WO2020134773A1 - Method for recovering and preparing lithium iron phosphate cathode material - Google Patents

Method for recovering and preparing lithium iron phosphate cathode material Download PDF

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Publication number
WO2020134773A1
WO2020134773A1 PCT/CN2019/120509 CN2019120509W WO2020134773A1 WO 2020134773 A1 WO2020134773 A1 WO 2020134773A1 CN 2019120509 W CN2019120509 W CN 2019120509W WO 2020134773 A1 WO2020134773 A1 WO 2020134773A1
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acid
lithium
iron phosphate
lithium iron
liquid phase
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PCT/CN2019/120509
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French (fr)
Chinese (zh)
Inventor
林永寿
赵丰刚
刘晓梅
郑先锋
王国宝
王凡
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宁德时代新能源科技股份有限公司
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Publication of WO2020134773A1 publication Critical patent/WO2020134773A1/en

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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00Phosphorus; Compounds thereof
    • C01B25/16Oxyacids of phosphorus; Salts thereof
    • C01B25/26Phosphates
    • C01B25/45Phosphates containing plural metal, or metal and ammonium
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/54Reclaiming serviceable parts of waste accumulators
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/84Recycling of batteries or fuel cells

Definitions

  • the invention relates to the field of electrochemistry, in particular to a method for recovering and preparing lithium iron phosphate cathode material.
  • an object of the present invention is to provide a method for recovering and preparing lithium iron phosphate cathode material and the recovered lithium iron phosphate cathode material obtained by the preparation, and further to provide the recovered iron phosphate Lithium ion batteries with lithium cathode materials are used to solve the problems in the prior art.
  • one aspect of the present invention provides a method for recovering and preparing lithium iron phosphate cathode material, including:
  • step b) Adjust the pH value of the first liquid phase provided in step a), and obtain the first lithium-containing solution and the first precipitate by solid-liquid separation;
  • step b) Adjust the pH value of the first lithium-containing solution provided in step b), and obtain the second lithium-containing solution and the second precipitate by solid-liquid separation;
  • step d) mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second liquid phase;
  • step d) Adjust the content of Li element, Fe element, P element, and C element in the second liquid phase provided in step d) to obtain a third liquid phase;
  • step f) removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor
  • step f) The lithium iron phosphate precursor provided in step f) is calcined under a reducing environment to obtain a lithium iron phosphate cathode material.
  • Another aspect of the present invention provides a recovered lithium iron phosphate cathode material prepared and obtained by the foregoing method for recycling lithium iron phosphate cathode material.
  • Another aspect of the present invention provides a lithium ion battery including the recovered lithium iron phosphate cathode material.
  • the present invention has the following beneficial effects:
  • the recovery method is simple. After disassembling the cell, it is directly contacted with the acid solution, and the simple separation directly synthesizes the lithium iron phosphate cathode material without the steps of mechanical separation of the positive and negative plates, the separation membrane, and the separation of the pole piece and the active material. .
  • the recycling rate is high, the lithium iron phosphate battery has a stoichiometric ratio of lithium source, iron source, and phosphorus source, and the lithium salt in the electrolyte supplements the available lithium salt, the organic matter in the battery, and the carbon material on the negative electrode. , To supplement the available carbon source.
  • the present invention makes full use of the lithium element in the electrolyte and the carbon material in the negative electrode sheet, so that only a small amount of elements lost in the recovery process need to be added in step d, and even no additional elements need to be added to synthesize the lithium iron phosphate cathode material.
  • the lithium iron phosphate cathode material used in the battery needs to limit the content of heavy metal impurity ions, and the present invention is equivalent to the further recovery and purification on the basis of the system that controls the content of heavy metal ions, and the impurity metal is newly added in the recovery process
  • the ions come only from copper and aluminum in the substrate, and they are basically free of other transition metal impurity elements, which is easy to handle.
  • Recycled synthetic lithium iron phosphate cathode material has very good comprehensive performance.
  • Figure 1 shows a schematic diagram of the results of an embodiment of the present invention.
  • the lithium ion battery of the present invention and its preparation method are described in detail below.
  • a first aspect of the present invention provides a method for recovering and preparing lithium iron phosphate cathode material, including:
  • step b) Adjust the pH value of the first liquid phase provided in step a), and obtain the first lithium-containing solution and the first precipitate by solid-liquid separation;
  • step b) Adjust the pH value of the first lithium-containing solution provided in step b), and obtain the second lithium-containing solution and the second precipitate by solid-liquid separation;
  • step d) mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second liquid phase;
  • step d) Adjust the content of Li element, Fe element, P element, and C element in the second liquid phase provided in step d) to obtain a third liquid phase;
  • step f) removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor
  • step f) calcining the lithium iron phosphate precursor provided in step f) in the presence of a reducing gas to obtain a lithium iron phosphate cathode material
  • the method for recovering and preparing lithium iron phosphate cathode material provided by the present invention can be directly contacted with an acid solution after disassembling the battery cell, and can be directly separated and directly synthesized in one step to synthesize lithium iron phosphate cathode material, which can be fully utilized by recycling in the entire preparation process
  • the lithium element in the electrolyte and the final preparation of the lithium iron phosphate cathode material have less impurity content.
  • the lithium iron phosphate battery generally refers to a lithium ion battery using lithium iron phosphate as a positive electrode material, and the chemical formula of the lithium iron phosphate may be LiFe y Mn 1-yz M” z PO 4 /C b (b ⁇ 0, M” One or more combinations selected from Cr, Mg, Ti, Al, Zn, W, Nb, and Zr (0.1 ⁇ y ⁇ 1.0, 0 ⁇ z ⁇ 0.9).
  • the method for recovering and preparing lithium iron phosphate cathode material may include: contacting the recovered battery core material with an acid solution, and solid-liquid separation to obtain a first liquid phase.
  • Those skilled in the art can choose a suitable way to obtain recycled battery core materials, and the recycled battery core materials usually include positive pole pieces.
  • those skilled in the art can use lithium iron phosphate battery cells without removing the casing.
  • the cell material includes a battery metal (usually Al or steel) shell or polymer case, positive and negative electrode plates, separators and electrolyte; for another example, those skilled in the art can use a lithium iron phosphate battery with the case removed Core to obtain a cell including a positive pole piece, more specifically a bare cell including a positive pole piece; for another example, the cell material may be a positive pole piece, and a person skilled in the art may obtain the positive pole piece
  • the cells of the sheet are further separated to obtain a positive pole piece.
  • the recovered battery cell is usually a discharged battery cell, for example, the battery cell can be discharged to 2.5 V or less to ensure the safety of the treatment process.
  • the recovered battery cell may be a whole-recovered battery cell, that is, after disassembly, the components of the battery cell are not further separated.
  • the recovered battery cell material may generally include a positive pole piece, and may also include an isolation film and / Or negative electrode, etc., may also include electrolyte, because the electrolyte is recovered electrolyte, so the electrolyte usually contains a certain amount of lithium element, the content of lithium element in the electrolyte is usually in the electrolyte The content in is 0.5% ⁇ 2%. Due to the difference in the amount of liquid injected into the battery cell, the element content in the electrolyte is also different.
  • the lithium element content is 0.2% ⁇ 0.8%, 0.2% ⁇ 0.4 relative to the positive electrode active material percentage %, 0.4% to 0.6%, or 0.6% to 0.8%.
  • the acid solution is usually an aqueous solution, and the molar concentration of the acid solution may be 0.5 to 10M, 0.5 to 1M, 1 to 2M, 2 to 3M, 3 to 4M, 4 to 5M, 5 to 6M, 6 to 8M, or 8 to 10M, preferably 1 to 6M.
  • the acid in the acid solution may be an inorganic acid and/or an organic acid.
  • the inorganic acid in the acid solution is preferably an inorganic strong acid, which may specifically include but not limited to hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, chloric acid, etc. One or more combinations.
  • the organic acid in the acid solution is preferably an organic strong acid, which may specifically include but not limited to 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, tri A combination of one or more of fluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, KMD acid, etc.
  • the acid solution may also have oxidizing properties.
  • the acid in the acid solution may be an oxidizing acid.
  • the acid solution may include hydrogen peroxide, specifically an acidic hydrogen peroxide solution.
  • the molar concentration of hydrogen peroxide in the acid solution may be 0.5 to 10M, 0.5 to 1M, 1 to 2M, 2 to 3M, 3 to 4M, 4 to 5M, 5 to 6M, 6 to 8M, or 8 to 10M, preferably It can be 1 ⁇ 6M.
  • the concentration of Fe 2+ in the first liquid phase may be ⁇ 30 ppm, ⁇ 40 ppm, ⁇ 50 ppm, ⁇ 60 ppm, ⁇ 80 ppm, or ⁇ 100 ppm, preferably, preferably, the concentration of Fe 2+ in the first liquid phase is ⁇ 50 ppm.
  • Skill in the art can select a suitable adjusting the concentration of Fe 2+ in the first liquid phase, for example, may have the acid solution by using an oxidizing, reducing to Fe 2+ solution, and then, for example, a step ) May also include: performing oxidation treatment on the first liquid phase.
  • the oxidation treatment generally refers to a treatment method of contacting the first liquid phase with an oxidizing substance, thereby oxidizing a reducing substance (for example, ferrous ion Fe 2+ ) in the first liquid phase.
  • a reducing substance for example, ferrous ion Fe 2+
  • the recovery rate of the separated Fe element in the subsequent pH adjustment is higher, because the pH is less than 3, the iron phosphate is basically completely precipitated, and the ferrous phosphate is completely precipitated.
  • the pH needs to be> 5 , Al and Cu precipitation cross.
  • the concentration of Fe 2+ can be measured using phenanthroline spectrophotometry.
  • the method of oxidizing the first liquid phase should be known to those skilled in the art.
  • the first liquid phase may be contacted with an oxidant, and the oxidant may be, for example, oxygen, etc.
  • the oxidant may be, for example, oxygen, etc.
  • a gas containing oxygen may be introduced into the first liquid phase, and the gas containing oxygen may include but is not limited to Combination of one or more of oxygen, air, a mixture of oxygen and other suitable gases (eg, inert gas, etc.), etc.
  • the temperature conditions of the contact between the recovery cell and the acid solution may be 10°C to 60°C, 10°C to 20°C, 20°C to 30°C, 30°C to 40°C, 40°C to 50°C, or 50 °C ⁇ 60 °C, preferably 15 °C ⁇ 40 °C, more preferably 20 °C ⁇ 35 °C, for example, the recovery battery and acid contact time can be 0.5h ⁇ 5h, 0.5h ⁇ 1h, 1h ⁇ 2h , 2h to 3h, 3h to 4h, or 4h to 5h, preferably 1h to 3h.
  • first liquid phase usually It can dissolve the lithium iron phosphate active material in the recovered battery, lithium in the graphite negative electrode, aluminum foil, copper foil and other components.
  • the main elements in the first liquid phase can be Fe, P, Li, Al, Cu, C, O, H, etc.
  • the second precipitate obtained by separation can generally include graphite, conductive carbon, binder, separator, substrate, etc.
  • the second precipitate obtained by separation can be further separated to obtain Graphite, these methods should be known to those skilled in the art, for example, it can be filtered with a filter of different pore sizes to obtain graphite by sieving.
  • the method for recovering and preparing the lithium iron phosphate cathode material provided by the present invention may further include: adjusting the pH value of the first liquid phase provided in step a), and solid-liquid separation to obtain the first lithium-containing solution and the first precipitate.
  • the pH value of the first liquid phase provided in step a) is generally strongly acidic, and those skilled in the art can appropriately adjust the amount of the acid solution according to the pH value of the first liquid phase, for example, the The pH value may be ⁇ 0.8, ⁇ 1, ⁇ 1.2, ⁇ 1.4., ⁇ 1.6, ⁇ 1.8, or ⁇ 2.
  • the pH value of the first liquid phase may be ⁇ 1.
