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WO2016110261A1 - 电池复合材料及其前驱物的制备方法 - Google Patents

电池复合材料及其前驱物的制备方法 Download PDF

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Publication number
WO2016110261A1
WO2016110261A1 PCT/CN2016/070382 CN2016070382W WO2016110261A1 WO 2016110261 A1 WO2016110261 A1 WO 2016110261A1 CN 2016070382 W CN2016070382 W CN 2016070382W WO 2016110261 A1 WO2016110261 A1 WO 2016110261A1
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Prior art keywords
battery composite
containing compound
precursor
lithium
preparing
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PCT/CN2016/070382
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English (en)
French (fr)
Inventor
林翔斌
谢瀚纬
黄安锋
黄俊铭
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台湾立凯电能科技股份有限公司
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Priority to US15/540,309 priority Critical patent/US10266410B2/en
Priority to CN201680004656.8A priority patent/CN107112525A/zh
Priority to EP16734921.6A priority patent/EP3244473B1/en
Priority to JP2017535921A priority patent/JP6419343B2/ja
Priority to CA2972567A priority patent/CA2972567C/en
Priority to KR1020177018755A priority patent/KR101939930B1/ko
Publication of WO2016110261A1 publication Critical patent/WO2016110261A1/zh

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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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/04—Processes of manufacture in general
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • 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
    • 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
    • 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

Definitions

  • the present disclosure relates to a method of preparation, and more particularly to a method of preparing a battery composite and a precursor thereof.
  • lithium batteries have become widely accepted in the market because of their high energy density, no memory effect, long cycle life and no pollution.
  • lithium manganese phosphate (LiMnPO 4 ) is used as the cathode material.
  • the battery has the advantages of high energy density, high charge and discharge capacity, high stability and safety, abundant raw material sources and relatively low price, and has become a positive electrode material for lithium batteries with great development potential.
  • the preparation method of the existing lithium manganese phosphate mostly adopts a hydrothermal method or an organic solution method, and the steps thereof are cumbersome. At the same time, the temperature conditions required for preparation are high and energy consumption, and the phase formation of lithium manganese phosphate is also unstable. In addition, lithium manganese phosphate is more commonly considered a reactant in the transition phase.
  • the main object of the present disclosure is to provide a method of preparing a battery composite and a precursor thereof to solve and ameliorate the problems and disadvantages of the foregoing prior art.
  • Another object of the present disclosure is to provide a method for preparing a battery composite material and a precursor thereof, which can be prepared by reacting a simple aqueous solution method in an acidic environment to prepare a battery composite material, and the process steps are relatively simple and effective. The preparation time is saved, and the effect of improving the preparation efficiency is achieved.
  • Another object of the present disclosure is to provide a method for preparing a battery composite material and a precursor thereof, which can reduce energy consumption and reduce precursor energy by forming a precursor at a low temperature and a short time in a process by a low temperature phase forming method.
  • the phase formation is also relatively stable, which in turn reduces the cost of preparation and effectively improves product quality.
  • a broader embodiment of the present disclosure provides a method for preparing a battery composite, comprising at least the 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 H 3 PO 4 ; (b) reacting the manganese-containing compound, the phosphoric acid with a portion of the deionized water to form a first product; (c) placing the first product in a first At least a first time at a temperature to generate a first precursor having a chemical formula of Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 ; and (d) at least The first precursor, the lithium-containing compound is reacted with a portion of the deionized water, and the carbon source is added and calcined to form a battery composite.
  • another broad embodiment of the present disclosure provides a method for preparing a precursor of a battery composite, which comprises (a) providing a manganese-containing compound, phosphoric acid, a lithium-containing compound, and deionized water, wherein the phosphoric acid a chemical formula of H 3 PO 4 ; (b) reacting the manganese-containing compound, the phosphoric acid with a portion of the deionized water to form a first product; and (c) placing the first product at a first temperature At least a first time to generate a first precursor having a chemical formula of Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 .
  • another broad embodiment of the present disclosure provides a method for preparing a battery composite, comprising at least the step of using Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 as a precursor. And reacting the precursor with the lithium-containing compound and deionized water, and adding a carbon source to perform calcination to form a battery composite material, wherein the battery composite has a chemical formula of LiMnPO 4 .
  • another broad embodiment of the present disclosure provides a method for preparing a battery composite, comprising at least the steps of: (a) providing a manganese-containing compound, an iron-containing compound, a phosphoric acid, a lithium-containing compound, a carbon source, and Deionized water, wherein the chemical formula of the phosphoric acid is H 3 PO 4 ; (b) reacting the manganese-containing compound, the iron-containing compound, the phosphoric acid with a portion of the deionized water to form a second product; And placing the second product at the first temperature for at least a first time to generate a second precursor having a chemical formula of (Mn x, Fe 1-x ) 5 (HPO 4 ) 2 (PO 4 2 (H 2 O) 4 , wherein x is greater than 0.5 and less than or equal to 1; and (d) reacting the second precursor, the lithium-containing compound with a portion of the deionized water, and adding the carbon source
  • the calcination is performed
  • FIG. 1 is a flow chart of a method for preparing a battery composite material according to a preferred embodiment of the present disclosure.
  • FIG. 2 is a detailed flow chart of a method of preparing a battery composite of the present disclosure.
  • FIG. 3 is a flow chart of a method for preparing a battery composite material according to another preferred embodiment of the present disclosure.
  • 4A is an X-ray diffraction analysis diagram of a precursor of an embodiment of the present disclosure.
  • 4B is an electron microscope analysis diagram of a precursor of an embodiment of the present disclosure.
  • 5A is an X-ray diffraction analysis diagram of a precursor of another embodiment of the present disclosure.
  • 5B is an electron microscopic analysis diagram of a precursor of another embodiment of the present disclosure.
  • 6A is an X-ray diffraction analysis diagram of a precursor of another embodiment of the present disclosure.
  • 6B is an electron microscopic analysis diagram of a precursor of another embodiment of the present disclosure.
