WO2023109020A1 - Method for preparing phosphate positive electrode material - Google Patents

Method for preparing phosphate positive electrode material Download PDF

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WO2023109020A1
WO2023109020A1 PCT/CN2022/095534 CN2022095534W WO2023109020A1 WO 2023109020 A1 WO2023109020 A1 WO 2023109020A1 CN 2022095534 W CN2022095534 W CN 2022095534W WO 2023109020 A1 WO2023109020 A1 WO 2023109020A1
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sodium
lithium
phosphate
source
potassium
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PCT/CN2022/095534
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French (fr)
Chinese (zh)
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夏永高
高洁
刘翔
张国栋
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中国科学院宁波材料技术与工程研究所
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Publication of WO2023109020A1 publication Critical patent/WO2023109020A1/en

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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of lithium ion batteries, and in particular relates to a preparation method of a phosphate cathode material.
  • Phosphate cathode materials due to their high capacity, long cycle life, good thermal stability, environmental friendliness, and low cost, are widely used in electric vehicles and large-scale energy storage facilities, accounting for one-third of the entire lithium-ion battery market one.
  • the methods for preparing phosphate cathode materials are mainly hydrothermal method and solid-phase sintering method.
  • the hydrothermal method needs to be reacted in a high-pressure environment, which has high requirements for equipment, and there is a safety hazard of excessive pressure, and A lot of wastewater is produced and the process is complicated; while the high-temperature solid-phase method needs to be reacted at a temperature above 500°C, requires high-temperature resistant equipment, consumes a lot of energy, and takes a long time to react. In order to reduce energy consumption and reduce carbon emissions, it is urgent to develop a low-carbon, environmentally friendly and safe preparation method for phosphate cathode materials.
  • the technical problem to be solved in the present invention is to provide a method for preparing a phosphate positive electrode material, the method for preparing a phosphate positive electrode material provided by the present invention can be carried out under lower temperature and pressure conditions, reducing energy consumption and carbon emissions.
  • the invention provides a kind of preparation method of phosphate cathode material, comprises the following steps:
  • the phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn, Mo , one or more of W, N is one or more of Fe, Mn, Co, Ni, 0 ⁇ x ⁇ 0.1, 0.9 ⁇ y ⁇ 1;
  • the phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.1, 0.9 ⁇ b ⁇ 1.
  • the temperature of the reaction is ⁇ 50°C, and the pressure of the reaction is ⁇ 0.5MPa.
  • the lithium source is selected from one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium formate and lithium tetraborate;
  • the sodium source is selected from one or more of sodium hydroxide, sodium acetate, sodium nitrate, sodium oxalate, sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium iodide, sodium sulfite and sodium bisulfite .
  • the potassium source is selected from one or more of potassium hydroxide, potassium nitrate, potassium sulfate, potassium chloride, potassium iodide, potassium sulfite and potassium bisulfite.
  • the reducing agent is selected from one or more of sodium sulfite, sodium bisulfite, hydrogen sulfide, sulfur dioxide, oxalate, iodine salt, formaldehyde, sodium borohydride, ascorbic acid and sodium sulfide.
  • the molar ratio of at least one of lithium in the lithium source, sodium in the sodium source, and potassium in the potassium source to the phosphate is (1-5):1;
  • the molar ratio of the reducing agent to the phosphate is (0.1-5):1.
  • the phosphate is prepared according to the following method:
  • the phosphate alkali metal compound, oxidizing agent, acid and water are mixed and reacted to obtain phosphate.
  • the oxidant is selected from one or more of hydrogen peroxide, oxygen, ozone, sodium peroxide, hypochlorous acid, hypoiodous acid and peracetic acid;
  • the acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid and oxalic acid;
  • the temperature of mixing the phosphate alkali metal compound, oxidizing agent, acid and water to react is 0-100° C. and the time is 0.1-10 h.
  • At least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water are mixed and reacted at a temperature of 0-50° C., a pressure of 0.08-0.5 MPa, and a time of 0.1-10 hours.
  • At least one of the lithium source, the sodium source and the potassium source, the phosphate, the reducing agent and water are mixed and reacted under normal temperature and pressure conditions.
  • a solid-liquid mixture is obtained;
  • the solid-liquid mixture is sequentially filtered, washed with water, and dried to obtain a phosphate cathode material.
  • the present invention provides a method for preparing a phosphate cathode material, comprising the following steps: mixing at least one of a lithium source, a sodium source and a potassium source, phosphate, a reducing agent and water for reaction , to obtain a phosphate positive electrode material;
  • the phosphate is an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, One or more of Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, 0 ⁇ x ⁇ 0.1, 0.9 ⁇ y ⁇ 1.
  • the phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.1, 0.9 ⁇ b ⁇ 1.
  • the present invention can react under lower temperature and pressure conditions, even under normal temperature and normal pressure conditions, has short reaction time, simple and safe process, low energy consumption, effectively reduces carbon emissions, and has great cost advantages.
  • Fig. 1 is the XRD pattern of the lithium iron phosphate material prepared in Example 1 of the present invention
  • Fig. 2 is the charging and discharging curve diagram of the lithium iron phosphate material prepared in Example 1 of the present invention
  • Fig. 3 is the XRD pattern of the iron phosphate material prepared by the present invention.
  • Fig. 4 is the XRD figure of commercially available iron phosphate material
  • Fig. 5 is the XRD comparative figure of iron phosphate prepared by the present invention and commercially available iron phosphate;
  • Fig. 6 is the comparison of solid XRD crystal forms before and after the reaction of Comparative Example 2;
  • Fig. 7 is the XRD figure of the iron phosphate doped with Al prepared by the present invention.
  • Fig. 8 is an XRD pattern of the sodium iron phosphate material prepared in Example 6 of the present invention.
  • the invention provides a kind of preparation method of phosphate cathode material, comprises the following steps:
  • the phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn, Mo , one or more of W, N is one or more of Fe, Mn, Co, Ni, 0 ⁇ x ⁇ 0.1, 0.9 ⁇ y ⁇ 1.
  • the phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.1, 0.9 ⁇ b ⁇ 1.
  • At least one of the lithium source, the sodium source and the potassium source is dissolved in water to obtain a solution containing lithium ions and/or sodium ions and/or potassium ions,
  • the lithium source is selected from one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium formate and lithium tetraborate.
  • the sodium source is selected from one or more of sodium hydroxide, sodium acetate, sodium nitrate, sodium oxalate, sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium iodide, sodium sulfite and sodium bisulfite .
  • the potassium source is selected from one or more of potassium hydroxide, potassium nitrate, potassium sulfate, potassium chloride, potassium iodide, potassium sulfite and potassium bisulfite.
  • the water used has no special requirements and can be a conventional choice in this field.
  • phosphate is added to the solution containing lithium ions and/or sodium ions and/or potassium ions and stirred.
  • the stirring time is 0.1-5 h, preferably 0.5, 1, 2, 3, 4, 5, or any value between 0.1-5 h.
  • the molar ratio of at least one molar number of lithium in the lithium source, sodium in the sodium source, and potassium in the potassium source to the phosphate is (1-5):1, preferably 1:1, 2:1, 3:1, 4:1, 5:1, or (1 ⁇ 5): any value between 1.
  • the phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn , one or more of Mo, W, N is one or more of Fe, Mn, Co, Ni, 0 ⁇ x ⁇ 0.1, 0.9 ⁇ y ⁇ 1;
  • the phosphate of the olivine structure is preferably prepared according to the following method:
  • the phosphate alkali metal compound, oxidizing agent, acid and water are mixed and reacted to obtain phosphate.
  • the phosphate alkali metal compound is an olivine type phosphate alkali metal compound.
  • the alkali metal in the phosphate alkali metal compound is selected from one or more of lithium, sodium and potassium.