  • the components in the solution can be sequentially precipitated to achieve the purpose of separating the components.
  • a person skilled in the art can select suitable pH treatment conditions.
  • the pH of the first liquid phase can be adjusted, and solid-liquid separation (for example, filtration or the like) can be performed to obtain the first precipitate and the first lithium-containing solution.
  • the main component of the first precipitation is usually iron phosphate, and the first lithium-containing solution may be a treatment liquid after the iron phosphate is fully analyzed.
  • the pH of the first liquid phase can be adjusted to 1 to 3, 1 to 1.5, 1.5 to 2, 2 to 2.5, or 2.5 to 3, and preferably the pH of the first liquid phase can be adjusted to 1.5 to 2.5 , So that components such as iron phosphate in the first liquid phase can be fully precipitated, while the remaining components are still dissolved in the solution.
  • the method for recovering a lithium iron phosphate cathode material provided by the invention may further include: adjusting the pH value of the first lithium-containing solution provided in step b), and solid-liquid separation to obtain a second lithium-containing solution and a second precipitate.
  • adjusting the pH value of the first lithium-containing solution with the gradual increase of the pH value, the components in the solution can be successively precipitated to achieve the purpose of separating the components.
  • a person skilled in the art can select suitable pH treatment conditions.
  • the pH of the first lithium-containing solution can be adjusted, and solid-liquid separation (eg, filtration or the like) can be performed to obtain the second lithium-containing solution and the second precipitate.
  • the second lithium-containing solution is a lithium salt solution whose main component is a lithium salt.
  • the lithium salt contained in the second lithium-containing solution may be LiCl, LiNO 3, etc.
  • the second precipitation may mainly be Including aluminum phosphate, copper phosphate, copper hydroxide, etc.
  • the pH of the first lithium-containing solution can be adjusted to 4-11, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, or 10-11, preferably it can be adjusted
  • the pH value of the first lithium-containing solution is 6 to 10, so that metals such as Al and Cu (usually impurity components) can be fully precipitated to form a second precipitate, while most lithium-containing compounds are still dissolved in the solution
  • the Al element content in the second lithium-containing solution is not higher than 30 ppm.
  • the base may be an inorganic base and/or an organic base.
  • the inorganic base may include but not limited to a combination of one or more of ammonia, sodium hydroxide, potassium hydroxide, etc.
  • the organic base may include but not Limited to methylamine, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, tripropylamine, butylamine, isobutylamine, tert-butylamine, hexylamine A combination of one or more of amine, octylamine, cyclohexylamine, etc.
  • the method for recovering and preparing lithium iron phosphate cathode material provided by the present invention may further include: mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second Liquid phase.
  • the second liquid phase may be a uniform solution or a uniformly dispersed suspension.
  • the auxiliary agent is generally used to increase the solubility of the solution system to iron phosphate, which can help to form a solution with a uniform distribution of various ions.
  • the quality of the auxiliary agent can be 0.1% to 20%, 0.1% to 0.5%, 0.5% to 1%, 1% to 2%, 2% to 3%, 3% of the mass of iron phosphate and lithium-containing solution ⁇ 5%, 5% ⁇ 10%, 10% ⁇ 15%, or 15% ⁇ 20%
  • the components constituting the auxiliary agent can usually include but not limited to acids, dispersants, surfactants, chelating agents, etc. One or more combinations.
  • the acid in the auxiliary agent may be an inorganic acid and/or an organic acid
  • the inorganic acid in the auxiliary agent is preferably a strong inorganic acid, which may specifically include but not limited to one of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, chloric acid, etc.
  • the organic acid in the auxiliary agent is preferably a strong organic acid, which may specifically include but not limited to 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, trifluoroacetic acid , Trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, KMD acid, etc. one or more combinations.
  • the dispersing agent may include but not limited to water, ethanol, acetone, propanol, isopropanol, methanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether methylene chloride, chloroform, dimethyl sulfoxide, dimethyl methyl alcohol A combination of one or more of amides and the like.
  • the surfactant may include but is not limited to cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, poly A combination of one or more of ethylene glycol, polyethylene oxide, polyacrylamide or carboxymethyl cellulose, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and the like.
  • the chelating agent may be one of but not limited to nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, oxalic acid, acetic acid, salicylic acid, etc. Or a combination of multiple.
  • the method for recovering and preparing lithium iron phosphate cathode material provided by the present invention may further include: adjusting the content of Li element, Fe element, P element and C element in the second liquid phase provided in step d) to obtain a third liquid phase.
  • a person skilled in the art can determine the content of Li, Fe, P, and C elements in the third liquid phase according to the type of lithium iron phosphate cathode material to be prepared, for example, the molar ratio between Fe and P elements Usually it is basically the same amount.
  • the molar ratio between Fe and P can be 1:0.95 ⁇ 1.05.
  • Li and C have a certain loss (volatility) during the final heat treatment, so the amount of Li used It is usually excessive, specifically, the molar ratio between Li element and Fe element can be (1 to 1.5): (0.95 to 1.05), and the molar ratio between Li element and P element can be (1 to 1.5): (0.95 to 1.05), the molar ratio between the Li element and the C element may be (1 to 1.5): (0.5 to 4).
  • the content of elements in the system can be determined by a suitable analytical method.
  • analytical methods may include but are not limited to ICP , One or more of chemical titration, liquid chromatography, precipitation method, carbon and sulfur analysis method to determine the element content in the system.
  • the method of adjusting each element in the liquid phase should be known to those skilled in the art, and can usually be adjusted by introducing one or more combinations of corresponding lithium source, iron source, phosphorus source, carbon source, etc.
  • the content of each element in the second liquid phase, the lithium source, iron source, phosphorus source, and carbon source may generally be various raw materials suitable for preparing lithium iron phosphate cathode materials, for example, the lithium source used may include but Not limited to one or more combinations of lithium carbonate, lithium dihydrogen phosphate, lithium phosphate, lithium acetate, lithium hydroxide, lithium oxalate, lithium nitrate, etc.
  • the iron source used may include but is not limited to dioxide One or more of iron, ferric oxide, ferric phosphate, ferrous phosphate, ferric nitrate, ferric chloride, ferrous nitrate, ferrous chloride, ferric acetate, ferric carbonate, ferrous carbonate, ferric acetylacetonate, etc.
  • a combination of species, the phosphorus source used may be one or more combinations including but not limited to ammonium dihydrogen phosphate, lithium dihydrogen phosphate, iron phosphate, ferrous phosphate, phosphoric acid, etc.
  • the carbon source used may be Is a combination of one or more of graphite, conductive carbon, acetylene black, conductive carbon black, carbon fiber, carbon nanotubes, nanocarbon microspheres, glucose, sucrose, fructose, polyacrylonitrile, etc.
  • the carbon source is preferably a soluble carbon source.
  • the iron source for adjusting the content of the iron element in the second liquid phase may include at least part of the first precipitate provided in the step b), so that sufficient recovery and application of iron phosphate can be achieved.
  • the carbon source for adjusting the content of the carbon element in the second liquid phase may include at least a part of the carbon source obtained by sieving the insoluble matter in the step a), so that sufficient material can be achieved Recycling.
  • the Fe element introduced when adjusting the element ratio usually does not exceed 25%, 20%, 15%, 10%, or 5% of the total Fe element in the third liquid phase.
  • the introduced Li element usually does not exceed 25%, 20%, 15%, 10%, or 5% of the total Li element in the third liquid phase
  • the P element introduced when adjusting the element ratio usually does not exceed the third liquid phase 25%, 20%, 15%, 10%, or 5% of the total amount of P element
  • the C element introduced when adjusting the element ratio may account for 50% to 100%, 50% of the total amount of C element in the third liquid phase ⁇ 60%, 60% ⁇ 70%, 70% ⁇ 80%, 80% ⁇ 90%, or 90% ⁇ 100%.
  • the method for recovering and preparing a lithium iron phosphate cathode material provided by the present invention may further include: removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor.
  • a person skilled in the art may select a suitable method to remove the solvent of the third liquid phase provided in step e), for example, the method of removing the solvent may be dried, etc., and more specifically may include, but not limited to, atmospheric drying and vacuum drying , Spray drying, boiling drying, freeze drying, etc. one or more combinations.
  • the method for recovering and preparing a lithium iron phosphate cathode material provided by the present invention may further include: calcining the lithium iron phosphate precursor provided in step f) under a reducing environment to obtain a lithium iron phosphate cathode material.
  • the reducing environment may be provided by a reducing gas and/or a reducing liquid, specifically by hydrogen And/or carbon monoxide, or those gases and/or liquids capable of generating hydrogen and/or carbon monoxide under heating conditions
  • the reducing gas and/or reducing liquid used to provide the reducing environment may include but is not limited to hydrogen, A combination of one or more of carbon monoxide, acetylene, methanol, ethanol, methane, ethane, etc.
  • the calcination temperature may be 500° C. to 700° C., 500° C.
  • the calcination time may be 10 min to 300 min, 10 min ⁇ 20min, 20min ⁇ 30min, 30min ⁇ 50min, 50min ⁇ 100min, 100min ⁇ 150min, 150min ⁇ 200min, or 200min ⁇ 300min.
  • the impurity metal ions of the recovered recovered lithium iron phosphate cathode material only come from copper and aluminum in the substrate, and are substantially free of other transition metal impurity elements, such as , Basically does not contain Ni, Co, Mn, K and other metal ions, specifically, the sum of Cu, Al impurity ion content ⁇ 200ppm, the sum of heavy metal impurity ion content except Cu, Al can be less than 200ppm, sodium potassium content The sum can be less than 300ppm.
  • the second aspect of the present invention provides a recovered lithium iron phosphate cathode material prepared by the method provided in the first aspect of the present invention.
  • the impurity metal ions only come from copper and aluminum in the base material, and basically do not contain other transition metal impurity elements.
  • the sum of Cu and Al impurity ion content is less than 200ppm, except Cu,
  • the sum of the content of heavy metal impurities ions other than Al may be less than 200 ppm, and the sum of the content of sodium and potassium elements may be less than 300 ppm.
  • a third aspect of the present invention provides a lithium ion battery, including the lithium iron phosphate cathode material prepared and recovered as provided in the second aspect of the present invention.
  • the lithium ion battery generally includes a positive electrode tab, and the positive electrode tab generally includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, and the positive electrode active material layer may generally include as provided in the first aspect of the present invention Of recycled lithium iron phosphate cathode material.
  • the lithium-ion battery may also include other components that can be used in the lithium-ion battery, for example, it may also include a negative pole piece, a battery separator, an electrolyte, an external electrode, a tab, a packaging case, and the like.
  • one or more of the method steps mentioned in the present invention does not exclude that there may be other method steps before or after the combination step or that other method steps may be inserted between these explicitly mentioned steps unless otherwise Explained; It should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices or those mentioned explicitly in these before and after the combined device/device Other devices/apparatuses can also be inserted between the two devices/apparatuses unless otherwise stated.
  • each method step is only a convenient tool to identify each method step, not to limit the order of each method step or to limit the scope of the present invention, the change or adjustment of its relative relationship, in If the technical content is not substantially changed, it should be regarded as the scope of the invention.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the pole ears, put the winding core ( ⁇ 600g) and residual electrolyte ( ⁇ 20g) into 1.5L of 5M hydrochloric acid Then, add 250ml of 3M hydrogen peroxide solution to the solution, and stir and soak for 2h at 25°C.
  • Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 1g of iron phosphate to make the suspension
  • the molar ratio of lithium element: iron element: phosphorus element: carbon element is 1.12:1:1:1:0.8.
  • Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
  • Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 5 hours, during which hydrogen-argon mixed gas is introduced to prepare a recovered lithium iron phosphate cathode material 1.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the pole ears, put the winding core ( ⁇ 600g) and residual electrolyte ( ⁇ 20g) into 1.5L of 3M nitric acid In the solution, at 30°C, stir and soak for 3h.
  • the above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase.