  • FIG. 7A is an X-ray diffraction analysis diagram of a precursor of another embodiment of the present disclosure.
  • 7B is an electron microscopic analysis diagram of a precursor of another embodiment of the present disclosure.
  • FIG. 8A is an X-ray diffraction analysis diagram of a precursor of another embodiment of the present disclosure.
  • 8B is an electron microscopic analysis diagram of a precursor of another embodiment of the present disclosure.
  • 9A is an X-ray diffraction analysis diagram of a battery composite prepared by the production method of the present disclosure.
  • 9B is an electron microscopic analysis diagram of a battery composite prepared by the production method of the present disclosure.
  • 9C is an electron microscopic analysis diagram of another battery composite prepared by the production method of the present disclosure.
  • FIG. 10A is an X-ray diffraction analysis diagram of another battery composite prepared by the production method of the present disclosure.
  • FIG. 10B is an electron microscopic analysis diagram of another battery composite prepared by the production method of the present disclosure.
  • 11A is an X-ray diffraction analysis diagram of another battery composite prepared by the production method of the present disclosure.
  • 11B is an electron microscopic analysis diagram of another battery composite prepared by the production method of the present disclosure.
  • Fig. 12 is a graph showing the charge and discharge of a button type battery made of a battery composite prepared by the production method of the present disclosure.
  • Figure 13 is a graph showing the charge and discharge of a button type battery made of another battery composite material prepared by the production method of the present disclosure.
  • FIG. 1 is a flow chart of a method for preparing a battery composite material according to a preferred embodiment of the present disclosure.
  • the method for preparing a battery composite of the present disclosure includes the following steps: First, as shown in step S100, a manganese-containing compound, an iron-containing compound, a phosphoric acid, a lithium-containing compound, a carbon source, and deionized water are provided, wherein The chemical formula of phosphoric acid is H 3 PO 4 .
  • the manganese-containing compound can be, for example, but not limited to, manganese carbonate (chemical formula MnCO 3 ), manganese nitrate (chemical formula Mn(NO 3 ) 2 ), manganese sulfate (chemical formula MnSO 4 ), or other manganese-bearing
  • the ionic compound, the lithium-containing compound may be, for example but not limited to, lithium carbonate (chemical formula: Li 2 CO 3 ), lithium hydroxide (chemical formula: LiOH), lithium acetate (chemical formula: LiCH 3 COO), or other compound having lithium ions.
  • the carbon source may be a saccharide, an organic compound, a polymer or a polymer material, but is not limited thereto.
  • Step S200 a reaction is carried out with a manganese-containing compound, phosphoric acid and a portion of deionized water to produce a first product.
  • Step S200 may further include the steps of: performing a grinding and dispersing action on the first product and a drying operation, the grinding action being performed by a ball mill, and the drying action may be achieved by rolling dehydration or spray drying, but not limit.
  • the drying method of the pressure dehydration can perform the drying operation of the first product in a large amount and quickly, and the yield of the first product which is dried is extremely high.
  • the first product is placed at the first temperature for at least a first time to generate a first precursor, wherein the chemical formula of the first precursor is Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 .
  • the first temperature is greater than or equal to 60 degrees Celsius and less than or equal to 100 degrees Celsius, that is, 60 ° C, the first temperature ⁇ 100 ° C, the first time is greater than or equal to 18 hours, that is, the first Time is 18 hours.
  • step S400 at least a first precursor, a lithium-containing compound, and a portion of deionized water are reacted, and a carbon source is added, followed by calcination to form a battery composite material, such as lithium manganese phosphate (chemical formula: LiMnPO) 4 ).
  • a battery composite material such as lithium manganese phosphate (chemical formula: LiMnPO) 4 ).
  • step S400 may also react the first precursor with the iron-containing compound, the lithium-containing compound, and a portion of the deionized water, wherein the iron-containing compound may be, for example, but not limited to, hepta-hexaphosphate (chemical formula: Fe 7) (PO 4 ) 6 ), iron phosphate dihydrate (chemical formula: FePO 4 ⁇ 2H 2 O) or other compound with iron ions, and after adding a carbon source, calcining to form a battery composite material, such as lithium iron phosphate Manganese (chemical formula is LiMn x Fe 1-x PO 4 , where x is greater than 0.5 and less than or equal to 1).
  • the iron-containing compound may be, for example, but not limited to, hepta-hexaphosphate (chemical formula: Fe 7) (PO 4 ) 6 ), iron phosphate dihydrate (chemical formula: FePO 4 ⁇ 2H 2 O) or other compound with iron ions, and after adding a carbon source, calcining to form a
  • the method for preparing a battery composite material and a precursor thereof of the present invention is a simple aqueous solution method for reacting in an acidic environment to produce a precursor, and then reacting with a lithium-containing compound to prepare a battery composite material, and the process steps are relatively simple.
  • the invention can effectively save the preparation time and achieve the effect of improving the preparation efficiency.
  • the energy consumption can be reduced, and the phase formation of the precursor is also relatively stable, thereby reducing the cost of preparation and effectively improving the product quality.
  • FIG. 2 is a detailed flow chart of a method for preparing a battery composite material according to the present disclosure.
  • the detailed process of the step S400 of the method for preparing a battery composite of the present disclosure includes the following steps: as shown in step S401, the first precursor, the lithium-containing compound and a part of deionized water are reacted.
  • step S402 performing a grinding action and adding a carbon source to obtain a first precursor solution, wherein the grinding The action is achieved by a ball mill, but not limited thereto.
  • step S403 the first precursor solution is subjected to a spray drying operation and a heat treatment operation to generate a battery composite material such as lithium manganese phosphate (chemical formula LiMnPO 4 ).
  • step S403 the spray drying operation is achieved through a rotary disc spray dryer, but not limited thereto.
  • the heat treatment operation heat-treats the finished product at a temperature of more than 600 degrees Celsius for at least 5 hours, for example, sintering at 600 ° C to form a phase, holding the temperature for 5 hours, but not limited thereto.