  • the phosphate alkali metal compound is A f D c E d PO 4 ,
  • A is one or more of Li, Na, K
  • D is Li, Na, K, Ca, Al, Mg, Cu, F, B, one or more of Ni, Co, Mn, Ti, Nb, Sn, Mo, W
  • E is one or more of Fe, Mn, Co, Ni, 0.5 ⁇ f ⁇ 1.05, 0 ⁇ c ⁇ 0.1, 0.9 ⁇ d ⁇ 1.
  • the oxidizing agent is selected from one or more of hydrogen peroxide, oxygen, ozone, sodium peroxide, hypochlorous acid, hypoiodous acid and peracetic acid.
  • the acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid and oxalic acid.
  • the molar ratio of the phosphate alkali metal compound, oxidizing agent and acid is 1:(1-5):(1-5), preferably 1:(2-4):(2-4).
  • the temperature for mixing the phosphate alkali metal compound, oxidant, acid and water for reaction is 0-100°C, preferably 0, 5, 10, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 , or any value between 0 and 100°C, preferably at room temperature, for 0.1 to 10 hours, preferably 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or Any value between 0.1 and 10h.
  • a reducing agent During the above process of adding phosphate for stirring, add a reducing agent and continue stirring to obtain a solid-liquid mixture.
  • the time for continuing stirring is 0.1-10 h, preferably 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 0.1-10 h.
  • the reducing agent is selected from one or more of sodium sulfite, sodium bisulfite, hydrogen sulfide, sulfur dioxide, oxalate, iodine salt, formaldehyde, sodium borohydride, ascorbic acid and sodium sulfide.
  • the molar ratio of the reducing agent to the phosphate is (0.1-5):1, preferably 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, or (0.1 ⁇ 5): Any value between 1.
  • the temperature of the reaction is ⁇ 50°C, and the pressure of the reaction is ⁇ 0.5MPa; in some embodiments of the present invention, the temperature of the reaction is 0-50°C, preferably 0, 5, 15, 20, 25, 30, 50, or any value at 0 to 50°C, the pressure is 0.08 to 0.5 MPa, preferably 0.08, 0.1, 0.15, 0.2, or any value between 0.08 to 0.5 MPa; in the present invention
  • the temperature may be normal temperature
  • the pressure may be normal pressure.
  • the solid-liquid mixture is sequentially filtered, washed with water, and dried to obtain a phosphate positive electrode material.
  • the phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1 ⁇ z ⁇ 0.1, 0 ⁇ a ⁇ 0.1, 0.9 ⁇ b ⁇ 1.
  • the equipment used for filtering, washing and drying in the present invention has no special requirements, and can be conventional selection in this field.
  • the method of the present invention uses cheap phosphate as a raw material, matches corresponding lithium source, sodium source, potassium source, and can react under lower temperature and pressure conditions, even under normal temperature and pressure conditions.
  • the time is short, the process is simple, safe, low energy consumption, effectively reduces carbon emissions, and has great cost advantages.
  • the phosphate with olivine structure used is prepared according to the following method:
  • ferric phosphate of embodiment 1 ⁇ embodiment 4 is prepared according to the following method:
  • Fig. 3 is an XRD pattern of the iron phosphate material prepared in the present invention.
  • the Al-doped iron phosphate of embodiment 5 is prepared according to the following method:
  • FIG. 7 is an XRD pattern of the Al-doped iron phosphate material prepared in the present invention.
  • the iron phosphate of embodiment 6 and embodiment 7 is prepared according to the following method:
  • the manganese phosphate of embodiment 8 is prepared according to the following method:
  • the ferromanganese phosphate of embodiment 9 is prepared according to the following method:
  • the cobalt iron phosphate of embodiment 10 is prepared according to the following method:
  • the ferronickel phosphate of embodiment 11 is prepared according to the following method:
  • the iron phosphate of embodiment 12 is prepared according to the following method:
  • step (2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 0.99 FePO 4 .
  • step (2) Add 60g of iron phosphate to the solution obtained in step (1), then stir with a stirrer for 0.5h at a speed of 360 rpm;
  • step (3) Add 80 g of sodium oxalate during the stirring process of step (2), and continue stirring for 6 hours to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 1.00 FePO 4 .
  • step (2) Add 60g of ferric phosphate to the solution obtained in step (1), then stir for 0.2h with a stirrer at a speed of 360 rpm;
  • step (3) Add 100 g of potassium oxalate during the stirring process of step (2), and continue stirring for 5 hours to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 0.99 FePO 4 .
  • step (2) Add 70g of ferric phosphate to the solution obtained in step (1), then stir for 0.2h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70 g of ascorbic acid during the stirring process of step (2), and continue stirring for 3 h at 50° C. and 0.5 MPa to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 1.01 FePO 4 .
  • step (2) Add 70g of Al-doped ferric phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain a doped Al Lithium iron phosphate material, Li 0.99 Al 0.01 Fe 0.99 PO 4 .
  • step (2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • FIG. 8 is an XRD pattern of the sodium iron phosphate material prepared in Example 6 of the present invention.
  • step (2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain sodium ferric phosphate Lithium material, Li 0.73 Na 0.26 FePO 4 .
  • step (1) add 70g manganese phosphate in the solution that step (1) obtains, then stir 0.5h with the rotating speed of 360 rev/mins with agitator;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium manganese phosphate Material, Li 0.98 MnPO 4 .
  • step (2) Add 50g of ferromanganese phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying 10h to obtain ferromanganese phosphate Lithium material, Li 1.0 Fe 0.63 Mn 0.37 PO 4 .
  • step (2) Add 60g of cobalt-iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 50 g of ascorbic acid and 20 g of ammonium oxalate during the stirring process of step (2), and continue stirring for 4 hours to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain ferric cobalt phosphate Lithium material, Li 0.97 Fe 0.58 Co 0.41 PO 4 .
  • step (2) Add 60g nickel-iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) Add 50g ascorbic acid and 30g ammonium iodide during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10h to obtain iron nickel phosphate Lithium material, Li 0.99 Fe 0.48 Ni 0.51 PO 4 .
  • step (2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
  • step (3) add 70g ascorbic acid during the stirring process of step (2), continue to stir for 5h, obtain solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain K 0.21 Na 0.78 FePO 4 .
  • Fig. 4 is the XRD pattern of commercially available ferric phosphate
  • FIG. 5 is a comparison chart of XRD of iron phosphate prepared by the present invention and commercially available iron phosphate.
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10h, and cannot obtain ferric phosphate lithium material.
  • step (2) Add 70 g of commercially available ferric phosphate to the solution obtained in step (1), then stir for 0.5 h with a stirrer at a speed of 360 rpm;
  • step (3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
  • step (1) Place the hydrothermal kettle in step (1) in a blast oven at 180°C and heat for 24 hours to obtain a solid-liquid mixture;
  • step (3) Filter the solid-liquid mixture obtained in step (2) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material.
  • step (3) The lithium iron phosphate material prepared in step (3) was subjected to an electrochemical performance test according to the method described in Test Example 1.
  • the discharge capacity at 0.5C rate was 147.6mAh/g, and the first-time efficiency at 0.5C was 97%.
  • the electrochemical performance test is carried out according to the following method: Weigh 2g of the lithium iron phosphate material prepared in Example 1 and PVDF (polyvinylidene fluoride), Super P carbon is compounded with a mass ratio of 80:10:10, and NMP ( N-methylpyrrolidone) is used as a dispersant to slurry, coated on a flat aluminum foil, dried in a blast dryer for 12h, and punched into a positive electrode sheet with a diameter of 14mm after rolling.
  • PVDF polyvinylidene fluoride
  • Super P carbon is compounded with a mass ratio of 80:10:10
  • NMP N-methylpyrrolidone
  • the results of the electrochemical performance test are shown in Figure 2.