  • Step d) The separated first precipitate and second lithium-containing solution are mixed, and a mixed solution containing 2M nitric acid, 1M polyethylene oxide, and 1M malic acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon and sulfur analyzer to test the content of element C, add 17g of the carbon source (mainly graphite) obtained in the previous step a), and 0.8g of ferric oxide and 1.0g Phosphoric acid is such that the molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution is 1.12:1:1:1:0.5.
  • Step f) After fully stirring the above solution, it is dried under reduced pressure at 90°C to obtain a precursor powder.
  • Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 hours, during which a mixture of carbon monoxide and argon gas is introduced to prepare a recovered lithium iron phosphate cathode material 2.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core ( ⁇ 600g) and residual electrolyte ( ⁇ 20g) into 1.5L, and the concentration is 3M. Then add 250ml of 1M hydrogen peroxide solution to the chloroacetic acid solution, and immerse for 5 hours under stirring at 20°C.
  • the above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase.
  • Step d) The separated first precipitate and second lithium-containing solution are mixed, and a mixed solution containing 3M trichloroacetic acid, 1M cetyltrimethylammonium bromide and 1M oxalic acid is added dropwise during the stirring process until the solution becomes Even suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 25g of the carbon source (mainly graphite) obtained in the previous step a), 2.3g of iron nitrate and 0.9g of phosphoric acid, so that The molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution is 1.11:1:1:1:1:1.
  • Step f) After fully stirring the above solution, directly evaporate and dry at 100°C to obtain a precursor powder.
  • Step g) The above precursor powder is placed in an atmosphere furnace, and the temperature is raised to 600°C at 5°C/min and calcined for 3 hours, during which methane and argon gas mixture is passed to prepare a recovered lithium iron phosphate cathode material 3.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% attenuation, cut off the pole ears, put the winding core ( ⁇ 600g) and the residual electrolyte ( ⁇ 20g) into 3L of hydrochloric acid with a concentration of 0.8M In the solution, at 30 °C, stir and soak for 5h.
  • the above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase.
  • Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon and sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), 2g of ferric oxide and 3.1g of diphosphate
  • the ammonium hydrogen and phosphorus elements make the molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution 1.13:1:1:1:0.7.
  • Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
  • Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 h, during which hydrogen-argon mixed gas is introduced to prepare the recovered lithium iron phosphate cathode material 4.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core ( ⁇ 600g) and the residual electrolyte ( ⁇ 20g) into 1.5L of 2M hydrochloric acid In the solution, at 30°C, stir and soak for 3h.
  • the above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase.
  • Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 2.5g of iron phosphate to make lithium in the solution
  • iron element: phosphorus element: carbon element molar ratio is 1.12:1:1:1:1:0.7.
  • Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
  • Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 h, during which hydrogen-argon mixed gas is passed to prepare a recovered lithium iron phosphate cathode material 5.
  • Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core ( ⁇ 600g) and residual electrolyte ( ⁇ 20g) into 1.5L of 3M hydrochloric acid In the solution, at 30°C, stir and soak for 3h.
  • the above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase.
  • Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
  • Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 2.1g of iron phosphate to make lithium in the solution
  • iron element: phosphorus element: carbon element molar ratio is 1.11:1:1:1:1:0.7.
  • Step f) After fully stirring the above solution, it is dried at 90°C under reduced pressure to obtain a precursor powder.
  • Step g) Put the above-mentioned precursor powder in an atmosphere furnace, raise the temperature at 5°C/min to 600°C and calcine for 3 hours, during which hydrogen-argon mixed gas is introduced to prepare the recovered lithium iron phosphate cathode material 6.
  • the pH adjustment changes are shown in the following table, in which the pH value is measured using a pH meter, and the ion concentration is detected using ICP:
  • the content of metal impurity ions in lithium iron phosphate synthesized in Example 1 was synthesized by ICP. The results are shown in Table 2. It can be seen that the concentration of each metal impurity ion is at a very low content level, and Ni and Co are not detected. , Mn, K metal ions, Li element recovery rate is 93%, iron element recovery rate is 96%, phosphorus element recovery rate is 96%.
  • the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.

Abstract

Disclosed is a method for recovering and preparing a lithium iron phosphate cathode material, comprising contacting a recycled battery cell material with an acid solution, followed by performing solid-liquid separation to obtain a first liquid phase and an insoluble matter; adjusting the pH value of the first liquid phase, followed by performing solid-liquid separation to obtain a first lithium-containing solution and a first precipitate; mixing the first precipitate and a second lithium-containing solution with an auxiliary agent to obtain a second liquid phase; adjusting the contents of Li , Fe , P and C in the second liquid phase to obtain a third liquid phase; removing a solvent in the third liquid phase to obtain a lithium iron phosphate precursor; and calcining the precursor in a reducing environment to obtain the lithium iron phosphate cathode material. Also disclosed is a lithium iron phosphate cathode material recovered and prepared by the method, and a lithium ion battery comprising the lithium iron phosphate cathode material. The method has the advantages of a simple process, high recovery and recycling rate, and low impurity content in the product, among others, and has a good prospect for industrialization.

Description

一种回收制备磷酸铁锂正极材料的方法Method for recovering and preparing lithium iron phosphate cathode material 技术领域Technical field
本发明涉及电化学领域,特别是涉及一种回收制备磷酸铁锂正极材料的方法。The invention relates to the field of electrochemistry, in particular to a method for recovering and preparing lithium iron phosphate cathode material.
背景技术Background technique
随着政府对新能源汽车的大力支持,我国新能源汽车行业的快速发展,领跑全球。然而我们必须清晰的看到,越来越多退役的动力电池该如何处理。如果这些电池得不到妥善处理,不仅会对环境造成重大污染,同时也是对资源的一种浪费。With the government's strong support for new energy vehicles, the rapid development of my country's new energy vehicle industry leads the world. However, we must clearly see how more and more retired power batteries should be handled. If these batteries are not handled properly, it will not only cause significant pollution to the environment, but also a waste of resources.
目前国内外的研究者对磷酸铁锂电池的前处理和回收已经有了较多的研究,但是现有的方法依然有着各种缺陷。因此,开发一种简单、高效、回收成本低、环境污染少、杂质含量低的回收废旧磷酸铁锂电池的方法,对本领域具有非常重大的意义。At present, researchers at home and abroad have conducted more research on the pretreatment and recycling of lithium iron phosphate batteries, but the existing methods still have various defects. Therefore, the development of a simple, efficient, low recovery cost, less environmental pollution, and low impurity content method for recycling used lithium iron phosphate batteries is of great significance in the art.
发明内容Summary of the invention
鉴于以上所述现有技术的缺点,本发明的目的在于提供一种回收制备磷酸铁锂正极材料的方法及其制备获得的回收的磷酸铁锂正极材料,并进一步提供包括所述回收的磷酸铁锂正极材料的锂离子电池,用于解决现有技术中的问题。In view of the above-mentioned shortcomings of the prior art, an object of the present invention is to provide a method for recovering and preparing lithium iron phosphate cathode material and the recovered lithium iron phosphate cathode material obtained by the preparation, and further to provide the recovered iron phosphate Lithium ion batteries with lithium cathode materials are used to solve the problems in the prior art.
为实现上述目的及其他相关目的,本发明一方面提供一种回收制备磷酸铁锂正极材料的方法,包括:In order to achieve the above object and other related objects, one aspect of the present invention provides a method for recovering and preparing lithium iron phosphate cathode material, including:
a)将回收的电芯材料与酸溶液接触,固液分离得到第一液相和不溶物;a) Contacting the recovered battery material with the acid solution, solid-liquid separation to obtain the first liquid phase and insolubles;
b)调节步骤a)所提供的第一液相的pH值,固液分离得到第一含锂溶液和第一沉淀;b) Adjust the pH value of the first liquid phase provided in step a), and obtain the first lithium-containing solution and the first precipitate by solid-liquid separation;
c)调节步骤b)所提供的第一含锂溶液的pH值,固液分离得到第二含锂溶液和第二沉淀;c) Adjust the pH value of the first lithium-containing solution provided in step b), and obtain the second lithium-containing solution and the second precipitate by solid-liquid separation;
d)将步骤b)所提供的第一沉淀、步骤c)所提供的第二含锂溶液与助剂混合,得到第二液相;d) mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second liquid phase;
e)调节步骤d)所提供的第二液相中Li元素、Fe元素、P元素、C元素的含量,得到第三液相;e) Adjust the content of Li element, Fe element, P element, and C element in the second liquid phase provided in step d) to obtain a third liquid phase;
f)脱除步骤e)所提供的第三液相的溶剂,得到磷酸铁锂前驱体;f) removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor;
g)将步骤f)所提供的磷酸铁锂前驱体在还原环境下煅烧,得到磷酸铁锂正极材料。g) The lithium iron phosphate precursor provided in step f) is calcined under a reducing environment to obtain a lithium iron phosphate cathode material.
本发明另一方面提供一种回收制备的磷酸铁锂正极材料,通过所述的回收制备磷酸铁锂正极材料的方法制备获得。Another aspect of the present invention provides a recovered lithium iron phosphate cathode material prepared and obtained by the foregoing method for recycling lithium iron phosphate cathode material.
本发明另一方面提供一种锂离子电池,包括所述的回收制备的磷酸铁锂正极材料。Another aspect of the present invention provides a lithium ion battery including the recovered lithium iron phosphate cathode material.
相对于现有技术,本发明具有以下有益效果:Compared with the prior art, the present invention has the following beneficial effects:
1、回收方法简单,将电芯拆解后直接于酸溶液接触,进行简单分离直接一步合成磷酸铁锂正极材料,无需进行正负极片、隔离膜机械分离以及极片和活性材料分离的步骤。1. The recovery method is simple. After disassembling the cell, it is directly contacted with the acid solution, and the simple separation directly synthesizes the lithium iron phosphate cathode material without the steps of mechanical separation of the positive and negative plates, the separation membrane, and the separation of the pole piece and the active material. .
2、回收利用率高,磷酸铁锂电芯中具有化学计量比的锂源、铁源、磷源,且电解液中的锂盐为补充可用的锂盐,电池中的有机物和负极片上的碳材料,为补充可用的碳源。本发明充分利用电解液中的锂元素和负极片中的碳材料,使得在步骤d中仅需添加回收过程少量损失的元素,甚至完全不需要添加额外的元素即可合成磷酸铁锂正极材料。2. The recycling rate is high, the lithium iron phosphate battery has a stoichiometric ratio of lithium source, iron source, and phosphorus source, and the lithium salt in the electrolyte supplements the available lithium salt, the organic matter in the battery, and the carbon material on the negative electrode. , To supplement the available carbon source. The present invention makes full use of the lithium element in the electrolyte and the carbon material in the negative electrode sheet, so that only a small amount of elements lost in the recovery process need to be added in step d, and even no additional elements need to be added to synthesize the lithium iron phosphate cathode material.
3、用于电池的磷酸铁锂正极材料,需要对重金属杂质离子含量有所限制,而本发明相当于在已控制重金属离子含量的体系之基础上,进一步回收提纯,回收过程中新增杂质金属离子仅来自于基材中的铜和铝,基本不含其它过渡金属杂质元素,处理简便。3. The lithium iron phosphate cathode material used in the battery needs to limit the content of heavy metal impurity ions, and the present invention is equivalent to the further recovery and purification on the basis of the system that controls the content of heavy metal ions, and the impurity metal is newly added in the recovery process The ions come only from copper and aluminum in the substrate, and they are basically free of other transition metal impurity elements, which is easy to handle.
4、回收成本低,节省中间工序,一步合成最终磷酸铁锂正极材料产品,节约回收成本。4. Low recycling cost, save intermediate process, one-step synthesis of final lithium iron phosphate cathode material product, save recycling cost.
5、回收合成的磷酸铁锂正极材料具有很好的综合性能。5. Recycled synthetic lithium iron phosphate cathode material has very good comprehensive performance.