  • FIG. 3 is a flow chart of a method for preparing a battery composite material according to another preferred embodiment of the present disclosure.
  • the method for preparing another battery composite material of the present disclosure includes the following steps: First, as shown in step S500, a manganese-containing compound, an iron-containing compound, a phosphoric acid, a lithium-containing compound, a carbon source, and deionized water are provided. Wherein the chemical formula of phosphoric acid is H 3 PO 4 .
  • the manganese-containing compound can be, for example, but not limited to, manganese carbonate (chemical formula MnCO 3 ), manganese nitrate (chemical formula Mn(NO 3 ) 2 ), manganese sulfate (chemical formula MnSO 4 ), or other manganese-bearing
  • the ionic compound, the iron-containing compound may be, for example but not limited to, ferrous acetate (Fe(CH 3 COO) 2 ), iron oxalate dihydrate (chemical formula: FeC 2 O 4 ⁇ 2H 2 O), and the lithium-containing compound may be, for example, However, it is not limited to lithium carbonate (chemical formula: Li 2 CO 3 ), lithium hydroxide (chemical formula: LiOH), lithium acetate (chemical formula: LiCH 3 COO) or other compounds having lithium ions, and the carbon source may be sugar or organic. Compound, polymer or polymer material, but not limited to this.
  • Step S600 a manganese-containing compound, an iron-containing compound, phosphoric acid, and a portion of deionized water are reacted to form a second product.
  • Step S600 may further include the step of performing a grinding and dispersing action and a drying action on the second product.
  • step S700 the second product is placed at the first temperature for at least a first time to generate a second precursor having a chemical formula of (Mn x, Fe 1-x ) 5 (HPO) 4 ) 2 (PO 4 ) 2 (H 2 O) 4 , wherein 0.5 ⁇ x ⁇ 1, 60 ° C ⁇ first temperature ⁇ 100 ° C, and the first time ⁇ 18 hours.
  • step S800 reacting with at least a second precursor, a lithium-containing compound, and a portion of deionized water, and adding a carbon source, followed by calcination to form a battery composite, wherein the chemical formula of the battery composite is LiMn x Fe 1-x PO 4 .
  • a first product 574.7 g of manganese carbonate (MnCO 3 ) is supplied with 85.1% by weight of phosphoric acid (H 3 PO 4 ) 575.61 g and 2 liters of deionized water to produce a first product, followed by a ball mill.
  • the first product is ground and dispersed, and then dried at a temperature of 60 ° C to 100 ° C for at least 18 hours to form a low temperature phase to form a precursor.
  • the obtained precursor was analyzed by X-ray diffraction (XRD) as shown in Fig. 4A, and after confirming the standard diffraction pattern (JCPDS Card), the structure was confirmed to be Mn 5 (HPO 4 ) 2 (PO 4 ) 2 . (H 2 O) 4 , a scanning electron microscope (SEM) analysis chart of the surface morphology is shown in Fig. 4B.
  • XRD X-ray diffraction
  • 574.7 g of manganese carbonate (MnCO 3 ) is supplied with 85.1% by weight of phosphoric acid (H 3 PO 4 ) 575.61 g and 2 liters of deionized water to produce a first product, followed by a ball mill.
  • the first product is ground and dispersed, and then subjected to press molding dehydration, and then placed at a temperature of 60 ° C to 100 ° C for at least 18 hours to form a low temperature phase to form a precursor.
  • the obtained precursor was analyzed by X-ray diffraction as shown in Fig. 4A.
  • 574.7 g of manganese carbonate (MnCO 3 ) is supplied with 85.1% by weight of phosphoric acid (H 3 PO 4 ) 575.61 g and 2 liters of deionized water to produce a first product, followed by a ball mill.
  • the first product is ground and dispersed, dried by atomization drying, and then placed at a temperature of 60 ° C to 100 ° C for at least 18 hours to form a low temperature phase to form a precursor.
  • the obtained precursor was analyzed by X-ray diffraction as shown in Fig. 4A.
  • 894.9 g of manganese nitrate (Mn(NO 3 ) 2 ) is supplied with 85.1% by weight of phosphoric acid (H 3 PO 4 ) 575.61 g and 2 liters of deionized water to form a first product.
  • the pH is adjusted to 7-8 with ammonia water (NH 4 ), and the first product is formed after sedimentation.
  • the first product is ground and dispersed by ball milling, and then dried at 60 ° C to 100 ° C. At 18 hours, a low temperature phase was formed to form a precursor.
  • the obtained precursor was analyzed by X-ray diffraction as shown in Fig. 5A.
  • MnCO 3 manganese carbonate
  • Fe(CH 3 COO) 2 ferrous acetate
  • H 3 PO 4 phosphoric acid
  • the ionized water is reacted to form a first product, and then the first product is ground and dispersed by ball milling, and then dried at 60 ° C to 100 ° C for at least 18 hours to form a low temperature phase to generate a precursor. Things.
  • the obtained precursor was analyzed by X-ray diffraction as shown in Fig.
  • the precursor Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 obtained in the previous examples was reacted with 799.88 g and 184.7 g of lithium carbonate (Li 2 CO 3 ) and 2 liters of deionized water.
  • a carbon source is added to obtain a precursor solution, the precursor solution is dried by a spray drying method, and sintered at 600 ° C to form a phase, and the battery composite obtained after holding for 5 hours is X-ray diffraction.
  • the analysis results are shown in Fig. 9A. After comparison with the standard diffraction pattern, it was confirmed that the structure was lithium manganese phosphate (LiMnPO 4 ), and the scanning electron microscope analysis pattern of the surface morphology was as shown in Fig. 9B.
  • the precursor Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 obtained in the foregoing examples was reacted with 799.88 g and 209.7 g of lithium hydroxide (LiOH) and 2 liters of deionized water to be dispersed.