  • the electrochemical performance of the lithium iron phosphate positive electrode material prepared by the present invention has a discharge capacity of 152.1mAh/g at a rate of 0.5C, and an initial efficiency of 98% at 0.5C, indicating that the preparation of the present invention
  • the obtained lithium iron phosphate material has good electrical properties.
  • the process for preparing lithium iron phosphate material in the present invention can be carried out at normal temperature and pressure, with low energy consumption, low carbon emissions, no need for high-pressure and high-temperature-resistant equipment, safe and controllable, and great cost advantages.

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Abstract

The present invention provides a method for preparing a phosphate positive electrode material. The method comprises the following step: mixing at least one of a lithium source, a sodium source and a potassium source with a phosphate, a reducing agent and water to perform a reaction, so as to obtain a phosphate positive electrode material product. In the present invention, the reaction can be performed under the conditions of a relatively low temperature and a relatively low pressure, or even under the conditions of normal atmospheric temperature and normal pressure. The reaction time is short; the process is simple and safe; and the energy consumption is low, thereby effectively reducing the carbon emission.

Description

一种磷酸盐正极材料的制备方法A kind of preparation method of phosphate cathode material
本申请要求于2021年12月16日提交中国专利局、申请号为202111543018.2、发明名称为“一种磷酸盐正极材料的制备方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。This application claims the priority of the Chinese patent application submitted to the China Patent Office on December 16, 2021, with the application number 202111543018.2 and the title of the invention "a method for preparing a phosphate cathode material", the entire contents of which are incorporated herein by reference. Applying.
技术领域technical field
本发明属于锂离子电池技术领域，具体涉及一种磷酸盐正极材料的制备方法。The invention belongs to the technical field of lithium ion batteries, and in particular relates to a preparation method of a phosphate cathode material.
背景技术Background technique
磷酸盐正极材料，由于其容量高、循环寿命长、热稳定性好、环境友好、成本低等特点，被广泛应用于电动汽车和大规模的储能设施，占有整个锂离子电池市场的三分之一。目前制备磷酸盐正极材料的方法主要是水热法和固相烧结法，其中，水热法需要在高压的环境下进行反应，对设备具有较高的要求，存在压力过大的安全隐患，而且产生的废水多，工艺复杂；而高温固相法则需要在500℃以上进行反应，需要耐高温设备，且耗能大，反应时间长。为了降低能耗，减少碳排放，亟需发展出一种低碳环保且安全的磷酸盐正极材料的制备方法。Phosphate cathode materials, due to their high capacity, long cycle life, good thermal stability, environmental friendliness, and low cost, are widely used in electric vehicles and large-scale energy storage facilities, accounting for one-third of the entire lithium-ion battery market one. At present, the methods for preparing phosphate cathode materials are mainly hydrothermal method and solid-phase sintering method. Among them, the hydrothermal method needs to be reacted in a high-pressure environment, which has high requirements for equipment, and there is a safety hazard of excessive pressure, and A lot of wastewater is produced and the process is complicated; while the high-temperature solid-phase method needs to be reacted at a temperature above 500°C, requires high-temperature resistant equipment, consumes a lot of energy, and takes a long time to react. In order to reduce energy consumption and reduce carbon emissions, it is urgent to develop a low-carbon, environmentally friendly and safe preparation method for phosphate cathode materials.
发明内容Contents of the invention
有鉴于此，本发明要解决的技术问题在于提供一种磷酸盐正极材料的制备方法，本发明提供的磷酸盐正极材料的制备方法可以在较低的温度和压力条件下进行，降低了能耗以及碳排量。In view of this, the technical problem to be solved in the present invention is to provide a method for preparing a phosphate positive electrode material, the method for preparing a phosphate positive electrode material provided by the present invention can be carried out under lower temperature and pressure conditions, reducing energy consumption and carbon emissions.
本发明提供了一种磷酸盐正极材料的制备方法，包括以下步骤：The invention provides a kind of preparation method of phosphate cathode material, comprises the following steps:
将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应，得到磷酸盐正极材料；Mixing and reacting at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water to obtain phosphate positive electrode material;
所述磷酸盐为橄榄石结构，为M xN yPO 4，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，0≤x≤0.1，0.9≤y≤1； The phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn, Mo , one or more of W, N is one or more of Fe, Mn, Co, Ni, 0≤x≤0.1, 0.9≤y≤1;
所述磷酸盐正极材料为Q 1-zM aN bPO 4，Q为Li、Na、K中的一种或多种，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，-0.1≤z≤ 0.1，0≤a≤0.1，0.9≤b≤1。 The phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1≤z≤0.1, 0≤a≤0.1, 0.9≤b≤1.
优选的，所述反应的温度≤50℃，所述反应的压力≤0.5MPa。Preferably, the temperature of the reaction is ≤50°C, and the pressure of the reaction is ≤0.5MPa.
优选的，所述锂源选自氢氧化锂、醋酸锂、硝酸锂、草酸锂、硫酸锂、氯化锂、碳酸锂、碳酸氢锂、甲酸锂和四硼酸锂中的一种或多种；Preferably, the lithium source is selected from one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium formate and lithium tetraborate;
所述钠源选自氢氧化钠、醋酸钠、硝酸钠、草酸钠、硫酸钠、氯化钠、碳酸钠、碳酸氢钠、碘化钠、亚硫酸钠和亚硫酸氢钠中的一种或多种。The sodium source is selected from one or more of sodium hydroxide, sodium acetate, sodium nitrate, sodium oxalate, sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium iodide, sodium sulfite and sodium bisulfite .
所述钾源选自氢氧化钾、硝酸钾、硫酸钾、氯化钾、碘化钾、亚硫酸钾和亚硫酸氢钾中的一种或多种。The potassium source is selected from one or more of potassium hydroxide, potassium nitrate, potassium sulfate, potassium chloride, potassium iodide, potassium sulfite and potassium bisulfite.
优选的，所述还原剂选自亚硫酸钠、亚硫酸氢钠、硫化氢、二氧化硫、草酸盐、碘盐、甲醛、硼氢化钠、抗坏血酸和硫化钠中的一种或多种。Preferably, the reducing agent is selected from one or more of sodium sulfite, sodium bisulfite, hydrogen sulfide, sulfur dioxide, oxalate, iodine salt, formaldehyde, sodium borohydride, ascorbic acid and sodium sulfide.
优选的，所述锂源中锂、钠源中钠和钾源中钾的至少一种的摩尔数与所述磷酸盐的摩尔比为(1～5)：1；Preferably, the molar ratio of at least one of lithium in the lithium source, sodium in the sodium source, and potassium in the potassium source to the phosphate is (1-5):1;
所述还原剂与所述磷酸盐的摩尔比为(0.1～5):1。The molar ratio of the reducing agent to the phosphate is (0.1-5):1.
优选的，所述磷酸盐按照如下方法进行制备：Preferably, the phosphate is prepared according to the following method:
将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应，得到磷酸盐。The phosphate alkali metal compound, oxidizing agent, acid and water are mixed and reacted to obtain phosphate.
优选的，所述氧化剂选自过氧化氢、氧气、臭氧、过氧化钠、次氯酸、次碘酸和过氧乙酸中的一种或多种；Preferably, the oxidant is selected from one or more of hydrogen peroxide, oxygen, ozone, sodium peroxide, hypochlorous acid, hypoiodous acid and peracetic acid;
所述酸选自硫酸、盐酸、硝酸、碳酸和草酸中的一种或多种；The acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid and oxalic acid;
将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应的温度为0～100℃，时间为0.1～10h。The temperature of mixing the phosphate alkali metal compound, oxidizing agent, acid and water to react is 0-100° C. and the time is 0.1-10 h.
优选的，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应的温度为0～50℃，压力为0.08～0.5MPa，时间为0.1～10小时。Preferably, at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water are mixed and reacted at a temperature of 0-50° C., a pressure of 0.08-0.5 MPa, and a time of 0.1-10 hours.