附图说明BRIEF DESCRIPTION
图1显示为本发明实施例结果示意图。Figure 1 shows a schematic diagram of the results of an embodiment of the present invention.
具体实施方式detailed description
下面详细说明本发明的锂离子电池及其制备方法。The lithium ion battery of the present invention and its preparation method are described in detail below.
本发明第一方面提供一种回收制备磷酸铁锂正极材料的方法,包括:A first aspect of the present invention provides a method for recovering and preparing lithium iron phosphate cathode material, including:
a)将回收的电芯材料与酸溶液接触,固液分离得到第一液相和不溶物;a) Contacting the recovered battery material with the acid solution, solid-liquid separation to obtain the first liquid phase and insolubles;
b)调节步骤a)所提供的第一液相的pH值,固液分离得到第一含锂溶液和第一沉淀;b) Adjust the pH value of the first liquid phase provided in step a), and obtain the first lithium-containing solution and the first precipitate by solid-liquid separation;
c)调节步骤b)所提供的第一含锂溶液的pH值,固液分离得到第二含锂溶液和第二沉淀;c) Adjust the pH value of the first lithium-containing solution provided in step b), and obtain the second lithium-containing solution and the second precipitate by solid-liquid separation;
d)将步骤b)所提供的第一沉淀、步骤c)所提供的第二含锂溶液与助剂混合,得到第二液相;d) mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second liquid phase;
e)调节步骤d)所提供的第二液相中Li元素、Fe元素、P元素、C元素的含量,得到第三液相;e) Adjust the content of Li element, Fe element, P element, and C element in the second liquid phase provided in step d) to obtain a third liquid phase;
f)脱除步骤e)所提供的第三液相的溶剂,得到磷酸铁锂前驱体;f) removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor;
g)将步骤f)所提供的磷酸铁锂前驱体在还原性气体存在的条件下煅烧,得到磷酸铁 锂正极材料;g) calcining the lithium iron phosphate precursor provided in step f) in the presence of a reducing gas to obtain a lithium iron phosphate cathode material;
本发明所提供的回收制备磷酸铁锂正极材料的方法可以通过将电芯拆解后直接与酸溶液接触,可以简单分离直接一步合成磷酸铁锂正极材料,整个制备过程中通过回收套用可以充分利用电解液中的锂元素,最终制备获得的磷酸铁锂正极材料杂质含量少。所述磷酸铁锂电池通常指以磷酸铁锂作为正极材料的锂离子电池,所述磷酸铁锂的化学式可以是LiFe yMn 1-y-zM” zPO 4/C b(b≥0,M”选自Cr、Mg、Ti、Al、Zn、W、Nb、Zr中一种或多种的组合,0.1≤y≤1.0,0≤z≤0.9)。 The method for recovering and preparing lithium iron phosphate cathode material provided by the present invention can be directly contacted with an acid solution after disassembling the battery cell, and can be directly separated and directly synthesized in one step to synthesize lithium iron phosphate cathode material, which can be fully utilized by recycling in the entire preparation process The lithium element in the electrolyte and the final preparation of the lithium iron phosphate cathode material have less impurity content. The lithium iron phosphate battery generally refers to a lithium ion battery using lithium iron phosphate as a positive electrode material, and the chemical formula of the lithium iron phosphate may be LiFe y Mn 1-yz M” z PO 4 /C b (b≥0, M” One or more combinations selected from Cr, Mg, Ti, Al, Zn, W, Nb, and Zr (0.1≤y≤1.0, 0≤z≤0.9).
本发明所提供的回收制备磷酸铁锂正极材料的方法中,可以包括:将回收的电芯材料与酸溶液接触,固液分离得到第一液相。本领域技术人员可选择合适的方式获得回收的电芯材料,所述回收的电芯材料通常包括正极极片,例如,本领域技术人员可以使用未去除壳体的磷酸铁锂电池电芯,所述电芯材料包括电池金属(一般为Al或钢)壳或聚合物壳体、正负极片、隔离膜和电解液;再例如,本领域技术人员可以使用去除壳体的磷酸铁锂电池电芯,以获得包括正极极片的电芯,更具体可以是包括正极极片的裸电芯;再例如,所述电芯材料可以是正极极片,本领域技术人员可以将获得的包括正极极片的电芯进一步分离,以获得正极极片。所述回收的电芯通常为放电后的电芯,例如,可以将电芯放电至2.5V以下,以保证处理过程的安全性。所述回收的电芯可以为整体回收的电芯,即拆解以后并未进一步将电芯的各部件进行分离,所述回收的电芯材料通常可以包括正极极片,还可以包括隔离膜和/或负极极片等,还可以包括电解液,由于所述电解液为回收的电解液,所以所述电解液中通常含有一定量的锂元素,电解液中的锂元素的含量通常在电解液中的含量为0.5%~2%,由于电芯中注液量的不同,电解液中元素含量也有所区别,通常锂元素含量相对与正极活性物质百分比为0.2%~0.8%、0.2%~0.4%、0.4%~0.6%、或0.6%~0.8%。所述酸溶液通常为水溶液,酸溶液的摩尔浓度可以为0.5~10M、0.5~1M、1~2M、2~3M、3~4M、4~5M、5~6M、6~8M、或8~10M,优选可以为1~6M。所述酸溶液中的酸可以是无机酸和/或有机酸,酸溶液中的无机酸优选为无机强酸,具体可以是包括但不限于盐酸、硝酸、硫酸、高氯酸、氯酸等中的一种或多种的组合,酸溶液中的有机酸优选为有机强酸,具体可以是包括但不限于2,4,6-三硝基苯酚、2,4,6-三硝基苯甲酸、三氟乙酸、三氯乙酸、甲磺酸、苯磺酸、KMD酸等中的一种或多种的组合。所述酸溶液还可以具有氧化性,例如,所述酸溶液中的酸可以是具有氧化性的酸,再例如,所述酸溶液可以包括过氧化氢,具体可以是酸的过氧化氢溶液,过氧化氢在酸溶液中的摩尔浓度可以为0.5~10M、0.5~1M、1~2M、2~3M、3~4M、4~5M、5~6M、6~8M、或8~10M,优选可以为1~6M。The method for recovering and preparing lithium iron phosphate cathode material provided by the present invention may include: contacting the recovered battery core material with an acid solution, and solid-liquid separation to obtain a first liquid phase. Those skilled in the art can choose a suitable way to obtain recycled battery core materials, and the recycled battery core materials usually include positive pole pieces. For example, those skilled in the art can use lithium iron phosphate battery cells without removing the casing. The cell material includes a battery metal (usually Al or steel) shell or polymer case, positive and negative electrode plates, separators and electrolyte; for another example, those skilled in the art can use a lithium iron phosphate battery with the case removed Core to obtain a cell including a positive pole piece, more specifically a bare cell including a positive pole piece; for another example, the cell material may be a positive pole piece, and a person skilled in the art may obtain the positive pole piece The cells of the sheet are further separated to obtain a positive pole piece. The recovered battery cell is usually a discharged battery cell, for example, the battery cell can be discharged to 2.5 V or less to ensure the safety of the treatment process. The recovered battery cell may be a whole-recovered battery cell, that is, after disassembly, the components of the battery cell are not further separated. The recovered battery cell material may generally include a positive pole piece, and may also include an isolation film and / Or negative electrode, etc., may also include electrolyte, because the electrolyte is recovered electrolyte, so the electrolyte usually contains a certain amount of lithium element, the content of lithium element in the electrolyte is usually in the electrolyte The content in is 0.5%~2%. Due to the difference in the amount of liquid injected into the battery cell, the element content in the electrolyte is also different. Generally, the lithium element content is 0.2%~0.8%, 0.2%~0.4 relative to the positive electrode active material percentage %, 0.4% to 0.6%, or 0.6% to 0.8%. The acid solution is usually an aqueous solution, and the molar concentration of the acid solution may be 0.5 to 10M, 0.5 to 1M, 1 to 2M, 2 to 3M, 3 to 4M, 4 to 5M, 5 to 6M, 6 to 8M, or 8 to 10M, preferably 1 to 6M. The acid in the acid solution may be an inorganic acid and/or an organic acid. The inorganic acid in the acid solution is preferably an inorganic strong acid, which may specifically include but not limited to hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, chloric acid, etc. One or more combinations. The organic acid in the acid solution is preferably an organic strong acid, which may specifically include but not limited to 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, tri A combination of one or more of fluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, KMD acid, etc. The acid solution may also have oxidizing properties. For example, the acid in the acid solution may be an oxidizing acid. For another example, the acid solution may include hydrogen peroxide, specifically an acidic hydrogen peroxide solution. The molar concentration of hydrogen peroxide in the acid solution may be 0.5 to 10M, 0.5 to 1M, 1 to 2M, 2 to 3M, 3 to 4M, 4 to 5M, 5 to 6M, 6 to 8M, or 8 to 10M, preferably It can be 1~6M.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,在所述步骤a)中,所述第一液相中Fe 2+的浓度可以<30ppm、<40ppm、<50ppm、<60ppm、<80ppm、或<100ppm,优选的,优选的,第一液相中Fe 2+的浓度≤50ppm。本领域技术人员可选择合适的方法调节第一液相中的Fe 2+的浓度,例如,可以通过使用具有氧化性的酸溶液,以还原溶液中的Fe 2+,再例如,所述步骤a)还可以包括:将第一液相进行氧化处理。所述氧化处理通常指将第一液相与具有氧化性的物质接触,从而使第一液相中具有还原性的物质(例如,亚铁离子Fe 2+)被氧化的处理方法。溶液中的亚铁离子被转变成铁离子以后,在后续调pH值分离Fe元素的回收率更高,其原因在于pH<3,磷酸铁基本完全沉淀,而磷酸亚铁完全沉淀pH需>5,与Al、Cu沉淀有交叉。Fe 2+的浓度可以使用邻二氮菲分光光度法进行测定。将第一液相进行氧化处理的方法对于本领域技术人员来说应该是已知的,如果在第一液相中未添加过氧化氢溶液或者过氧化氢溶液含量不足,可以继续添加如下氧化剂,例如,可以将第一液相与氧化剂接触,所述氧化剂可以是例如氧气等,更具体可以是向第一液相中通入含有氧气的气体,所述含有氧气的气体可以是包括但不限于氧气、空气、氧气与其他合适气体的混合(例如,惰性气体等)等中的一种或多种的组合。 In the method for recovering and preparing a lithium iron phosphate cathode material provided by the present invention, in the step a), the concentration of Fe 2+ in the first liquid phase may be <30 ppm, <40 ppm, <50 ppm, <60 ppm, < 80 ppm, or <100 ppm, preferably, preferably, the concentration of Fe 2+ in the first liquid phase is ≤50 ppm. Skill in the art can select a suitable adjusting the concentration of Fe 2+ in the first liquid phase, for example, may have the acid solution by using an oxidizing, reducing to Fe 2+ solution, and then, for example, a step ) May also include: performing oxidation treatment on the first liquid phase. The oxidation treatment generally refers to a treatment method of contacting the first liquid phase with an oxidizing substance, thereby oxidizing a reducing substance (for example, ferrous ion Fe 2+ ) in the first liquid phase. After the ferrous ions in the solution are converted into iron ions, the recovery rate of the separated Fe element in the subsequent pH adjustment is higher, because the pH is less than 3, the iron phosphate is basically completely precipitated, and the ferrous phosphate is completely precipitated. The pH needs to be> 5 , Al and Cu precipitation cross. The concentration of Fe 2+ can be measured using phenanthroline spectrophotometry. The method of oxidizing the first liquid phase should be known to those skilled in the art. If no hydrogen peroxide solution is added to the first liquid phase or the content of hydrogen peroxide solution is insufficient, the following oxidant can be added continuously. For example, the first liquid phase may be contacted with an oxidant, and the oxidant may be, for example, oxygen, etc. More specifically, a gas containing oxygen may be introduced into the first liquid phase, and the gas containing oxygen may include but is not limited to Combination of one or more of oxygen, air, a mixture of oxygen and other suitable gases (eg, inert gas, etc.), etc.