  • a carbon source is added to obtain a precursor solution, the precursor solution is dried by a spray drying method, and sintered at 600 ° C to form a phase, and the battery composite obtained after holding for 5 hours is subjected to X-ray diffraction analysis.
  • Fig. 9A after confirming the standard diffraction pattern, it was confirmed that the structure was lithium manganese phosphate (LiMnPO 4 ), and the scanning electron microscope analysis pattern of the surface morphology was as shown in Fig. 9C.
  • the precursor Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 obtained in the foregoing examples was taken from 559.92 g and 226.23 g of hepta iron hexaphosphate (Fe 7 (PO 4 ) 6 ) and 184.7 g.
  • Lithium carbonate (Li 2 CO 3 ) and 2 liters of deionized water were reacted, and after dispersion grinding, a carbon source was added to obtain a precursor solution, and the precursor solution was dried by spray drying and sintered at 600 ° C.
  • the phase of the battery composite obtained after holding the temperature for 5 hours was analyzed by X-ray diffraction as shown in Fig. 10A. After comparison with the standard diffraction pattern, the structure was confirmed to be lithium iron iron manganese (LiMn 0.7 Fe 0.3 PO 4 ), the surface thereof.
  • the scanning electron microscope analysis pattern of the topography is shown in Fig. 10B.
  • the precursor Mn 5 (HPO 4 ) 2 (PO 4 ) 2 (H 2 O) 4 obtained in the foregoing examples was taken from 559.92 g and 226.23 g of iron phosphate dihydrate (FePO 4 ⁇ 2H 2 O) and 184.7 g.
  • Lithium carbonate (Li 2 CO 3 ) and 2 liters of deionized water were reacted, and after dispersion grinding, a carbon source was added to obtain a precursor solution, and the precursor solution was dried by spray drying and sintered at 600 ° C.
  • the phase of the battery composite obtained after holding the temperature for 5 hours was analyzed by X-ray diffraction as shown in Fig. 11A. After comparison with the standard diffraction pattern, the structure was confirmed to be lithium iron phosphate (LiMn 0.7 Fe 0.3 PO 4 ), the surface thereof.
  • the scanning electron microscope analysis pattern of the topography is shown in Fig. 11B.
  • the coated pole piece was placed in an oven and dried at a temperature of 110 ° C for 1 hour, and then taken out, and a circular plate having a diameter of 1.3 cm was drilled with lithium metal as a negative electrode, and a volume ratio of LiPF 6 to volume ratio of a molar concentration of 1 M was used.
  • the 3:7 EC and EMC are mixed into an electrolyte, which is made into a coin-type battery, and the charge and discharge machine is used for 0.1 coulomb charge and discharge for 2 cycles and 2 coulomb charge and discharge for 2 cycles. Test, the test results are shown in Figure 12, with a cut-off voltage of 2 to 4.5 volts.
  • the lithium iron manganese phosphate (LiMn x Fe 1-x PO 4 ) obtained in the foregoing examples was mixed with carbon black (Super P) and 4% binder (PVDF+NMP) at a ratio of 8.5:0.5:1, firstly, 0.5.
  • the coated pole piece was placed in an oven and dried at a temperature of 110 ° C for 1 hour, and then taken out, and a circular plate having a diameter of 1.3 cm was drilled with lithium metal as a negative electrode, and a volume ratio of LiPF 6 to volume ratio of a molar concentration of 1 M was used.
  • the 3:7 EC and EMC are mixed into an electrolyte, which is made into a coin-type battery, and the charge and discharge machine is used for 0.1 coulomb charge and discharge for 2 cycles and 2 coulomb charge and discharge for 2 cycles. Test, the test results are shown in Figure 13, and the cut-off voltage is 2 to 4.5 volts.
  • the battery composite material of the present disclosure and a method for preparing the same are prepared by reacting a simple aqueous solution in an acidic environment to produce a precursor, and then reacting with a lithium-containing compound to prepare a battery composite. It is relatively simple, which can effectively save the preparation time and achieve the effect of improving the preparation efficiency. At the same time, through the low temperature phase forming method in the process The formation of a precursor at a low temperature in a short period of time can reduce the energy consumption and the phase formation of the precursor is relatively stable, thereby reducing the cost of preparation and effectively improving product quality.