优选的，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应可以为常温常压条件。Preferably, at least one of the lithium source, the sodium source and the potassium source, the phosphate, the reducing agent and water are mixed and reacted under normal temperature and pressure conditions.
优选的，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应后，得到固液混合物；Preferably, after mixing at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water for reaction, a solid-liquid mixture is obtained;
将所述固液混合物依次进行过滤、水洗、干燥，得到磷酸盐正极材料。The solid-liquid mixture is sequentially filtered, washed with water, and dried to obtain a phosphate cathode material.
与现有技术相比，本发明提供了一种磷酸盐正极材料的制备方法，包括以下步骤：将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反 应，得到磷酸盐正极材料；所述磷酸盐为橄榄石结构，为M xN yPO 4，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，0≤x≤0.1，0.9≤y≤1。所述磷酸盐正极材料为Q 1-zM aN bPO 4，Q为Li、Na、K中的一种或多种，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，-0.1≤z≤0.1，0≤a≤0.1，0.9≤b≤1。本发明可以在较低的温度和压力条件下，甚至是常温常压条件下进行反应，反应时间短，工艺简单、安全、耗能低，有效降低了碳排放，具有极大的成本优势。 Compared with the prior art, the present invention provides a method for preparing a phosphate cathode material, comprising the following steps: mixing at least one of a lithium source, a sodium source and a potassium source, phosphate, a reducing agent and water for reaction , to obtain a phosphate positive electrode material; the phosphate is an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, One or more of Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, 0≤x≤0.1, 0.9≤y≤1. The phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1≤z≤0.1, 0≤a≤0.1, 0.9≤b≤1. The present invention can react under lower temperature and pressure conditions, even under normal temperature and normal pressure conditions, has short reaction time, simple and safe process, low energy consumption, effectively reduces carbon emissions, and has great cost advantages.
附图说明Description of drawings
图1为本发明实施例1制备的磷酸铁锂材料的XRD图；Fig. 1 is the XRD pattern of the lithium iron phosphate material prepared in Example 1 of the present invention;
图2为本发明实施例1制备的磷酸铁锂材料的充放电曲线图；Fig. 2 is the charging and discharging curve diagram of the lithium iron phosphate material prepared in Example 1 of the present invention;
图3为本发明制备的磷酸铁材料的XRD图；Fig. 3 is the XRD pattern of the iron phosphate material prepared by the present invention;
图4为市售磷酸铁材料的XRD图；Fig. 4 is the XRD figure of commercially available iron phosphate material;
图5为本发明制备的磷酸铁与市售磷酸铁的XRD比较图；Fig. 5 is the XRD comparative figure of iron phosphate prepared by the present invention and commercially available iron phosphate;
图6为对比例2反应前后固体XRD晶型比较；Fig. 6 is the comparison of solid XRD crystal forms before and after the reaction of Comparative Example 2;
图7为本发明制备的掺杂Al的磷酸铁的XRD图；Fig. 7 is the XRD figure of the iron phosphate doped with Al prepared by the present invention;
图8为本发明实施例6制备的磷酸铁钠材料的XRD图。Fig. 8 is an XRD pattern of the sodium iron phosphate material prepared in Example 6 of the present invention.
具体实施方式Detailed ways
本发明提供了一种磷酸盐正极材料的制备方法，包括以下步骤：The invention provides a kind of preparation method of phosphate cathode material, comprises the following steps:
将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应，得到磷酸盐正极材料；Mixing and reacting at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water to obtain phosphate positive electrode material;
所述磷酸盐为橄榄石结构，为M xN yPO 4，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，0≤x≤0.1，0.9≤y≤1。 The phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn, Mo , one or more of W, N is one or more of Fe, Mn, Co, Ni, 0≤x≤0.1, 0.9≤y≤1.
所述磷酸盐正极材料为Q 1-zM aN bPO 4，Q为Li、Na、K中的一种或多种，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，-0.1≤z≤0.1，0≤a≤0.1，0.9≤b≤1。 The phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1≤z≤0.1, 0≤a≤0.1, 0.9≤b≤1.
本发明首先将锂源、钠源和钾源中的至少一种溶解于水中，得到含有锂离子和/或钠离子和/或钾离子的溶液，In the present invention, at least one of the lithium source, the sodium source and the potassium source is dissolved in water to obtain a solution containing lithium ions and/or sodium ions and/or potassium ions,
其中，所述锂源选自氢氧化锂、醋酸锂、硝酸锂、草酸锂、硫酸锂、氯化锂、碳酸锂、碳酸氢锂、甲酸锂和四硼酸锂中的一种或多种。所述钠源选自氢氧化钠、醋酸钠、硝酸钠、草酸钠、硫酸钠、氯化钠、碳酸钠、碳酸氢钠、碘化钠、亚硫酸钠和亚硫酸氢钠中的一种或多种。所述钾源选自氢氧化钾、硝酸钾、硫酸钾、氯化钾、碘化钾、亚硫酸钾和亚硫酸氢钾中的一种或多种。所用的水没有特殊要求，可以为本领域的常规选择。Wherein, the lithium source is selected from one or more of lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium formate and lithium tetraborate. The sodium source is selected from one or more of sodium hydroxide, sodium acetate, sodium nitrate, sodium oxalate, sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium iodide, sodium sulfite and sodium bisulfite . The potassium source is selected from one or more of potassium hydroxide, potassium nitrate, potassium sulfate, potassium chloride, potassium iodide, potassium sulfite and potassium bisulfite. The water used has no special requirements and can be a conventional choice in this field.
然后，向所述含有锂离子和/或钠离子和/或钾离子的溶液中加入磷酸盐进行搅拌。所述搅拌的时间为0.1～5h，优选为0.5、1、2、3、4、5，或0.1～5h之间的任意值。所述锂源中锂、钠源中钠和钾源中钾的至少一种的摩尔数与所述磷酸盐的摩尔比为(1～5)：1，优选为1:1、2:1、3:1、4:1、5:1，或(1～5)：1之间的任意值。Then, phosphate is added to the solution containing lithium ions and/or sodium ions and/or potassium ions and stirred. The stirring time is 0.1-5 h, preferably 0.5, 1, 2, 3, 4, 5, or any value between 0.1-5 h. The molar ratio of at least one molar number of lithium in the lithium source, sodium in the sodium source, and potassium in the potassium source to the phosphate is (1-5):1, preferably 1:1, 2:1, 3:1, 4:1, 5:1, or (1～5): any value between 1.
其中，所述磷酸盐为橄榄石结构，为M xN yPO 4，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，0≤x≤0.1，0.9≤y≤1； Wherein, the phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn , one or more of Mo, W, N is one or more of Fe, Mn, Co, Ni, 0≤x≤0.1, 0.9≤y≤1;
在本发明中，所述橄榄石结构的磷酸盐优选按照如下方法进行制备：In the present invention, the phosphate of the olivine structure is preferably prepared according to the following method:
将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应，得到磷酸盐。The phosphate alkali metal compound, oxidizing agent, acid and water are mixed and reacted to obtain phosphate.
其中，所述磷酸盐碱金属化合物为橄榄石型磷酸盐碱金属化合物。所述磷酸盐碱金属化合物中碱金属选自锂、钠、钾中的一种或多种。Wherein, the phosphate alkali metal compound is an olivine type phosphate alkali metal compound. The alkali metal in the phosphate alkali metal compound is selected from one or more of lithium, sodium and potassium.
所述磷酸盐碱金属化合物为A fD cE dPO 4，A为Li、Na、K中的一种或多种，D为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，E为Fe、Mn、Co、Ni中的一种或多种，0.5≤f≤1.05，0≤c≤0.1，0.9≤d≤1。 The phosphate alkali metal compound is A f D c E d PO 4 , A is one or more of Li, Na, K, D is Li, Na, K, Ca, Al, Mg, Cu, F, B, one or more of Ni, Co, Mn, Ti, Nb, Sn, Mo, W, E is one or more of Fe, Mn, Co, Ni, 0.5≤f≤1.05, 0≤ c≤0.1, 0.9≤d≤1.