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,本领域技术人员可选择合适的回收的电芯材料与酸溶液接触的反应条件,以达到快速、充分溶解电芯中磷酸铁锂活性材料的目的,例如,回收电芯与酸溶液接触的温度条件可以为10℃~60℃、10℃~20℃、20℃~30℃、30℃~40℃、40℃~50℃、或50℃~60℃,优选可以为15℃~40℃,更优选可以为20℃~35℃,再例如,回收电芯与酸接触的时间可以为0.5h~5h、0.5h~1h、1h~2h、2h~3h、3h~4h、或4h~5h,优选可以为1h~3h。回收的电芯材料与酸溶液接触后,通常可以通过固液分离的方法,提供第一液相和其他不溶的第二沉淀(通常可以是杂质组分),所述第一液相中,通常可以溶解有回收电芯中的磷酸铁锂活性物质、石墨负极中的锂、铝箔、铜箔等组分,所述第一液相中的主要元素可以有Fe、P、Li、Al、Cu、C、O、H等,所述,分离所获得的第二沉淀中通常可以包括石墨、导电碳、粘结剂、隔离膜、基材等,分离所获得的第二沉淀可以进一步被分离以获取石墨,这些方法对于本领域技术人员来说应该是已知的,例如,可以采用不同孔径的滤网过滤,从而筛分获得石墨。In the method for recovering and preparing lithium iron phosphate cathode material provided by the present invention, a person skilled in the art may select a suitable reaction condition for contacting the recovered battery material with an acid solution to achieve rapid and sufficient dissolution of lithium iron phosphate activity in the battery The purpose of the material, for example, the temperature conditions of the contact between the recovery cell and the acid solution may be 10°C to 60°C, 10°C to 20°C, 20°C to 30°C, 30°C to 40°C, 40°C to 50°C, or 50 ℃ ~ 60 ℃, preferably 15 ℃ ~ 40 ℃, more preferably 20 ℃ ~ 35 ℃, for example, the recovery battery and acid contact time can be 0.5h ~ 5h, 0.5h ~ 1h, 1h ~ 2h , 2h to 3h, 3h to 4h, or 4h to 5h, preferably 1h to 3h. After contacting the recovered battery material with the acid solution, it is usually possible to provide a first liquid phase and other insoluble second precipitates (usually impurity components) by solid-liquid separation. In the first liquid phase, usually It can dissolve the lithium iron phosphate active material in the recovered battery, lithium in the graphite negative electrode, aluminum foil, copper foil and other components. The main elements in the first liquid phase can be Fe, P, Li, Al, Cu, C, O, H, etc. As mentioned, the second precipitate obtained by separation can generally include graphite, conductive carbon, binder, separator, substrate, etc. The second precipitate obtained by separation can be further separated to obtain Graphite, these methods should be known to those skilled in the art, for example, it can be filtered with a filter of different pore sizes to obtain graphite by sieving.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:调节步骤a)所提供的第一液相的pH值,固液分离得到第一含锂溶液和第一沉淀。步骤a)所提供的第一液相的pH值通常为强酸性,本领域技术人员可以根据第一液相的pH值,适当调整所述酸溶液的用量,例如,所述第一液相的pH值可以<0.8、<1、<1.2、<1.4.、<1.6、<1.8、或<2, 优选的,所述第一液相的pH值可以<1。通过调节第一液相的pH值,随着pH值的逐渐升高,可以使溶液中的组分先后析出,以达到分离组分的目的。本领域技术人员可选择合适的pH处理条件,例如,可以调节第一液相的pH值,固液分离(例如,可以是过滤等方法),以获得第一沉淀和第一含锂溶液,所述第一沉淀的主要组分通常是磷酸铁,所述第一含锂溶液可以是磷酸铁充分析出后的处理液。具体的,可以将第一液相的pH调节值至1~3、1~1.5、1.5~2、2~2.5、或2.5~3,优选可以将第一液相的pH值调节至1.5~2.5,以使得第一液相中磷酸铁等组分可以被充分地析出,而其余组分则依然溶解于溶液中。The method for recovering and preparing the lithium iron phosphate cathode material provided by the present invention may further include: adjusting the pH value of the first liquid phase provided in step a), and solid-liquid separation to obtain the first lithium-containing solution and the first precipitate. The pH value of the first liquid phase provided in step a) is generally strongly acidic, and those skilled in the art can appropriately adjust the amount of the acid solution according to the pH value of the first liquid phase, for example, the The pH value may be <0.8, <1, <1.2, <1.4., <1.6, <1.8, or <2. Preferably, the pH value of the first liquid phase may be <1. By adjusting the pH value of the first liquid phase, with the gradual increase of the pH value, the components in the solution can be sequentially precipitated to achieve the purpose of separating the components. A person skilled in the art can select suitable pH treatment conditions. For example, the pH of the first liquid phase can be adjusted, and solid-liquid separation (for example, filtration or the like) can be performed to obtain the first precipitate and the first lithium-containing solution. The main component of the first precipitation is usually iron phosphate, and the first lithium-containing solution may be a treatment liquid after the iron phosphate is fully analyzed. Specifically, the pH of the first liquid phase can be adjusted to 1 to 3, 1 to 1.5, 1.5 to 2, 2 to 2.5, or 2.5 to 3, and preferably the pH of the first liquid phase can be adjusted to 1.5 to 2.5 , So that components such as iron phosphate in the first liquid phase can be fully precipitated, while the remaining components are still dissolved in the solution.
发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:调节步骤b)所提供的第一含锂溶液的pH值,固液分离得到第二含锂溶液和第二沉淀。通过调节第一含锂溶液的pH值,随着pH值的逐渐升高,可以使溶液中的组分先后析出,以达到分离组分的目的。本领域技术人员可选择合适的pH处理条件,例如,可以调节第一含锂溶液的pH值,固液分离(例如,可以是过滤等方法),以获得第二含锂溶液和第二沉淀。所述第二含锂溶液为主要组分为锂盐的锂盐溶液,所述第二含锂溶液中,所含有的锂盐可以是LiCl、LiNO 3等,所述第二沉淀中,主要可以包括磷酸铝、磷酸铜、氢氧化铜等。具体的,可以调节第一含锂溶液的pH值至4~11、4~5、5~6、6~7、7~8、8~9、9~10、或10~11,优选可以调节第一含锂溶液的pH值至6~10,以使得Al、Cu等金属(通常为杂质组分)可以被充分地析出以形成第二沉淀,而含锂的化合物则大部分依然溶解于溶液中,例如,所述第二含锂溶液中的Al元素含量不高于30ppm。 The method for recovering a lithium iron phosphate cathode material provided by the invention may further include: adjusting the pH value of the first lithium-containing solution provided in step b), and solid-liquid separation to obtain a second lithium-containing solution and a second precipitate. By adjusting the pH value of the first lithium-containing solution, with the gradual increase of the pH value, the components in the solution can be successively precipitated to achieve the purpose of separating the components. A person skilled in the art can select suitable pH treatment conditions. For example, the pH of the first lithium-containing solution can be adjusted, and solid-liquid separation (eg, filtration or the like) can be performed to obtain the second lithium-containing solution and the second precipitate. The second lithium-containing solution is a lithium salt solution whose main component is a lithium salt. The lithium salt contained in the second lithium-containing solution may be LiCl, LiNO 3, etc. The second precipitation may mainly be Including aluminum phosphate, copper phosphate, copper hydroxide, etc. Specifically, the pH of the first lithium-containing solution can be adjusted to 4-11, 4-5, 5-6, 6-7, 7-8, 8-9, 9-10, or 10-11, preferably it can be adjusted The pH value of the first lithium-containing solution is 6 to 10, so that metals such as Al and Cu (usually impurity components) can be fully precipitated to form a second precipitate, while most lithium-containing compounds are still dissolved in the solution In, for example, the Al element content in the second lithium-containing solution is not higher than 30 ppm.
发明所提供的回收制备磷酸铁锂正极材料的方法中,本领域技术人员可选择合适的碱以用于调节第一液相的pH值和/或第一含锂溶液的pH值,所使用的碱可以是无机碱和/或有机碱,所述无机碱可以是包括但不限于氨水、氢氧化钠、氢氧化钾等中的一种或多种的组合,所述有机碱可以是包括但不限于甲胺、乙胺、乙醇胺、乙二胺、二甲胺、三甲胺、三乙胺、丙胺、异丙胺、1,3-丙二胺、三丙胺、丁胺、异丁胺、叔丁胺、己胺、辛胺、环己胺等中的一种或多种的组合。In the method for recovering and preparing lithium iron phosphate cathode material provided by the invention, a person skilled in the art can select a suitable base for adjusting the pH of the first liquid phase and/or the pH of the first lithium-containing solution. The base may be an inorganic base and/or an organic base. The inorganic base may include but not limited to a combination of one or more of ammonia, sodium hydroxide, potassium hydroxide, etc. The organic base may include but not Limited to methylamine, ethylamine, ethanolamine, ethylenediamine, dimethylamine, trimethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, tripropylamine, butylamine, isobutylamine, tert-butylamine, hexylamine A combination of one or more of amine, octylamine, cyclohexylamine, etc.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:将步骤b)所提供的第一沉淀、步骤c)所提供的第二含锂溶液与助剂混合,得到第二液相。所述第二液相可以是均匀的溶液,也可以是均匀分散的悬浮液。所述助剂通常用于增加溶液体系对于磷酸铁的溶解性,从而可以有助于形成各种离子分布均匀的溶液,本领域技术人员可选择合适种类和配比的组分,以提供所述助剂,助剂的使用质量可以是磷酸铁与含锂溶液质量的0.1%~20%、0.1%~0.5%、0.5%~1%、1%~2%、2%~3%、3%~5%、5%~10%、10%~15%、或 15%~20%,构成所述助剂的组分通常可以包括但不限于酸、分散剂、表面活性剂、螯合剂等中的一种或多种的组合。助剂中的酸可以是无机酸和/或有机酸,助剂中的无机酸优选为无机强酸,具体可以是包括但不限于盐酸、硝酸、硫酸、高氯酸、氯酸等中的一种或多种的组合,助剂中的有机酸优选为有机强酸,具体可以是包括但不限于2,4,6-三硝基苯酚、2,4,6-三硝基苯甲酸、三氟乙酸、三氯乙酸、甲磺酸、苯磺酸、KMD酸等中的一种或多种的组合。所述分散剂可以是包括但不限于水、乙醇、丙酮、丙醇、异丙醇、甲醇、正丁醇、乙腈、四氢呋喃、乙醚二氯甲烷、氯仿、二甲基亚砜、二甲基甲酰胺等中的一种或多种的组合。所述表面活性剂可以是包括但不限于十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、聚乙二醇、聚氧化乙烯、聚丙烯酰胺或羧甲基纤维素、聚乙烯吡咯烷酮、乙烯-丙烯酸共聚物、乙烯-醋酸乙烯共聚物等中的一种或多种的组合。所述螯合剂可以是包括但不限于次氨基三乙酸、1,2-环己二胺四乙酸、乙二胺四乙酸、柠檬酸、苹果酸、草酸、乙酸、水杨酸等中的一种或多种的组合。The method for recovering and preparing lithium iron phosphate cathode material provided by the present invention may further include: mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second Liquid phase. The second liquid phase may be a uniform solution or a uniformly dispersed suspension. The auxiliary agent is generally used to increase the solubility of the solution system to iron phosphate, which can help to form a solution with a uniform distribution of various ions. Those skilled in the art can select appropriate types and proportions of components to provide the described Auxiliary agent, the quality of the auxiliary agent can be 0.1% to 20%, 0.1% to 0.5%, 0.5% to 1%, 1% to 2%, 2% to 3%, 3% of the mass of iron phosphate and lithium-containing solution ~5%, 5%~10%, 10%~15%, or 15%~20%, the components constituting the auxiliary agent can usually include but not limited to acids, dispersants, surfactants, chelating agents, etc. One or more combinations. The acid in the auxiliary agent may be an inorganic acid and/or an organic acid, and the inorganic acid in the auxiliary agent is preferably a strong inorganic acid, which may specifically include but not limited to one of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, chloric acid, etc. Or a combination of multiple types, the organic acid in the auxiliary agent is preferably a strong organic acid, which may specifically include but not limited to 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, trifluoroacetic acid , Trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, KMD acid, etc. one or more combinations. The dispersing agent may include but not limited to water, ethanol, acetone, propanol, isopropanol, methanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether methylene chloride, chloroform, dimethyl sulfoxide, dimethyl methyl alcohol A combination of one or more of amides and the like. The surfactant may include but is not limited to cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, poly A combination of one or more of ethylene glycol, polyethylene oxide, polyacrylamide or carboxymethyl cellulose, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer, and the like. The chelating agent may be one of but not limited to nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, oxalic acid, acetic acid, salicylic acid, etc. Or a combination of multiple.