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Abstract

一种电池复合材料的制备方法，至少包括步骤：提供含锰化合物、磷酸、含锂化合物、碳源及去离子水（S100）；以含锰化合物、磷酸与部分的去离子水进行反应，以生成第一生成物（S200）；将第一生成物置于第一温度下至少第一时间，以生成第一前驱物，第一前驱物的化学式为Mn 5(HPO 4) 2(PO 4) 2(H 2O) 4（S300）；以及以至少第一前驱物、含锂化合物与部分的去离子水进行反应，并添加碳源后进行锻烧，以生成电池复合材料（S400）。透过低温成相法在制程中以低温于短时间内形成前驱物，可节省制备时间、减少耗能，且前驱物的成相较为稳定，进而达到降低制备成本且提升产品质量的效果。

Description

电池复合材料及其前驱物的制备方法 技术领域
本公开关于一种制备方法，尤指一种电池复合材料及其前驱物的制备方法。
背景技术
随着全球经济快速发展，资源的消耗与日俱增，且近年来环境保护观念逐渐受到重视，为克服能源短缺问题并同时注重永续经营，寻找环保、干净又不失效能的替代性能源即成为业界的重要发展方向。在现行各种的替代性能源当中，化学电池是目前相关产业积极投入研发的技术，不仅使制备电池的技术更为精进、电池的效能提升，同时也被广泛地应用于日常生活中，例如消费性电子产品、医疗器材、电动脚踏车及电动汽机车等。
于众多化学电池中，锂电池因为其高能量密度、无记忆效应、循环寿命长且无污染等特性，广为市场所接受而成为主流，其中，又以磷酸锰锂(LiMnPO4)作为正极材料的电池具有较高能量密度、高充放电容量、高稳定性与安全性、原料来源丰富以及价格相对低廉等优点，成为极具发展潜力的锂电池正极材料。
然而，现有磷酸锰锂的制备方法多采用水热法或有机溶液法，其步骤较为繁琐，同时，制备所需温度条件较高而耗能，且磷酸锰锂的成相亦较不稳定。此外，磷酸锰锂更是较常被视为过渡阶段的反应物。
因此，如何改善现有技术中的问题与缺点，并且简化制程步骤、减少耗费能量以及使磷酸锰锂的成相稳定，实为目前技术领域中的重点课题。
发明内容
本公开的主要目的为提供一种电池复合材料及其前驱物的制备方法，以解决并改善前述先前技术的问题与缺点。
本公开的另一目的为提供一种电池复合材料及其前驱物的制备方法，透过简单的水溶液法于酸性环境下反应产生前驱物，以制备电池复合材料，其制程步骤较为简易，可有效节省制备时间，达到提高制备效率的效果。
本公开的另一目的为提供一种电池复合材料及其前驱物的制备方法，透过低温成相法在制程中以低温于短时间内形成前驱物，可使耗费能量减少，且前驱物的成相亦较为稳定，进而降低制备所需成本并且有效提升产品质量。
为达上述目的，本公开的一较广实施方式为提供一种电池复合材料的制备方法，至少包括步骤：(a)提供含锰化合物、磷酸、含锂化合物、碳源及去离子水，其中该磷酸的化学式为H3PO4；(b)以该含锰化合物、该磷酸与部分的该去离子水进行反应，以生成第一生成物；(c)将该第一生成物置于一第一温度下至少一第一时间，以生成第一前驱物，该第一前 驱物的化学式为Mn5(HPO4)2(PO4)2(H2O)4；以及(d)以至少该第一前驱物、该含锂化合物与部分的该去离子水进行反应，并添加该碳源后进行锻烧，以生成电池复合材料。
为达上述目的，本公开的另一较广实施方式为提供一种电池复合材料的前驱物的制备方法，(a)提供含锰化合物、磷酸、含锂化合物及去离子水，其中该磷酸的化学式为H3PO4；(b)以该含锰化合物、该磷酸与部分的该去离子水进行反应，以生成第一生成物；以及(c)将该第一生成物置于一第一温度下至少一第一时间，以生成第一前驱物，该第一前驱物的化学式为Mn5(HPO4)2(PO4)2(H2O)4。
为达上述目的，本公开的另一较广实施方式为提供一种电池复合材料的制备方法，至少包括步骤：以Mn5(HPO4)2(PO4)2(H2O)4为前驱物，并以该前驱物与含锂化合物及去离子水进行反应，并添加碳源后进行锻烧，以生成电池复合材料，其中该电池复合材料的化学式为LiMnPO4。
为达上述目的，本公开的另一较广实施方式为提供一种电池复合材料的制备方法，至少包括步骤：(a)提供含锰化合物、含铁化合物、磷酸、含锂化合物、碳源及去离子水，其中该磷酸的化学式为H3PO4；(b)以该含锰化合物、该含铁化合物、该磷酸与部分的该去离子水进行反应，以生成第二生成物；(c)将该第二生成物置于第一温度下至少第一时间，以生成第二前驱物，该第二前驱物的化学式为(Mnx,Fe1-x)5(HPO4)2(PO4)2(H2O)4，其中x大于0.5且小于或等于1；以及(d)以该第二前驱物、该含锂化合物与部分的该去离子水进行反应，并添加该碳源后进行锻烧，以生成电池复合材料，其中该电池复合材料的化学式为LiMnxFe1-xPO4。
附图说明
图1为本公开较佳实施例的电池复合材料的制备方法流程图。
图2为本公开电池复合材料的制备方法的一细部流程图。
图3为本公开另一较佳实施例的电池复合材料的制备方法流程图。
图4A为本公开一实施例的前驱物的X光衍射分析图。
图4B为本公开一实施例的前驱物的电子显微镜分析图。
图5A为本公开另一实施例的前驱物的X光衍射分析图。
图5B为本公开另一实施例的前驱物的电子显微镜分析图。
图6A为本公开另一实施例的前驱物的X光衍射分析图。
图6B为本公开另一实施例的前驱物的电子显微镜分析图。
图7A为本公开另一实施例的前驱物的X光衍射分析图。
图7B为本公开另一实施例的前驱物的电子显微镜分析图。
图8A为本公开另一实施例的前驱物的X光衍射分析图。
图8B为本公开另一实施例的前驱物的电子显微镜分析图。
图9A为以本公开的制备方法制备的一电池复合材料的X光衍射分析图。
图9B为以本公开的制备方法制备的一电池复合材料的电子显微镜分析图。
图9C为以本公开的制备方法制备的另一电池复合材料的电子显微镜分析图。
图10A为以本公开的制备方法制备的另一电池复合材料的X光衍射分析图。
图10B为以本公开的制备方法制备的另一电池复合材料的电子显微镜分析图。
图11A为以本公开的制备方法制备的另一电池复合材料的X光衍射分析图。
图11B为以本公开的制备方法制备的另一电池复合材料的电子显微镜分析图。
图12为以本公开的制备方法制备的电池复合材料制成的钮扣型电池的充放电性图。