所述氧化剂选自过氧化氢、氧气、臭氧、过氧化钠、次氯酸、次碘酸和过氧乙酸中的一种或多种。The oxidizing agent is selected from one or more of hydrogen peroxide, oxygen, ozone, sodium peroxide, hypochlorous acid, hypoiodous acid and peracetic acid.
所述酸选自硫酸、盐酸、硝酸、碳酸和草酸中的一种或多种。The acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid and oxalic acid.
所述磷酸盐碱金属化合物、氧化剂、酸的摩尔比为1：(1～5)：(1～5)，优选为1:(2～4)：(2～4)。The molar ratio of the phosphate alkali metal compound, oxidizing agent and acid is 1:(1-5):(1-5), preferably 1:(2-4):(2-4).
将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应的温度为0～100℃，优选为0、5、10、20、25、30、40、50、60、70、80、90、100，或0～100℃之间的任意值，优选为常温条件，时间为0.1～10h，优选为0.1、0.5、1、2、3、4、5、6、7、8、9、10，或0.1～10h之间的任意值。The temperature for mixing the phosphate alkali metal compound, oxidant, acid and water for reaction is 0-100°C, preferably 0, 5, 10, 20, 25, 30, 40, 50, 60, 70, 80, 90, 100 , or any value between 0 and 100°C, preferably at room temperature, for 0.1 to 10 hours, preferably 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or Any value between 0.1 and 10h.
在上述加入磷酸盐进行搅拌的过程中，加入还原剂继续搅拌，得到固液混合物。所述继续搅拌的时间为0.1～10h，优选为0.1、0.5、1、2、3、4、5、6、7、8、9、10，或0.1～10h之间的任意值。During the above process of adding phosphate for stirring, add a reducing agent and continue stirring to obtain a solid-liquid mixture. The time for continuing stirring is 0.1-10 h, preferably 0.1, 0.5, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, or any value between 0.1-10 h.
所述还原剂选自亚硫酸钠、亚硫酸氢钠、硫化氢、二氧化硫、草酸盐、碘盐、甲醛、硼氢化钠、抗坏血酸和硫化钠中的一种或多种。所述还原剂与所述磷酸盐的摩尔比为(0.1～5):1，优选为0.1：1、1：1、2：1、3：1、4：1、5：1，或(0.1～5):1之间的任意值。The reducing agent is selected from one or more of sodium sulfite, sodium bisulfite, hydrogen sulfide, sulfur dioxide, oxalate, iodine salt, formaldehyde, sodium borohydride, ascorbic acid and sodium sulfide. The molar ratio of the reducing agent to the phosphate is (0.1-5):1, preferably 0.1:1, 1:1, 2:1, 3:1, 4:1, 5:1, or (0.1 ~5): Any value between 1.
其中，所述反应的温度≤50℃，所述反应的压力≤0.5MPa；在本发明中的一些具体实施方式中，所述反应的温度为0～50℃，优选为0、5、15、20、25、30、50，或0～50℃时间的任意值，压力为0.08～0.5MPa，优选为0.08、0.1、0.15、0.2，或0.08～0.5MPa之间的任意值；在本发明的一些具体实施方式中，所述温度可以为常温、压力可以为常压。Wherein, the temperature of the reaction is ≤50°C, and the pressure of the reaction is ≤0.5MPa; in some embodiments of the present invention, the temperature of the reaction is 0-50°C, preferably 0, 5, 15, 20, 25, 30, 50, or any value at 0 to 50°C, the pressure is 0.08 to 0.5 MPa, preferably 0.08, 0.1, 0.15, 0.2, or any value between 0.08 to 0.5 MPa; in the present invention In some specific embodiments, the temperature may be normal temperature, and the pressure may be normal pressure.
得到固液混合物后，将所述固液混合物依次进行过滤、水洗、干燥，得到磷酸盐正极材料。After the solid-liquid mixture is obtained, the solid-liquid mixture is sequentially filtered, washed with water, and dried to obtain a phosphate positive electrode material.
所述磷酸盐正极材料为Q 1-zM aN bPO 4，Q为Li、Na、K中的一种或多种，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，-0.1≤z≤0.1，0≤a≤0.1，0.9≤b≤1。 The phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1≤z≤0.1, 0≤a≤0.1, 0.9≤b≤1.
本发明所述过滤、水洗、干燥所用的设备没有特殊要求，可以为本领域的常规选择。The equipment used for filtering, washing and drying in the present invention has no special requirements, and can be conventional selection in this field.
本发明所述的方法使用了价格便宜的磷酸盐为原材料，搭配相应的锂源、钠源、钾源，可以在较低的温度和压力条件下，甚至是常温常压条件下进行反应，反应时间短，工艺简单、安全、耗能低，有效降低了碳排放，具有极大的成本优势。The method of the present invention uses cheap phosphate as a raw material, matches corresponding lithium source, sodium source, potassium source, and can react under lower temperature and pressure conditions, even under normal temperature and pressure conditions. The time is short, the process is simple, safe, low energy consumption, effectively reduces carbon emissions, and has great cost advantages.
为了进一步理解本发明，下面结合实施例对本发明提供的磷酸盐正极材料 的制备方法进行说明，本发明的保护范围不受以下实施例的限制。In order to further understand the present invention, below in conjunction with embodiment the preparation method of phosphate cathode material provided by the present invention is described, protection scope of the present invention is not limited by following examples.
以下实施例中，所采用的具有橄榄石结构的磷酸盐按照以下方法进行制备：In the following examples, the phosphate with olivine structure used is prepared according to the following method:
实施例1～实施例4的磷酸铁按照如下方法进行制备：The ferric phosphate of embodiment 1～embodiment 4 is prepared according to the following method:
在常温条件下，将60g浓硫酸和60g双氧水以及150g磷酸铁锂加入到水溶液中，搅拌3h，得到142g磷酸铁和含锂溶液；Under normal temperature conditions, 60g of concentrated sulfuric acid, 60g of hydrogen peroxide and 150g of lithium iron phosphate were added to the aqueous solution, and stirred for 3 hours to obtain 142g of iron phosphate and lithium-containing solution;
参见图3，图3为本发明制备的磷酸铁材料的XRD图。Referring to Fig. 3, Fig. 3 is an XRD pattern of the iron phosphate material prepared in the present invention.
实施例5的掺杂Al的磷酸铁按照如下的方法进行制备：The Al-doped iron phosphate of embodiment 5 is prepared according to the following method:
在常温条件下，将30g浓硫酸和30g双氧水以及70g掺杂Al的磷酸铁锂加入到水溶液中，搅拌3h，得到62g掺杂Al的磷酸铁和含锂溶液；At room temperature, 30 g of concentrated sulfuric acid, 30 g of hydrogen peroxide, and 70 g of Al-doped lithium iron phosphate were added to the aqueous solution, and stirred for 3 hours to obtain 62 g of Al-doped iron phosphate and lithium-containing solution;
参见图7，图7为本发明制备的掺杂Al的磷酸铁材料的XRD图。Referring to FIG. 7, FIG. 7 is an XRD pattern of the Al-doped iron phosphate material prepared in the present invention.
实施例6和实施例7的磷酸铁按照如下的方法进行制备：The iron phosphate of embodiment 6 and embodiment 7 is prepared according to the following method:
在常温条件下，将60g浓硫酸和60g双氧水以及150g磷酸铁钠加入到水溶液中，搅拌4h，得到135g磷酸铁和含钠溶液；Under normal temperature conditions, 60g of concentrated sulfuric acid, 60g of hydrogen peroxide and 150g of sodium iron phosphate were added to the aqueous solution, and stirred for 4 hours to obtain 135g of iron phosphate and sodium-containing solution;
实施例8的磷酸锰按照如下的方法进行制备：The manganese phosphate of embodiment 8 is prepared according to the following method:
在常温条件下，将50g浓硫酸和50g双氧水以及120g磷酸锰锂加入到水溶液中，搅拌5h，得到109g磷酸锰和含锂溶液。At room temperature, 50 g of concentrated sulfuric acid, 50 g of hydrogen peroxide and 120 g of lithium manganese phosphate were added to the aqueous solution, and stirred for 5 hours to obtain 109 g of manganese phosphate and lithium-containing solution.