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:调节步骤d)所提供的第二液相中Li元素、Fe元素、P元素、C元素的含量,得到第三液相。本领域技术人员可根据所需制备的磷酸铁锂正极材料的种类,确定第三液相中Li元素、Fe元素、P元素、C元素的含量,例如,Fe元素和P元素之间的摩尔比通常是基本等量的,Fe元素和P元素之间的摩尔比具体可以是1:0.95~1.05,再例如,Li和C由于在最终热处理过程中有一定损耗(挥发),因而Li的使用量通常是过量的,具体可以是Li元素、Fe元素之间的摩尔比可以为(1~1.5):(0.95~1.05),Li元素、P元素之间的摩尔比可以为(1~1.5):(0.95~1.05),Li元素、C元素之间的摩尔比可以为(1~1.5):(0.5~4)。调整液相中各元素的含量时,可以通过合适的分析方法确定体系中的元素含量,这些方法对于本领域技术人员来说应该是已知的,可适用的分析方法可以是包括但不限于ICP、化学滴定、液相色谱、沉淀法、碳硫分析法等中的一种或者多种的组合确定体系中的元素含量。调整液相中各元素的方法对于本领域技术人员来说应该是已知的,通常可以通过引入对应的锂源、铁源、磷源、碳源等中的一种或多种的组合以调节第二液相中各元素的含量,所述锂源、铁源、磷源、碳源通常可以是各种适用于制备磷酸铁锂正极材料的原材料,例如,所使用的锂源可以是包括但不限于碳酸锂、磷酸二氢锂、磷酸锂、醋酸锂、氢氧化锂、草酸锂、硝酸锂等中的一种或多种的组合,所使用的铁源可以是包括但不限于三氧化二铁、四氧化三铁、磷酸铁、磷酸亚铁、硝酸铁、氯化铁、硝酸亚铁、氯化亚铁、醋酸铁、碳酸铁、碳酸亚铁、乙酰丙酮铁等中的一种或多种的组合,所使用的磷源可以是包括但不限于磷酸二氢铵、磷酸二氢锂、磷酸铁、磷酸亚铁、磷酸等中的一 种或多种的组合,所使用的碳源可以是包括但不限于石墨、导电碳、乙炔黑、导电炭黑、碳纤维、碳纳米管、纳米碳微球、葡萄糖、蔗糖、果糖、聚丙烯腈等中的一种或多种的组合,所述碳源优选为可溶性碳源。在所述步骤e)中,用于调节第二液相中铁元素的含量的铁源可以包括至少部分的步骤b)中所提供的第一沉淀,从而可以实现磷酸铁的充分回收套用。在所述步骤e)中,用于调节第二液相中碳元素的含量的碳源可以包括至少部分的步骤a)中所述不溶物经筛分得到的碳源,从而可以实现材料的充分回收套用。所述步骤e)中,调节元素比例时所引入的Fe元素通常不超过第三液相中Fe元素总量的25%、20%、15%、10%、或5%,调节元素比例时所引入的Li元素通常不超过第三液相中Li元素总量的25%、20%、15%、10%、或5%,调节元素比例时所引入的P元素通常不超过第三液相中P元素总量的25%、20%、15%、10%、或5%,调节元素比例时所引入的C元素可以占第三液相中C元素总量的50%~100%、50%~60%、60%~70%、70%~80%、80%~90%、或90%~100%。The method for recovering and preparing lithium iron phosphate cathode material provided by the present invention may further include: adjusting the content of Li element, Fe element, P element and C element in the second liquid phase provided in step d) to obtain a third liquid phase. A person skilled in the art can determine the content of Li, Fe, P, and C elements in the third liquid phase according to the type of lithium iron phosphate cathode material to be prepared, for example, the molar ratio between Fe and P elements Usually it is basically the same amount. The molar ratio between Fe and P can be 1:0.95~1.05. For another example, Li and C have a certain loss (volatility) during the final heat treatment, so the amount of Li used It is usually excessive, specifically, the molar ratio between Li element and Fe element can be (1 to 1.5): (0.95 to 1.05), and the molar ratio between Li element and P element can be (1 to 1.5): (0.95 to 1.05), the molar ratio between the Li element and the C element may be (1 to 1.5): (0.5 to 4). When adjusting the content of each element in the liquid phase, the content of elements in the system can be determined by a suitable analytical method. These methods should be known to those skilled in the art, and applicable analytical methods may include but are not limited to ICP , One or more of chemical titration, liquid chromatography, precipitation method, carbon and sulfur analysis method to determine the element content in the system. The method of adjusting each element in the liquid phase should be known to those skilled in the art, and can usually be adjusted by introducing one or more combinations of corresponding lithium source, iron source, phosphorus source, carbon source, etc. The content of each element in the second liquid phase, the lithium source, iron source, phosphorus source, and carbon source may generally be various raw materials suitable for preparing lithium iron phosphate cathode materials, for example, the lithium source used may include but Not limited to one or more combinations of lithium carbonate, lithium dihydrogen phosphate, lithium phosphate, lithium acetate, lithium hydroxide, lithium oxalate, lithium nitrate, etc. The iron source used may include but is not limited to dioxide One or more of iron, ferric oxide, ferric phosphate, ferrous phosphate, ferric nitrate, ferric chloride, ferrous nitrate, ferrous chloride, ferric acetate, ferric carbonate, ferrous carbonate, ferric acetylacetonate, etc. A combination of species, the phosphorus source used may be one or more combinations including but not limited to ammonium dihydrogen phosphate, lithium dihydrogen phosphate, iron phosphate, ferrous phosphate, phosphoric acid, etc. The carbon source used may be Is a combination of one or more of graphite, conductive carbon, acetylene black, conductive carbon black, carbon fiber, carbon nanotubes, nanocarbon microspheres, glucose, sucrose, fructose, polyacrylonitrile, etc. The carbon source is preferably a soluble carbon source. In the step e), the iron source for adjusting the content of the iron element in the second liquid phase may include at least part of the first precipitate provided in the step b), so that sufficient recovery and application of iron phosphate can be achieved. In the step e), the carbon source for adjusting the content of the carbon element in the second liquid phase may include at least a part of the carbon source obtained by sieving the insoluble matter in the step a), so that sufficient material can be achieved Recycling. In step e), the Fe element introduced when adjusting the element ratio usually does not exceed 25%, 20%, 15%, 10%, or 5% of the total Fe element in the third liquid phase. The introduced Li element usually does not exceed 25%, 20%, 15%, 10%, or 5% of the total Li element in the third liquid phase, and the P element introduced when adjusting the element ratio usually does not exceed the third liquid phase 25%, 20%, 15%, 10%, or 5% of the total amount of P element, the C element introduced when adjusting the element ratio may account for 50% to 100%, 50% of the total amount of C element in the third liquid phase ~60%, 60%~70%, 70%~80%, 80%~90%, or 90%~100%.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:脱除步骤e)所提供的第三液相的溶剂,得到磷酸铁锂前驱体。本领域技术人员可选择合适的方法脱除步骤e)所提供的第三液相的溶剂,例如,脱除溶剂的方法可以干燥等,更具体可以是包括但不限于常压干燥、减压干燥、喷雾干燥、沸腾干燥、冷冻干燥等中的一种或多种的组合。The method for recovering and preparing a lithium iron phosphate cathode material provided by the present invention may further include: removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor. A person skilled in the art may select a suitable method to remove the solvent of the third liquid phase provided in step e), for example, the method of removing the solvent may be dried, etc., and more specifically may include, but not limited to, atmospheric drying and vacuum drying , Spray drying, boiling drying, freeze drying, etc. one or more combinations.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,还可以包括:将步骤f)所提供的磷酸铁锂前驱体在还原环境下煅烧,得到磷酸铁锂正极材料。本领域技术人员可选择合适的方法,通过步骤f)所提供的前驱体以制备磷酸铁锂正极材料,例如,可以通过还原性气体和/或还原性液体提供所述还原环境,具体可以通过氢气和/或一氧化碳,或者那些在加热条件下能够产生氢气和/或一氧化碳的气体和/或液体,用于提供所述还原环境的还原性气体和/或还原性液体可以是包括但不限于氢气、一氧化碳、乙炔、甲醇、乙醇、甲烷、乙烷等中的一种或多种的组合。再例如,煅烧温度可以为500℃~700℃、500℃~550℃、550℃~600℃、600℃~650℃、或650℃~700℃;再例如,煅烧时间可以为10min~300min、10min~20min、20min~30min、30min~50min、50min~100min、100min~150min、150min~200min、或200min~300min。The method for recovering and preparing a lithium iron phosphate cathode material provided by the present invention may further include: calcining the lithium iron phosphate precursor provided in step f) under a reducing environment to obtain a lithium iron phosphate cathode material. A person skilled in the art may select a suitable method to prepare the lithium iron phosphate cathode material through the precursor provided in step f), for example, the reducing environment may be provided by a reducing gas and/or a reducing liquid, specifically by hydrogen And/or carbon monoxide, or those gases and/or liquids capable of generating hydrogen and/or carbon monoxide under heating conditions, the reducing gas and/or reducing liquid used to provide the reducing environment may include but is not limited to hydrogen, A combination of one or more of carbon monoxide, acetylene, methanol, ethanol, methane, ethane, etc. For another example, the calcination temperature may be 500° C. to 700° C., 500° C. to 550° C., 550° C. to 600° C., 600° C. to 650° C., or 650° C. to 700° C.; for another example, the calcination time may be 10 min to 300 min, 10 min ~20min, 20min~30min, 30min~50min, 50min~100min, 100min~150min, 150min~200min, or 200min~300min.
本发明所提供的回收制备磷酸铁锂正极材料的方法中,制备获得的回收的磷酸铁锂正极材料杂质金属离子仅来自于基材中的铜和铝,基本不含其它过渡金属杂质元素,例如,基本不含有Ni、Co、Mn、K等金属离子,具体的,Cu、Al杂质离子含量之和<200ppm,除Cu、Al以外的重金属杂质离子含量之和可以小于200ppm,钠钾元素含量之和可以小于300ppm。In the method for recovering and preparing lithium iron phosphate cathode material provided by the present invention, the impurity metal ions of the recovered recovered lithium iron phosphate cathode material only come from copper and aluminum in the substrate, and are substantially free of other transition metal impurity elements, such as , Basically does not contain Ni, Co, Mn, K and other metal ions, specifically, the sum of Cu, Al impurity ion content <200ppm, the sum of heavy metal impurity ion content except Cu, Al can be less than 200ppm, sodium potassium content The sum can be less than 300ppm.