图13为以本公开的制备方法制备的另一电池复合材料制成的钮扣型电池的充放电性图。
【符号说明】
S100、S200、S300、S400：步骤
S401、S402、S403：步骤
S500、S600、S700、S800：步骤
具体实施方式
体现本公开特征与优点的一些典型实施例将在后段的说明中详细叙述。应理解的是本公开能够在不同的方式上具有各种的变化，其皆不脱离本公开的范围，且其中的说明及附图在本质上当作说明之用，而非架构于限制本公开。
请参阅图1，其为本公开较佳实施例的电池复合材料的制备方法流程图。如图1所示，本公开的电池复合材料的制备方法包括步骤如下：首先，如步骤S100所示，提供含锰化合物、含铁化合物、磷酸、含锂化合物、碳源及去离子水，其中磷酸的化学式为H3PO4。于一些实施例中，含锰化合物可为例如但不限于碳酸锰(化学式为MnCO3)、硝酸锰(化学式为Mn(NO3)2)、硫酸锰(化学式为MnSO4)或其他带有锰离子的化合物，含锂化合物可为例如但不限于碳酸锂(化学式为Li2CO3)、氢氧化锂(化学式为LiOH)、醋酸锂(化学式为LiCH3COO)或其他带有锂离子的化合物，且碳源可为醣类、有机化合物、聚合物或高分子材料，但不以此为限。
其次，如步骤S200所示，以含锰化合物、磷酸与部分的去离子水进行反应，以生成第一生成物。步骤S200更可包括步骤：对第一生成物进行研磨分散动作以及干燥动作，该研磨动作可透过球磨机实现，且该干燥动作可透过辗压脱水或喷雾干燥实现，但皆不以此为限。其中，辗压脱水的干燥方法可大量且快速地对第一生成物进行干燥动作，其生成干燥的第一生成物的产率极高。
然后，如步骤S300所示，将第一生成物置于第一温度下至少第一时间，以生成第一前驱物，其中该第一前驱物的化学式为Mn5(HPO4)2(PO4)2(H2O)4。于一些实施例中，该第一温度大于或等于摄氏60度且小于或等于摄氏100度，亦即60℃≦第一温度≦100℃，该第一时间大于或等于18小时，亦即第一时间≧18小时。
最后，如步骤S400所示，以至少第一前驱物、含锂化合物与部分的去离子水进行反应，并添加碳源后进行锻烧，以生成电池复合材料，例如磷酸锂锰(化学式为LiMnPO4)。
于一些实施例中，步骤S400亦可以第一前驱物与含铁化合物、含锂化合物与部分的去离子水进行反应，其中含铁化合物可为例如但不限于六磷酸七铁(化学式为Fe7(PO4)6)、磷酸铁二水合物(化学式为FePO4·2H2O)或其他带有铁离子的化合物，并添加碳源后进行锻烧，以生成电池复合材料，例如磷酸锂铁锰(化学式为LiMnxFe1-xPO4，其中x大于0.5且小于或等于1)。
简言之，本公开电池复合材料及其前驱物的制备方法，透过简单的水溶液法于酸性环境下反应产生前驱物，再与含锂化合物进行反应以制备电池复合材料，其制程步骤较为简易，可有效节省制备时间，达到提高制备效率的效果。同时，透过低温成相法在制程中以低温于短时间内形成前驱物，可使耗费能量减少，且前驱物的成相亦较为稳定，进而降低制备所需成本并且有效提升产品质量。
请参阅图2并配合图1，其中图2为本公开电池复合材料的制备方法的一细部流程图。如图1及图2所示，本公开电池复合材料的制备方法的步骤S400的细部流程包括步骤如下：如步骤S401所示，以第一前驱物、含锂化合物与部分的去离子水进行反应并添加分散剂，其中分散剂可为非离子型接口活性剂，例如Triton X-100；接着，如步骤S402所示，进行研磨动作并添加碳源，以得到第一前驱物溶液，其中该研磨动作透过球磨机实现，但不以此为限；再来，如步骤S403所示，对第一前驱物溶液进行喷雾干燥动作及热处理动作，以生成电池复合材料，例如磷酸锂锰(化学式为LiMnPO4)。
于步骤S403中，该喷雾干燥动作的实现透过一转盘式喷雾干燥机，但不以此为限。此外，该热处理动作将经过喷雾干燥后的成品，于温度大于摄氏600度进行至少5小时的热处理，例如以600℃进行烧结成相，持温5小时，然亦不以此为限。
请参阅图3，其为本公开另一较佳实施例的电池复合材料的制备方法流程图。如图3所示，本公开的另一电池复合材料的制备方法包括步骤如下：首先，如步骤S500所示，提供含锰化合物、含铁化合物、磷酸、含锂化合物、碳源及去离子水，其中磷酸的化学式为H3PO4。于一些实施例中，含锰化合物可为例如但不限于碳酸锰(化学式为MnCO3)、硝酸锰(化学式为Mn(NO3)2)、硫酸锰(化学式为MnSO4)或其他带有锰离子的化合物，含铁化合物可为例如但不限于醋酸亚铁(Fe(CH3COO)2)、草酸铁二水合物(化学式为FeC2O4·2H2O)，含锂化合物可为例如但不限于碳酸锂(化学式为Li2CO3)、氢氧化锂(化学式为LiOH)、醋酸锂(化学式为LiCH3COO)或其他带有锂离子的化合物，且碳源可为醣类、有机化合物、聚合物或高分子材料，但不以此为限。
其次，如步骤S600所示，以含锰化合物、含铁化合物、磷酸与部分的去离子水进行反应，以生成第二生成物。步骤S600更可包括步骤：对第二生成物进行研磨分散动作以及干燥动作。
然后，如步骤S700所示，将第二生成物置于第一温度下至少第一时间，以生成第二前驱物，该第二前驱物的化学式为(Mnx,Fe1-x)5(HPO4)2(PO4)2(H2O)4，其中0.5<x≦1，60℃≦第一温度≦100℃，且第一时间≧18小时。
最后，如步骤S800所示，以至少第二前驱物、含锂化合物及部分的去离子水进行反应，并添加碳源后进行锻烧，以生成电池复合材料，其中该电池复合材料的化学式为LiMnxFe1-xPO4。
以下将以示范性实施例辅助说明本公开的电池复合材料及其前驱物的制备方法：
实施例1
首先提供574.7克的碳酸锰(MnCO3)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再置于60℃至100℃温度条件下至少干燥18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射(X-ray Diffraction,XRD)分析结果如图4A所示，对照标准衍射图谱(JCPDS Card)后，确认其结构为Mn5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜(SEM)分析图则如图4B所示。
实施例2