实施例9的磷酸锰铁按照如下的方法进行制备：The ferromanganese phosphate of embodiment 9 is prepared according to the following method:
在常温条件下，将80g盐酸和60g双氧水以及100g磷酸锰铁锂加入到水溶液中，搅拌2h，得到82g磷酸锰铁和含锂溶液。At room temperature, 80g of hydrochloric acid, 60g of hydrogen peroxide and 100g of lithium iron manganese phosphate were added to the aqueous solution, and stirred for 2 hours to obtain 82g of ferromanganese phosphate and lithium-containing solution.
实施例10的磷酸钴铁按照如下的方法进行制备：The cobalt iron phosphate of embodiment 10 is prepared according to the following method:
在常温条件下，将盐酸和氧气以及磷酸钴铁锂加入到水溶液中，搅拌8h，得到磷酸钴铁和含锂溶液。Under normal temperature conditions, hydrochloric acid, oxygen and lithium cobalt iron phosphate were added into the aqueous solution, and stirred for 8 hours to obtain a cobalt iron phosphate and lithium-containing solution.
实施例11的磷酸镍铁按照如下的方法进行制备：The ferronickel phosphate of embodiment 11 is prepared according to the following method:
在常温条件下，将盐酸和氧气以及磷酸镍铁锂加入到水溶液中，搅拌8h，得到磷酸镍铁和含锂溶液。Under the condition of normal temperature, hydrochloric acid, oxygen and lithium nickel iron phosphate were added into the aqueous solution, and stirred for 8 hours to obtain nickel iron phosphate and lithium-containing solution.
实施例12的磷酸铁按照如下的方法进行制备：The iron phosphate of embodiment 12 is prepared according to the following method:
在常温条件下，将盐酸和氧气以及磷酸铁锂加入到水溶液中，搅拌4h，得到磷酸铁和含锂溶液。Under normal temperature conditions, hydrochloric acid, oxygen and lithium iron phosphate were added to the aqueous solution, and stirred for 4 hours to obtain iron phosphate and lithium-containing solution.
实施例1Example 1
(1)在25℃和0.1MPa下，用10L去离子水溶解24g氢氧化锂得到含有锂离子的溶液；(1) Dissolve 24g of lithium hydroxide with 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸铁锂材料，Li 0.99FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 0.99 FePO 4 .
实施例2Example 2
(1)在25℃和0.1MPa下，用15L去离子水溶解50g硫酸锂得到含有锂离子的溶液；(1) Dissolve 50g of lithium sulfate with 15L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入60g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 60g of iron phosphate to the solution obtained in step (1), then stir with a stirrer for 0.5h at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入80g草酸钠，继续搅拌6h，得到固液混合物；(3) Add 80 g of sodium oxalate during the stirring process of step (2), and continue stirring for 6 hours to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸铁锂材料，Li 1.00FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 1.00 FePO 4 .
实施例3Example 3
(1)在25℃和0.1MPa下，用5L去离子水溶解40g氯化锂得到含有锂离子的溶液；(1) Dissolve 40g of lithium chloride with 5L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入60g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.2h；(2) Add 60g of ferric phosphate to the solution obtained in step (1), then stir for 0.2h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入100g草酸钾，继续搅拌5h，得到固液混合物；(3) Add 100 g of potassium oxalate during the stirring process of step (2), and continue stirring for 5 hours to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷 酸铁锂材料，Li 0.99FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 0.99 FePO 4 .
实施例4Example 4
(1)用10L去离子水溶解24g氢氧化锂得到含有锂离子的溶液；(1) Dissolve 24g lithium hydroxide with 10L deionized water to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.2h；(2) Add 70g of ferric phosphate to the solution obtained in step (1), then stir for 0.2h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，在50℃，0.5MPa条件下继续搅拌3h，得到固液混合物；(3) Add 70 g of ascorbic acid during the stirring process of step (2), and continue stirring for 3 h at 50° C. and 0.5 MPa to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸铁锂材料，Li 1.01FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material, Li 1.01 FePO 4 .
实施例5Example 5
(1)在25℃和0.1MPa下，用10L去离子水溶解24g氢氧化锂得到含有锂离子的溶液；(1) Dissolve 24g of lithium hydroxide with 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g掺杂Al的磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70g of Al-doped ferric phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌4h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到掺杂Al的磷酸铁锂材料，Li 0.99Al 0.01Fe 0.99PO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain a doped Al Lithium iron phosphate material, Li 0.99 Al 0.01 Fe 0.99 PO 4 .
实施例6Example 6
(1)在25℃和0.1MPa下，用10L去离子水溶解40g氢氧化钠得到含有钠离子的溶液；(1) Dissolve 40g of sodium hydroxide with 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing sodium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷 酸铁钠材料，Na 0.97FePO 4。参见图8，图8为本发明实施例6制备的磷酸铁钠材料的XRD图。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain sodium ferric phosphate Material, Na 0.97 FePO 4 . Referring to FIG. 8, FIG. 8 is an XRD pattern of the sodium iron phosphate material prepared in Example 6 of the present invention.
实施例7Example 7
(1)在25℃和0.1MPa下，用10L去离子水溶解40g氢氧化钠和24g氢氧化锂得到含有锂离子和钠离子的溶液；(1) Dissolve 40g of sodium hydroxide and 24g of lithium hydroxide in 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions and sodium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸铁钠锂材料，Li 0.73Na 0.26FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain sodium ferric phosphate Lithium material, Li 0.73 Na 0.26 FePO 4 .
实施例8Example 8
(1)在25℃和0.1MPa下，用10L去离子水溶解70g氯化锂得到含有锂离子的溶液；(1) Dissolve 70g of lithium chloride with 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸锰，然后用搅拌机以360转/分的转速搅拌0.5h；(2) add 70g manganese phosphate in the solution that step (1) obtains, then stir 0.5h with the rotating speed of 360 rev/mins with agitator;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸锰锂材料，Li 0.98MnPO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium manganese phosphate Material, Li 0.98 MnPO 4 .
实施例9Example 9
(1)在25℃和0.1MPa下，用20L去离子水溶解50g草酸锂得到含有锂离子的溶液；(1) Dissolve 50g of lithium oxalate with 20L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入50g磷酸锰铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 50g of ferromanganese phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌4h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸锰铁锂材料，Li 1.0Fe 0.63Mn 0.37PO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying 10h to obtain ferromanganese phosphate Lithium material, Li 1.0 Fe 0.63 Mn 0.37 PO 4 .
实施例10Example 10
(1)在25℃和0.1MPa下，用20L去离子水溶解50g氯化锂得到含有锂离子的溶液；(1) Dissolve 50g of lithium chloride with 20L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入60g磷酸钴铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 60g of cobalt-iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入50g抗坏血酸和20g草酸铵，继续搅拌4h，得到固液混合物；(3) Add 50 g of ascorbic acid and 20 g of ammonium oxalate during the stirring process of step (2), and continue stirring for 4 hours to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸钴铁锂材料，Li 0.97Fe 0.58Co 0.41PO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain ferric cobalt phosphate Lithium material, Li 0.97 Fe 0.58 Co 0.41 PO 4 .