本发明第二方面提供一种回收制备的磷酸铁锂正极材料,由本发明第一方面所提供的回收制备磷酸铁锂正极材料的方法制备获得。在所述回收制备的磷酸铁锂正极材料中,杂质金属离子仅来自于基材中的铜和铝,基本不含其它过渡金属杂质元素,Cu、Al杂质离子含量之和<200ppm,除Cu、Al以外的重金属杂质离子含量之和可以小于200ppm,钠钾元素含量之和可以小于300ppm。The second aspect of the present invention provides a recovered lithium iron phosphate cathode material prepared by the method provided in the first aspect of the present invention. In the recovered lithium iron phosphate cathode material, the impurity metal ions only come from copper and aluminum in the base material, and basically do not contain other transition metal impurity elements. The sum of Cu and Al impurity ion content is less than 200ppm, except Cu, The sum of the content of heavy metal impurities ions other than Al may be less than 200 ppm, and the sum of the content of sodium and potassium elements may be less than 300 ppm.
本发明第三方面提供一种锂离子电池,包括如本发明第二方面所提供的回收制备的磷酸铁锂正极材料。所述锂离子电池通常包括正极极片,所述正极极片通常包括正极集流体和位于正极集流体上的正极活性物质层,所述正极活性物质层通常可以包括如本发明第一方面所提供的回收的磷酸铁锂正极材料。所述锂离子电池还可以包括其他可以用于锂离子电池的部件,例如,还可以包括负极极片、电池隔膜、电解液、外接电极、极耳、包装壳等。A third aspect of the present invention provides a lithium ion battery, including the lithium iron phosphate cathode material prepared and recovered as provided in the second aspect of the present invention. The lithium ion battery generally includes a positive electrode tab, and the positive electrode tab generally includes a positive electrode current collector and a positive electrode active material layer on the positive electrode current collector, and the positive electrode active material layer may generally include as provided in the first aspect of the present invention Of recycled lithium iron phosphate cathode material. The lithium-ion battery may also include other components that can be used in the lithium-ion battery, for example, it may also include a negative pole piece, a battery separator, an electrolyte, an external electrode, a tab, a packaging case, and the like.
以下通过特定的具体实例说明本发明的实施方式,本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用,本说明书中的各项细节也可以基于不同观点与应用,在没有背离本发明的精神下进行各种修饰或改变。The following describes the embodiments of the present invention through specific specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the contents disclosed in this specification. The present invention can also be implemented or applied through different specific embodiments, and the details in this specification can also be based on different viewpoints and applications, and various modifications or changes can be made without departing from the spirit of the present invention.
须知,下列实施例中未具体注明的工艺设备或装置均采用本领域内的常规设备或装置。It should be noted that, the process equipment or devices not specifically mentioned in the following embodiments adopt conventional equipment or devices in the art.
此外应理解,本发明中提到的一个或多个方法步骤并不排斥在所述组合步骤前后还可以存在其他方法步骤或在这些明确提到的步骤之间还可以插入其他方法步骤,除非另有说明;还应理解,本发明中提到的一个或多个设备/装置之间的组合连接关系并不排斥在所述组合设备/装置前后还可以存在其他设备/装置或在这些明确提到的两个设备/装置之间还可以插入其他设备/装置,除非另有说明。而且,除非另有说明,各方法步骤的编号仅为鉴别各方法步骤的便利工具,而非为限制各方法步骤的排列次序或限定本发明可实施的范围,其相对关系的改变或调整,在无实质变更技术内容的情况下,当亦视为本发明可实施的范畴。In addition, it should be understood that one or more of the method steps mentioned in the present invention does not exclude that there may be other method steps before or after the combination step or that other method steps may be inserted between these explicitly mentioned steps unless otherwise Explained; It should also be understood that the combined connection relationship between one or more devices/devices mentioned in the present invention does not exclude that there may be other devices/devices or those mentioned explicitly in these before and after the combined device/device Other devices/apparatuses can also be inserted between the two devices/apparatuses unless otherwise stated. Moreover, unless otherwise stated, the number of each method step is only a convenient tool to identify each method step, not to limit the order of each method step or to limit the scope of the present invention, the change or adjustment of its relative relationship, in If the technical content is not substantially changed, it should be regarded as the scope of the invention.
实施例1Example 1
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入1.5L,浓度为5M的盐酸溶液中,然后加入250ml 3M双氧水溶液,25℃条件下,搅拌浸泡2h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the pole ears, put the winding core (~600g) and residual electrolyte (~20g) into 1.5L of 5M hydrochloric acid Then, add 250ml of 3M hydrogen peroxide solution to the solution, and stir and soak for 2h at 25℃.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相,第一液相的pH值pH(a)=0.6。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase, and the pH value of the first liquid phase is pH(a) = 0.6.
步骤b)向上述溶液中滴加5M的氨水溶液,至pH(b)=2.0,过滤生成主要组分为磷酸铁 的第一沉淀(~230g)和第一含锂溶液。Step b) A 5M aqueous ammonia solution was added dropwise to the above solution to pH (b) = 2.0, and filtered to produce a first precipitate (~230g) and a first lithium-containing solution whose main component was iron phosphate.
步骤c)继续在上述第一含锂溶液中滴加5M的氨水溶液,至pH(c)=6.4,过滤后得到第二含锂溶液。Step c) Continue to add 5M aqueous ammonia solution dropwise to the first lithium-containing solution to pH (c) = 6.4, and obtain the second lithium-containing solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有5M盐酸、1M聚乙二醇、1M柠檬酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入18g前述步骤a)获得的碳源(主要为石墨),和1g磷酸铁,使得悬浊液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.12:1:1:1:0.8。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 1g of iron phosphate to make the suspension The molar ratio of lithium element: iron element: phosphorus element: carbon element is 1.12:1:1:1:1:0.8.
步骤f)将上述溶液充分搅拌后,采用喷雾干燥法,在喷雾干燥炉,加热至200℃进行喷雾干燥,获得前驱体粉料。Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧5h,期间通入氢氩混合气,制备获得回收的磷酸铁锂正极材料1。Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 5 hours, during which hydrogen-argon mixed gas is introduced to prepare a recovered lithium iron phosphate cathode material 1.
实施例2Example 2
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入1.5L,浓度为3M的硝酸溶液中,30℃条件下,搅拌浸泡3h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the pole ears, put the winding core (~600g) and residual electrolyte (~20g) into 1.5L of 3M nitric acid In the solution, at 30℃, stir and soak for 3h.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相,第一液相的pH值:pH(a)=0.8。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase. The pH value of the first liquid phase: pH(a ) = 0.8.
步骤b)向上述溶液中滴加三乙胺,至pH(b)=1.5,过滤生成主要组分为磷酸铁的第一沉淀(~229g),第一含锂溶液。Step b) Triethylamine is added dropwise to the above solution to pH (b) = 1.5, and filtered to generate a first precipitate (~229g) whose main component is iron phosphate, and a first lithium-containing solution.
步骤c)继续在上述第一含锂溶液中滴加三乙胺溶液,至pH(c)=5.0,过滤后得到第二含锂溶液。Step c) Continue to add the triethylamine solution dropwise to the above first lithium-containing solution until the pH (c) = 5.0, and obtain the second lithium-containing solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有2M硝酸、1M聚氧化乙烯、1M苹果酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and second lithium-containing solution are mixed, and a mixed solution containing 2M nitric acid, 1M polyethylene oxide, and 1M malic acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入17g前面步骤a)获得的碳源(主要为石墨),和0.8g三氧化二铁和1.0g磷酸,使得溶液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.12:1:1:1:0.5。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon and sulfur analyzer to test the content of element C, add 17g of the carbon source (mainly graphite) obtained in the previous step a), and 0.8g of ferric oxide and 1.0g Phosphoric acid is such that the molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution is 1.12:1:1:1:1:0.5.
步骤f)将上述溶液充分搅拌后,在90℃下减压干燥,获得前驱体粉料。Step f) After fully stirring the above solution, it is dried under reduced pressure at 90°C to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧3h,期间通入一氧化碳、氩气混合气,制备获得回收的磷酸铁锂正极材料2。Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 hours, during which a mixture of carbon monoxide and argon gas is introduced to prepare a recovered lithium iron phosphate cathode material 2.
实施例3Example 3
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入1.5L,浓度为3M的三氯乙酸溶液中,然后加入250ml 1M双氧水溶液,20℃条件下,搅拌浸泡5h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core (~600g) and residual electrolyte (~20g) into 1.5L, and the concentration is 3M. Then add 250ml of 1M hydrogen peroxide solution to the chloroacetic acid solution, and immerse for 5 hours under stirring at 20℃.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相。第一液相的pH值pH(a)=0.4。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase. The pH value of the first liquid phase is pH(a)=0.4.
步骤b)向上述溶液中滴加三乙胺,至pH(b)=1.0,过滤生成主要组分为磷酸铁的第一沉淀(~220g),第一含锂溶液。Step b) Triethylamine was added dropwise to the above solution to pH (b) = 1.0, and filtered to generate a first precipitate (~220g) whose main component is iron phosphate, and a first lithium-containing solution.
步骤c)继续在上述溶液中滴加三乙胺溶液,至pH(c)=7.0,过滤后得到第二含锂溶液。Step c) Continue to add the triethylamine solution dropwise to the above solution until the pH (c) = 7.0, and obtain the second lithium-containing solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有3M三氯乙酸、1M十六烷基三甲基溴化铵、1M草酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and second lithium-containing solution are mixed, and a mixed solution containing 3M trichloroacetic acid, 1M cetyltrimethylammonium bromide and 1M oxalic acid is added dropwise during the stirring process until the solution becomes Even suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入25g前面步骤a)获得的碳源(主要为石墨),2.3g硝酸铁和0.9g磷酸,使得溶液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.11:1:1:1:1。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 25g of the carbon source (mainly graphite) obtained in the previous step a), 2.3g of iron nitrate and 0.9g of phosphoric acid, so that The molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution is 1.11:1:1:1:1:1.
步骤f)将上述溶液充分搅拌后,100℃直接蒸发干燥,获得前驱体粉料。Step f) After fully stirring the above solution, directly evaporate and dry at 100°C to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧3h,期间通入甲烷氩气混合气,制备获得回收的磷酸铁锂正极材料3。Step g) The above precursor powder is placed in an atmosphere furnace, and the temperature is raised to 600°C at 5°C/min and calcined for 3 hours, during which methane and argon gas mixture is passed to prepare a recovered lithium iron phosphate cathode material 3.
对比例1Comparative Example 1
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入3L,浓度为0.8M的盐酸溶液中,30℃条件下,搅拌浸泡5h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% attenuation, cut off the pole ears, put the winding core (~600g) and the residual electrolyte (~20g) into 3L of hydrochloric acid with a concentration of 0.8M In the solution, at 30 ℃, stir and soak for 5h.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相。第一液相的pH值第一液相的pH值pH(a)=1.5。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase. The pH value of the first liquid phase The pH value of the first liquid phase pH (a) = 1.5.
步骤b)向上述溶液中滴加三乙胺,至pH(b)=2.4,过滤生成主要组分为磷酸铁的第一沉淀(~200g),第一含锂溶液。Step b) Triethylamine is added dropwise to the above solution to pH (b) = 2.4, and filtered to generate a first precipitate (~200g) whose main component is iron phosphate, and a first lithium-containing solution.
步骤c)继续在上述溶液中滴加三乙胺溶液,至pH(c)=9.5,过滤后得到第二含锂溶液。Step c) Continue to add the triethylamine solution dropwise to the above solution until the pH (c) = 9.5, and obtain the second lithium-containing solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有5M盐酸、1M聚乙二醇、1M柠檬酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入18g前面步骤a)获得的碳源(主要为石墨),2g三氧化二铁和3.1g磷酸二氢铵、磷元素,使得 溶液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.13:1:1:1:0.7。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon and sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), 2g of ferric oxide and 3.1g of diphosphate The ammonium hydrogen and phosphorus elements make the molar ratio of lithium element: iron element: phosphorus element: carbon element in the solution 1.13:1:1:1:1:0.7.
步骤f)将上述溶液充分搅拌后,采用喷雾干燥法,在喷雾干燥炉,加热至200℃进行喷雾干燥,获得前驱体粉料。Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧3h,期间通入氢氩混合气,制备获得回收的磷酸铁锂正极材料4。Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 h, during which hydrogen-argon mixed gas is introduced to prepare the recovered lithium iron phosphate cathode material 4.