首先提供574.7克的碳酸锰(MnCO3)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再进行辗压成型脱水后，置于60℃至100℃温度条件下至少18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图4A所示，对照标准衍射图谱后，确认其结构为Mn5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图4B所示。
实施例3
首先提供574.7克的碳酸锰(MnCO3)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再以雾化干燥法干燥后，置于60℃至100℃温度条件下至少18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图4A所示，对照标准衍射图谱后，确认其结构为Mn5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图4B所示。
实施例4
首先提供894.9克的硝酸锰(Mn(NO3)2)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，以氨水(NH4)调整pH值到7～8，沉降后生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再置于60℃至100℃温度条件下至少干燥18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图5A所示，对照标准衍射图谱后，确认其结构为Mn5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图5B所示。
实施例5
首先提供754.9克的硫酸锰(MnSO4)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以氨水(NH4)调整pH值到7～8，沉降后生成第一生成物，经过滤洗后的滤洗半成品，使用球磨的方式将第一生成物进行研磨分散，再置于60℃至100℃温度条件下至少干燥18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图6A所示，对照标准衍射图谱后，确认其结构为Mn5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图6B所示。
实施例6
首先提供402.3克的碳酸锰(MnCO3)以及260.9克的醋酸亚铁(Fe(CH3COO)2)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再置于60℃至100℃温度条件下至少干燥18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图7A所示，对照标准衍射图谱后，确认其结构为(Mn0.7,Fe0.3)5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图7B所示。
实施例7
首先提供402.3克的碳酸锰(MnCO3)以及269.8克的草酸铁二水合物(FeC2O4·2H2O)与重量百分浓度为85.1％的磷酸(H3PO4)575.61克以及2升的去离子水进行反应，以生成第一生成物，接着，使用球磨的方式将第一生成物进行研磨分散，再置于60℃至100℃温度条件下至少干燥18小时，进行低温成相以生成前驱物。所得的前驱物经X光衍射分析结果如图8A所示，对照标准衍射图谱后，确认其结构为(Mn0.7,Fe0.3)5(HPO4)2(PO4)2(H2O)4，其表面形貌的扫描式电子显微镜分析图则如图8B所示。
实施例8
将前述实施例所得的前驱物Mn5(HPO4)2(PO4)2(H2O)4取799.88克与184.7克的碳酸锂(Li2CO3)以及2升的去离子水进行反应，分散研磨后再添加碳源以得到前驱物溶液，将该前驱物溶液以喷雾干燥法进行干燥，并且以600℃进行烧结成相，持温5小时后得到的电池复合材料，经X光衍射分析结果如图9A所示，对照标准衍射图谱后，确认其结构为磷酸锂锰(LiMnPO4)，其表面形貌的扫描式电子显微镜分析图则如图9B所示。
实施例9
将前述实施例所得的前驱物Mn5(HPO4)2(PO4)2(H2O)4取799.88克与209.7克的氢氧化锂(LiOH)以及2升的去离子水进行反应，分散研磨后再添加碳源以得到前驱物溶液，将该前驱物溶液以喷雾干燥法进行干燥，并且以600℃进行烧结成相，持温5小时后得到的电池复合材料，经X光衍射分析结果如图9A所示，对照标准衍射图谱后，确认其结构为磷酸锂锰(LiMnPO4)，其表面形貌的扫描式电子显微镜分析图则如图9C所示。
实施例10
将前述实施例所得的前驱物Mn5(HPO4)2(PO4)2(H2O)4取559.92克与226.23克的六磷酸七铁(Fe7(PO4)6)和184.7克的碳酸锂(Li2CO3)以及2升的去离子水进行反应，分散研磨后再添加碳源以得到前驱物溶液，将该前驱物溶液以喷雾干燥法进行干燥，并且以600℃进行烧结成相，持温5小时后得到的电池复合材料，经X光衍射分析结果如图10A所示，对照标准衍射图谱后，确认其结构为磷酸锂铁锰(LiMn0.7Fe0.3PO4)，其表面形貌的扫描式电子显微镜分析图则如图10B所示。
实施例11
将前述实施例所得的前驱物Mn5(HPO4)2(PO4)2(H2O)4取559.92克与226.23克的磷酸铁二水合物(FePO4·2H2O)和184.7克的碳酸锂(Li2CO3)以及2升的去离子水进行反应，分散研磨后再添加碳源以得到前驱物溶液，将该前驱物溶液以喷雾干燥法进行干燥，并且以600℃进行烧结成相，持温5小时后得到的电池复合材料，经X光衍射分析结果如图11A所示，对照标准衍射图谱后，确认其结构为磷酸锂铁锰(LiMn0.7Fe0.3PO4)，其表面形貌的扫描式电子显微镜分析图则如图11B所示。
实施例12