实施例11Example 11
(1)在25℃和0.1MPa下，用20L去离子水溶解50g氯化锂得到含有锂离子的溶液；(1) Dissolve 50g of lithium chloride with 20L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入60g磷酸镍铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 60g nickel-iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入50g抗坏血酸和30g碘化铵，继续搅拌4h，得到固液混合物；(3) Add 50g ascorbic acid and 30g ammonium iodide during the stirring process of step (2), and continue stirring for 4h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸镍铁锂材料，Li 0.99Fe 0.48Ni 0.51PO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10h to obtain iron nickel phosphate Lithium material, Li 0.99 Fe 0.48 Ni 0.51 PO 4 .
实施例12Example 12
(1)在25℃和0.1MPa下，用10L去离子水溶解40g氯化钾和40g氯化钠，得到含有钾离子和钠离子的溶液；(1) Dissolve 40g potassium chloride and 40g sodium chloride with 10L deionized water at 25°C and 0.1MPa to obtain a solution containing potassium ions and sodium ions;
(2)向步骤(1)得到的溶液中加入70g磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70g of iron phosphate to the solution obtained in step (1), then stir for 0.5h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到 固液混合物；(3) add 70g ascorbic acid during the stirring process of step (2), continue to stir for 5h, obtain solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到K 0.21Na 0.78FePO 4。 (4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain K 0.21 Na 0.78 FePO 4 .
对比例1Comparative example 1
(1)在25℃和0.1MPa下，用10L去离子水溶解24g氢氧化锂得到含有锂离子的溶液；(1) Dissolve 24g of lithium hydroxide with 10L of deionized water at 25°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g市售磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h，参见图4，图4为市售磷酸铁的XRD图；(2) in the solution that step (1) obtains, add 70g commercially available ferric phosphate, then stir 0.5h with the rotating speed of 360 revs/min with agitator, referring to Fig. 4, Fig. 4 is the XRD pattern of commercially available ferric phosphate;
参见图5，图5为本发明制备的磷酸铁与市售磷酸铁的XRD比较图。Referring to Fig. 5, Fig. 5 is a comparison chart of XRD of iron phosphate prepared by the present invention and commercially available iron phosphate.
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，无法得到磷酸铁锂材料。(4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10h, and cannot obtain ferric phosphate lithium material.
对比例2Comparative example 2
(1)在80℃和0.1MPa下，用10L去离子水溶解24g氢氧化锂得到含有锂离子的溶液；(1) Dissolve 24g of lithium hydroxide with 10L of deionized water at 80°C and 0.1MPa to obtain a solution containing lithium ions;
(2)向步骤(1)得到的溶液中加入70g市售磷酸铁，然后用搅拌机以360转/分的转速搅拌0.5h；(2) Add 70 g of commercially available ferric phosphate to the solution obtained in step (1), then stir for 0.5 h with a stirrer at a speed of 360 rpm;
(3)在步骤(2)的搅拌过程中加入70g抗坏血酸，继续搅拌5h，得到固液混合物；(3) Add 70g of ascorbic acid during the stirring process of step (2), and continue stirring for 5h to obtain a solid-liquid mixture;
(4)用过滤器对步骤(3)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，对滤渣进行XRD检测，结果见图6，图6为反应前后固体XRD晶型比较，由图6可知，反应前后固体XRD晶型保持不变，即没有得到磷酸铁锂材料(反应前固体为磷酸铁，反应后固体为干燥后滤渣)。(4) Filter the solid-liquid mixture obtained in step (3) with a filter, then wash the filter residue 5 times with deionized water, finally put the washed filter residue into a blast drying oven for drying for 10h, and carry out XRD to the filter residue Detection, the results are shown in Figure 6, Figure 6 is the comparison of solid XRD crystal forms before and after the reaction, as can be seen from Figure 6, the solid XRD crystal form before and after the reaction remains unchanged, that is, no lithium iron phosphate material is obtained (the solid before the reaction is iron phosphate, after the reaction The solid is the residue after drying).
对比例3Comparative example 3
(1)将2.3g磷酸二氢铵，0.85g一水合氢氧化锂，3.04g硫酸亚铁加入到 体积为100ml的水热釜内衬中，再加入80ml去离子水；(1) 2.3g ammonium dihydrogen phosphate, 0.85g lithium hydroxide monohydrate, and 3.04g ferrous sulfate are added into the hydrothermal kettle lining whose volume is 100ml, then add 80ml deionized water;
(2)将步骤(1)中的水热釜放置在180℃鼓风干燥箱中加热24h，得到固液混合物；(2) Place the hydrothermal kettle in step (1) in a blast oven at 180°C and heat for 24 hours to obtain a solid-liquid mixture;
(3)用过滤器对步骤(2)得到的固液混合物进行过滤，然后再用去离子水对滤渣水洗5次，最后将水洗干净的滤渣放入鼓风干燥箱干燥10h，得到磷酸铁锂材料。(3) Filter the solid-liquid mixture obtained in step (2) with a filter, then wash the filter residue 5 times with deionized water, and finally put the washed filter residue into a blast drying oven for drying for 10 hours to obtain lithium iron phosphate Material.
(4)将步骤(3)制备得到的磷酸铁锂材料按照测试例1所述方法进行电化学性能测试，在0.5C倍率下的放电容量为147.6mAh/g，0.5C首次效率为97％。(4) The lithium iron phosphate material prepared in step (3) was subjected to an electrochemical performance test according to the method described in Test Example 1. The discharge capacity at 0.5C rate was 147.6mAh/g, and the first-time efficiency at 0.5C was 97%.
测试例1test case 1
对实施例1制得的磷酸铁锂材料进行XRD测试，所得XRD结果如图1所示，实施例1制得的磷酸铁锂材料的XRD谱图与磷酸铁锂标准卡片对比，特征峰明显，无多余杂峰，材料表现出较好的晶体结构，表明实施例1成功制得了磷酸铁锂材料。Carry out XRD test to the lithium iron phosphate material obtained in Example 1, the obtained XRD result is shown in Figure 1, the XRD spectrogram of the lithium iron phosphate material prepared in Example 1 is compared with the lithium iron phosphate standard card, and the characteristic peak is obvious, There are no extra peaks, and the material exhibits a good crystal structure, indicating that the lithium iron phosphate material was successfully prepared in Example 1.
电化学性能测试按照以下方法执行：称取2g实施例1制得的磷酸铁锂材料与PVDF(聚偏氟乙烯)、Super P碳以80：10：10的质量比例进行复配，以NMP(N-甲基吡咯烷酮)作分散剂进行调浆，涂布在平整的铝箔上，在鼓风干燥器中干燥12h，辊压后冲压成14mm直径的正极片，在惰性手套箱中，以金属锂片作为负极材料，以Celgard 2400膜作为隔膜，以在EC(碳酸乙烯酯)：DMC(碳酸二甲酯)＝3：7(体积比)混合液中溶有1mol/L六氟磷酸锂的溶液作为电解液，组装成扣式电池。控制测试电压范围在2.5～4.2V之间进行扣式电池测试。The electrochemical performance test is carried out according to the following method: Weigh 2g of the lithium iron phosphate material prepared in Example 1 and PVDF (polyvinylidene fluoride), Super P carbon is compounded with a mass ratio of 80:10:10, and NMP ( N-methylpyrrolidone) is used as a dispersant to slurry, coated on a flat aluminum foil, dried in a blast dryer for 12h, and punched into a positive electrode sheet with a diameter of 14mm after rolling. In an inert glove box, lithium metal The sheet is used as the negative electrode material, the Celgard 2400 film is used as the separator, and the solution of 1mol/L lithium hexafluorophosphate dissolved in the mixed solution of EC (ethylene carbonate): DMC (dimethyl carbonate) = 3:7 (volume ratio) is used as the electrolyte , assembled into a button cell. Control the test voltage range between 2.5 ~ 4.2V to carry out the button battery test.
