion battery |
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| US10266410B2 (en) | 2019-04-23 |
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