将前述实施例所得的磷酸锂锰(LiMnPO4)与碳黑(Super P)及4％黏合剂(PVDF+NMP)以8.5：0.5：1比例混合，首先将0.5克碳黑(Super P)与25克黏合剂(PVDF：NMP＝40：960)以转速1200rpm混合10分钟，随后添加磷酸锂锰(LiMnPO4)8.5克，再混合10分钟，接着以刮刀涂布机将分散完成的浆料涂布在铝基板上，涂布厚度为0.3毫米。将涂好的极片放入烘箱中以温度110℃烘干1小时后取出，以锂金属当作负极打出直径为1.3公分的圆形极板，以体积莫耳浓度1M的LiPF6与体积比为3：7的EC及EMC混合为电解液，将其制作成钮扣型电池(coin-cell)，利用充放电机进行0.1库仑充放2个循环以及2库仑充放2个循环的电性测试，测试结果如图12所示，其截止电压为2至4.5伏特。
实施例13
将前述实施例所得的磷酸锂铁锰(LiMnxFe1-xPO4)与碳黑(Super P)及4％黏合剂(PVDF+NMP)以8.5：0.5：1比例混合，首先，将0.5克碳黑(Super P)与25克黏合剂(PVDF：NMP＝40：960)以转速1200rpm混合10分钟，随后添加磷酸锂铁锰(LiMnxFe1-xPO4)8.5克，再混合10分钟，接着以刮刀涂布机将分散完成的浆料涂布在铝基板上，涂布厚度为0.3毫米。将涂好的极片放入烘箱中以温度110℃烘干1小时后取出，以锂金属当作负极打出直径为1.3公分的圆形极板，以体积莫耳浓度1M的LiPF6与体积比为3：7的EC及EMC混合为电解液，将其制作成钮扣型电池(coin-cell)，利用充放电机进行0.1库仑充放2个循环以及2库仑充放2个循环的电性测试，测试结果如图13所示，其截止电压为2至4.5伏特。
综上所述，本公开的电池复合材料及其前驱物的制备方法，透过简单的水溶液法于酸性环境下反应产生前驱物，再与含锂化合物进行反应以制备电池复合材料，其制程步骤较为简易，可有效节省制备时间，达到提高制备效率的效果。同时，透过低温成相法在制程 中以低温于短时间内形成前驱物，可使耗费能量减少，且前驱物的成相亦较为稳定，进而降低制备所需成本并且有效提升产品质量。
纵使本发明已由上述实施例详细叙述而可由熟悉本技艺人士任施匠思而为诸般修饰，然皆不脱如附申请专利范围所欲保护者。

Claims (15)

  1. 一种电池复合材料的制备方法，至少包括步骤：
    (a)提供含锰化合物、磷酸、含锂化合物、碳源及去离子水，其中该磷酸的化学式为H3PO4；
    (b)以该含锰化合物、该磷酸与部分的该去离子水进行反应，以生成第一生成物；
    (c)将该第一生成物置于一第一温度下至少一第一时间，以生成第一前驱物，该第一前驱物的化学式为Mn5(HPO4)2(PO4)2(H2O)4；以及
    (d)以至少该第一前驱物、该含锂化合物与部分的该去离子水进行反应，并添加该碳源后进行锻烧，以生成电池复合材料。
  2. 如权利要求1所述的电池复合材料的制备方法，其中该含锰化合物为碳酸锰、硝酸锰或硫酸锰，该含锂化合物为碳酸锂、氢氧化锂或醋酸锂。
  3. 如权利要求1所述的电池复合材料的制备方法，其中该电池复合材料的化学式为LiMnPO4。
  4. 如权利要求1所述的电池复合材料的制备方法，其中该步骤(d)以该第一前驱物与含铁化合物、该含锂化合物与部分的该去离子水进行反应，并添加该碳源后进行锻烧，以生成该电池复合材料，其中该电池复合材料的化学式为LiMnxFe1-xPO4，其中x大于0.5且小于或等于1。
  5. 如权利要求4所述的电池复合材料的制备方法，其中该含铁化合物为六磷酸七铁，化学式为Fe7(PO4)6，或磷酸铁二水合物，化学式为FePO4·2H2O。
  6. 如权利要求1所述的电池复合材料的制备方法，其中该步骤(b)更包括步骤(b1)：对该第一生成物进行一研磨分散动作以及一干燥动作。
  7. 如权利要求6所述的电池复合材料的制备方法，其中该研磨分散动作透过球磨机实现。
  8. 如权利要求6所述的电池复合材料的制备方法，其中该干燥动作透过辗压脱水或喷雾干燥实现。
  9. 如权利要求1所述的电池复合材料的制备方法，其中该步骤(d)更包括步骤：
    (d1)以该第一前驱物、该含锂化合物与部分的该去离子水进行反应并添加分散剂；
    (d2)进行一研磨动作并添加该碳源，以得到第一前驱物溶液；
    (d3)对该第一前驱物溶液进行一喷雾干燥动作及一热处理动作，以生成该电池复合材料。
  10. 如权利要求9所述的电池复合材料的制备方法，其中该热处理动作于温度大于摄氏600度进行至少5小时的热处理。
  11. 如权利要求1所述的电池复合材料的制备方法，其中该第一温度大于或等于摄氏60度且小于或等于摄氏100度。
  12. 如权利要求1所述的电池复合材料的制备方法，其中该第一时间大于或等于18小 时。
  13. 一种电池复合材料的前驱物的制备方法，至少包括步骤：
    (a)提供含锰化合物、磷酸及去离子水，其中该磷酸的化学式为H3PO4；
    (b)以该含锰化合物、该磷酸与该去离子水进行反应，以生成第一生成物；以及
    (c)将该第一生成物置于第一温度下至少第一时间，以生成第一前驱物，该第一前驱物的化学式为Mn5(HPO4)2(PO4)2(H2O)4。
  14. 一种电池复合材料的制备方法，至少包括步骤：
    以Mn5(HPO4)2(PO4)2(H2O)4为前驱物，并以该前驱物与含锂化合物及去离子水进行反应，并添加碳源后进行锻烧，以生成电池复合材料，其中该电池复合材料的化学式为LiMnPO4。
  15. 一种电池复合材料的制备方法，至少包括步骤：
    (a)提供含锰化合物、含铁化合物、磷酸、含锂化合物、碳源及去离子水，其中该磷酸的化学式为H3PO4；
    (b)以该含锰化合物、该含铁化合物、该磷酸与部分的该去离子水进行反应，以生成第二生成物；
    (c)将该第二生成物置于第一温度下至少第一时间，以生成第二前驱物，该第二前驱物的化学式为(Mnx,Fe1-x)5(HPO4)2(PO4)2(H2O)4，其中x大于0.5且小于或等于1；以及
    (d)以至少该第二前驱物、该含锂化合物与部分的该去离子水进行反应，并添加该碳源后进行锻烧，以生成电池复合材料，其中该电池复合材料的化学式为LiMnxFe1-xPO4。
PCT/CN2016/070382 2015-01-08 2016-01-07 电池复合材料及其前驱物的制备方法 WO2016110261A1 (zh)

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