电化学性能测试结果如图2所示，本发明制备的磷酸铁锂正极材料的电化学性能在0.5C倍率下的放电容量为152.1mAh/g，0.5C首次效率为98％，表明本发明制备出的磷酸铁锂材料具有较好的电性能。此外，本发明制备磷酸铁锂材料的工艺可以在常温常压的环境下进行，耗能低、碳排放少，无需耐高压和耐高温的设备，安全可控，具有极大的成本优势。The results of the electrochemical performance test are shown in Figure 2. The electrochemical performance of the lithium iron phosphate positive electrode material prepared by the present invention has a discharge capacity of 152.1mAh/g at a rate of 0.5C, and an initial efficiency of 98% at 0.5C, indicating that the preparation of the present invention The obtained lithium iron phosphate material has good electrical properties. In addition, the process for preparing lithium iron phosphate material in the present invention can be carried out at normal temperature and pressure, with low energy consumption, low carbon emissions, no need for high-pressure and high-temperature-resistant equipment, safe and controllable, and great cost advantages.
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以做出若干改进和润饰， 这些改进和润饰也应视为本发明的保护范围。The above descriptions are only preferred implementations of the present invention, and it should be pointed out that for those skilled in the art, some improvements and modifications can also be made without departing from the principle of the present invention. It should be regarded as the protection scope of the present invention.

Claims (10)

  1. 一种磷酸盐正极材料的制备方法，其特征在于，包括以下步骤：A kind of preparation method of phosphate cathode material, is characterized in that, comprises the following steps:
    将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应，得到磷酸盐正极材料；Mixing and reacting at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water to obtain phosphate positive electrode material;
    所述反应的温度≤50℃；The temperature of the reaction is ≤50°C;
    所述磷酸盐为橄榄石结构，为M xN yPO 4，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，0≤x≤0.1，0.9≤y≤1； The phosphate has an olivine structure, M x N y PO 4 , M is Li, Na, K, Ca, Al, Mg, Cu, F, B, Ni, Co, Mn, Ti, Nb, Sn, Mo , one or more of W, N is one or more of Fe, Mn, Co, Ni, 0≤x≤0.1, 0.9≤y≤1;
    所述磷酸盐正极材料为Q 1-zM aN bPO 4，Q为Li、Na、K中的一种或多种，M为Li、Na、K、Ca、Al、Mg、Cu、F、B、Ni、Co、Mn、Ti、Nb、Sn、Mo、W中的一种或多种，N为Fe、Mn、Co、Ni中的一种或多种，-0.1≤z≤0.1，0≤a≤0.1，0.9≤b≤1。 The phosphate cathode material is Q 1-z M a N b PO 4 , Q is one or more of Li, Na, K, M is Li, Na, K, Ca, Al, Mg, Cu, F , one or more of B, Ni, Co, Mn, Ti, Nb, Sn, Mo, W, N is one or more of Fe, Mn, Co, Ni, -0.1≤z≤0.1, 0≤a≤0.1, 0.9≤b≤1.
  2. 根据权利要求1所述的制备方法，其特征在于，所述反应的压力≤0.5Mpa。The preparation method according to claim 1, characterized in that the pressure of the reaction is ≤0.5Mpa.
  3. 根据权利要求1所述的制备方法，其特征在于，所述锂源选自氢氧化锂、醋酸锂、硝酸锂、草酸锂、硫酸锂、氯化锂、碳酸锂、碳酸氢锂、甲酸锂和四硼酸锂中的一种或多种；preparation method according to claim 1, is characterized in that, described lithium source is selected from lithium hydroxide, lithium acetate, lithium nitrate, lithium oxalate, lithium sulfate, lithium chloride, lithium carbonate, lithium bicarbonate, lithium formate and One or more of lithium tetraborate;
    所述钠源选自氢氧化钠、醋酸钠、硝酸钠、草酸钠、硫酸钠、氯化钠、碳酸钠、碳酸氢钠、碘化钠、亚硫酸钠和亚硫酸氢钠中的一种或多种；The sodium source is selected from one or more of sodium hydroxide, sodium acetate, sodium nitrate, sodium oxalate, sodium sulfate, sodium chloride, sodium carbonate, sodium bicarbonate, sodium iodide, sodium sulfite and sodium bisulfite ;
    所述钾源选自氢氧化钾、硝酸钾、硫酸钾、氯化钾、碘化钾、亚硫酸钾和亚硫酸氢钾中的一种或多种。The potassium source is selected from one or more of potassium hydroxide, potassium nitrate, potassium sulfate, potassium chloride, potassium iodide, potassium sulfite and potassium bisulfite.
  4. 根据权利要求1所述的制备方法，其特征在于，所述还原剂选自亚硫酸钠、亚硫酸氢钠、硫化氢、二氧化硫、草酸盐、碘盐、甲醛、硼氢化钠、抗坏血酸和硫化钠中的一种或多种。The preparation method according to claim 1, wherein the reducing agent is selected from sodium sulfite, sodium bisulfite, hydrogen sulfide, sulfur dioxide, oxalate, iodine salt, formaldehyde, sodium borohydride, ascorbic acid and sodium sulfide one or more of .
  5. 根据权利要求1所述的制备方法，其特征在于，所述锂源中锂、钠源中钠和钾源中钾的至少一种的摩尔数与所述磷酸盐的摩尔比为(1～5)：1；The preparation method according to claim 1, characterized in that, the molar ratio of at least one of lithium in the lithium source, sodium in the sodium source, and potassium in the potassium source to the phosphate is (1～5 ):1;
    所述还原剂与所述磷酸盐的摩尔比为(0.1～5):1。The molar ratio of the reducing agent to the phosphate is (0.1-5):1.
  6. 根据权利要求1所述的制备方法，其特征在于，所述磷酸盐按照如下 方法进行制备：preparation method according to claim 1, is characterized in that, described phosphate is prepared according to the following method:
    将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应，得到磷酸盐。The phosphate alkali metal compound, oxidizing agent, acid and water are mixed and reacted to obtain phosphate.
  7. 根据权利要求6所述的制备方法，其特征在于，所述氧化剂选自过氧化氢、氧气、臭氧、过氧化钠、次氯酸、次碘酸和过氧乙酸中的一种或多种；The preparation method according to claim 6, wherein the oxidizing agent is selected from one or more of hydrogen peroxide, oxygen, ozone, sodium peroxide, hypochlorous acid, hypoiodous acid and peracetic acid;
    所述酸选自硫酸、盐酸、硝酸、碳酸和草酸中的一种或多种；The acid is selected from one or more of sulfuric acid, hydrochloric acid, nitric acid, carbonic acid and oxalic acid;
    将磷酸盐碱金属化合物、氧化剂、酸和水混合进行反应的温度为0～100℃，时间为0.1～10h。The temperature of mixing the phosphate alkali metal compound, oxidizing agent, acid and water to react is 0-100° C. and the time is 0.1-10 h.
  8. 根据权利要求1所述的制备方法，其特征在于，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应的温度为0～50℃，压力为0.08～0.5MPa，时间为0.1～10小时。The preparation method according to claim 1, characterized in that at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water are mixed and reacted at a temperature of 0-50°C and a pressure of 0.08 ～0.5MPa, the time is 0.1～10 hours.
  9. 根据权利要求1所述的制备方法，其特征在于，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应为常温常压条件。The preparation method according to claim 1, characterized in that at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water are mixed and reacted under normal temperature and pressure conditions.
  10. 根据权利要求1所述的制备方法，其特征在于，将锂源、钠源和钾源中的至少一种、磷酸盐、还原剂和水混合进行反应后，得到固液混合物；The preparation method according to claim 1, characterized in that, after mixing and reacting at least one of lithium source, sodium source and potassium source, phosphate, reducing agent and water, a solid-liquid mixture is obtained;
    将所述固液混合物依次进行过滤、水洗、干燥，得到磷酸盐正极材料。The solid-liquid mixture is sequentially filtered, washed with water, and dried to obtain a phosphate cathode material.
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