对比例2Comparative Example 2
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入1.5L,浓度为2M的盐酸溶液中,30℃条件下,搅拌浸泡3h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core (~600g) and the residual electrolyte (~20g) into 1.5L of 2M hydrochloric acid In the solution, at 30℃, stir and soak for 3h.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相。第一液相的pH值pH(a)=1.0。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase. The pH value of the first liquid phase is pH(a)=1.0.
步骤b)向上述溶液中滴加三乙胺,至pH(b)=3.6,过滤生成主要组分为磷酸铁的第一沉淀(~218g),第一含锂溶液。Step b) Triethylamine was added dropwise to the above solution to pH (b) = 3.6, and the first precipitate (~218g) containing iron phosphate as the main component was filtered to produce the first lithium-containing solution.
步骤c)继续在上述溶液中滴加三乙胺溶液,至pH(c)=6.8,过滤后得到第二含锂溶液。Step c) Continue to add the triethylamine solution dropwise to the above solution until the pH (c) = 6.8, and obtain the second lithium-containing solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有5M盐酸、1M聚乙二醇、1M柠檬酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入18g前面步骤a)获得的碳源(主要为石墨),和2.5g磷酸铁,使得溶液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.12:1:1:1:0.7。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon-sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 2.5g of iron phosphate to make lithium in the solution Element: iron element: phosphorus element: carbon element molar ratio is 1.12:1:1:1:1:0.7.
步骤f)将上述溶液充分搅拌后,采用喷雾干燥法,在喷雾干燥炉,加热至200℃进行喷雾干燥,获得前驱体粉料。Step f) After the above solution is fully stirred, a spray drying method is used to heat the spray drying furnace to 200° C. for spray drying to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧3h,期间通入氢氩混合气,制备获得回收的磷酸铁锂正极材料5。Step g) The above precursor powder is placed in an atmosphere furnace, and heated to 600° C. at 5° C./min for 3 h, during which hydrogen-argon mixed gas is passed to prepare a recovered lithium iron phosphate cathode material 5.
对比例3Comparative Example 3
步骤a)拆解一个35Ah容量衰减到80%的磷酸铁锂硬壳电芯,剪去极耳,将卷芯(~600g)和残余电解液(~20g)投入1.5L,浓度为3M的盐酸溶液中,30℃条件下,搅拌浸泡3h。Step a) Dismantle a 35Ah lithium iron phosphate hard shell battery with 80% capacity reduction, cut off the tabs, put the winding core (~600g) and residual electrolyte (~20g) into 1.5L of 3M hydrochloric acid In the solution, at 30℃, stir and soak for 3h.
将上述混合物通过100目筛网进行筛分,除去不溶杂质,得到悬浊液;将悬浊液减压过滤,获得回收碳源和第一液相。第一液相的pH值pH(a)=0.4。The above mixture is sieved through a 100-mesh screen to remove insoluble impurities to obtain a suspension; the suspension is filtered under reduced pressure to obtain a recovered carbon source and a first liquid phase. The pH value of the first liquid phase is pH(a)=0.4.
步骤b)向上述溶液中滴加三乙胺,至pH(b)=2.8,过滤生成主要组分为磷酸铁的第一沉淀(~231g),第一含锂溶液。Step b) Triethylamine is added dropwise to the above solution to pH (b) = 2.8, and filtered to generate a first precipitate (~231g) whose main component is iron phosphate, and a first lithium-containing solution.
步骤c)继续在上述溶液中滴加三乙胺溶液,至pH(c)=3.9,过滤后得到第二锂盐溶液。Step c) Continue to add the triethylamine solution dropwise to the above solution until the pH (c) = 3.9, and obtain the second lithium salt solution after filtration.
步骤d)将分离得到的第一沉淀和第二含锂溶液混合,在搅拌过程中滴加含有5M盐酸、1M聚乙二醇、1M柠檬酸混合溶液至溶液变成均匀的悬浊液。Step d) The separated first precipitate and the second lithium-containing solution are mixed, and a mixed solution containing 5M hydrochloric acid, 1M polyethylene glycol and 1M citric acid is added dropwise during the stirring process until the solution becomes a uniform suspension.
步骤e)通过ICP测试锂、铁、磷元素含量,使用碳硫分析仪测试C元素含量,加入18g前面步骤a)获得的碳源(主要为石墨),和2.1g磷酸铁,使得溶液中锂元素:铁元素:磷元素:碳元素的摩尔比为1.11:1:1:1:0.7。Step e) Test the content of lithium, iron and phosphorus by ICP, use a carbon sulfur analyzer to test the content of element C, add 18g of the carbon source (mainly graphite) obtained in the previous step a), and 2.1g of iron phosphate to make lithium in the solution Element: iron element: phosphorus element: carbon element molar ratio is 1.11:1:1:1:1:0.7.
步骤f)将上述溶液充分搅拌后,采用90℃,减压干燥,获得前驱体粉料。Step f) After fully stirring the above solution, it is dried at 90°C under reduced pressure to obtain a precursor powder.
步骤g)将上述前驱体粉料置于气氛炉中,5℃/min升温至600℃煅烧3h,期间通入氢氩混合气,制备获得回收的磷酸铁锂正极材料6。Step g) Put the above-mentioned precursor powder in an atmosphere furnace, raise the temperature at 5°C/min to 600°C and calcine for 3 hours, during which hydrogen-argon mixed gas is introduced to prepare the recovered lithium iron phosphate cathode material 6.
实施例与对比例中,pH调节变化情况,如下表所示,其中pH值使用pH计进行测量,离子浓度使用ICP进行检测:In the examples and comparative examples, the pH adjustment changes are shown in the following table, in which the pH value is measured using a pH meter, and the ion concentration is detected using ICP:
表1Table 1
Figure PCTCN2019120509-appb-000001
Figure PCTCN2019120509-appb-000001
从上述结果可以看出,当pH(a)值大于等于1时,第一沉淀质量明显降低,这主要是由于磷酸铁锂溶解不完全造成的,损失较多的磷酸铁;当pH(b)值大于3时,第一沉淀中Cu含量明显增加,这主要是由于pH(b)>3,磷酸铜开始沉淀;随着pH(b)增加,第一含锂溶液Fe含量减少,但是差异不大;当pH(c)小于5,第二含锂溶液中Al含量明显升高,而当pH(c)大于7后,第二含锂溶液中Al含量差异不大。It can be seen from the above results that when the pH(a) value is greater than or equal to 1, the quality of the first precipitation is significantly reduced, which is mainly due to the incomplete dissolution of lithium iron phosphate, and the loss of more iron phosphate; when the pH(b) When the value is greater than 3, the Cu content in the first precipitate increases significantly. This is mainly because the pH(b)>3, copper phosphate begins to precipitate; as the pH(b) increases, the Fe content in the first lithium-containing solution decreases, but the difference is not Large; when the pH (c) is less than 5, the Al content in the second lithium-containing solution increases significantly, and when the pH (c) is greater than 7, the Al content in the second lithium-containing solution is not much different.
通过ICP测试所合成实施例1中磷酸铁锂中金属杂质离子的含量,结果如表2所示,可以看出各项金属杂质离子浓度均处于非常低的含量水平,并且未检测出Ni、Co、Mn、K金属离子,Li元素的回收利用率为93%,铁元素的回收利用率为96%,磷元素的回收利用率为 96%。The content of metal impurity ions in lithium iron phosphate synthesized in Example 1 was synthesized by ICP. The results are shown in Table 2. It can be seen that the concentration of each metal impurity ion is at a very low content level, and Ni and Co are not detected. , Mn, K metal ions, Li element recovery rate is 93%, iron element recovery rate is 96%, phosphorus element recovery rate is 96%.
表2Table 2
元素element 含量/ppmContent/ppm
LiLi 4487844878
NiNi ---
CoCo ---
MnMn ---
AlAl 112112
CaCa 2020
CrCr 55
CuCu 5858
FeFe 348230348230
KK ---
MgMg 55
NaNa 117117
TiTi ---
PP 196289196289
使用实施例1制备的磷酸铁锂作为正极材料,SP为导电剂,聚偏氟乙烯为粘结剂,氮甲基吡咯烷酮为溶剂,LiFePO4:SP:PVDF:NMP=92:4:4:100,使用铝箔为正极集流体,冲切成直径14mm的小圆片,制备成磷酸铁锂正极极片,以直径为16mm的金属锂为负极,是有直径为18mm的PE隔离膜,电解液使用EC:EMC:DEC=1:1:1,1mol/L的六氟磷酸锂的电解液,组装扣电半电池,正极活性物质面密度为15mg/cm 2将制备获得的电池在2.0~3.75V的电压范围内进行充放电测试,具体方法如下: Use lithium iron phosphate prepared in Example 1 as the positive electrode material, SP as the conductive agent, polyvinylidene fluoride as the binder, nitromethylpyrrolidone as the solvent, LiFePO4: SP: PVDF: NMP = 92: 4: 4: 100, Using aluminum foil as the positive electrode current collector, die-cut into small discs with a diameter of 14mm to prepare lithium iron phosphate positive pole pieces, with metal lithium with a diameter of 16mm as the negative electrode, a PE separator with a diameter of 18mm, and the electrolyte using EC : EMC: DEC = 1: 1 : 1,1mol / L of lithium phosphate hexafluoride electrolyte half cell power button assembly, a positive electrode active material surface density of 15mg / cm 2 obtained in the preparation of the battery voltage in the range of 2.0 ~ 3.75V Carry out charge and discharge test, the specific method is as follows:
0.1C充电至3.75V,恒压至0.05C,然后0.1C放电至2.0V。Charge 0.1C to 3.75V, constant voltage to 0.05C, then discharge 0.1C to 2.0V.
结果如图1所示,从图中可以看出,此款回收合成的磷酸铁锂0.1C放电克容量可达159mAh/g,充放电效率达97.9%。The results are shown in Figure 1. From the figure, it can be seen that this recovered lithium iron phosphate 0.1C discharge gram capacity can reach 159mAh/g, and the charge and discharge efficiency reaches 97.9%.
综上所述,本发明有效克服了现有技术中的种种缺点而具高度产业利用价值。In summary, the present invention effectively overcomes various shortcomings in the prior art and has high industrial utilization value.
上述实施例仅例示性说明本发明的原理及其功效,而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下,对上述实施例进行修饰或改变。因此,举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变,仍应由本发明的权利要求所涵盖。The above-mentioned embodiments only exemplarily illustrate the principle and efficacy of the present invention, and are not intended to limit the present invention. Anyone familiar with this technology can modify or change the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or changes made by those with ordinary knowledge in the technical field without departing from the spirit and technical ideas disclosed in the present invention should still be covered by the claims of the present invention.

Claims (21)

  1. 一种回收制备磷酸铁锂正极材料的方法,包括:A method for recovering and preparing lithium iron phosphate cathode material includes:
    a)将回收的电芯材料与酸溶液接触,固液分离得到第一液相和不溶物;a) Contacting the recovered battery material with the acid solution, solid-liquid separation to obtain the first liquid phase and insolubles;
    b)调节步骤a)所提供的第一液相的pH值,固液分离得到第一含锂溶液和第一沉淀;b) Adjust the pH value of the first liquid phase provided in step a), and obtain the first lithium-containing solution and the first precipitate by solid-liquid separation;
    c)调节步骤b)所提供的第一含锂溶液的pH值,固液分离得到第二含锂溶液和第二沉淀;c) Adjust the pH value of the first lithium-containing solution provided in step b), and obtain the second lithium-containing solution and the second precipitate by solid-liquid separation;
    d)将步骤b)所提供的第一沉淀、步骤c)所提供的第二含锂溶液与助剂混合,得到第二液相;d) mixing the first precipitation provided in step b) and the second lithium-containing solution provided in step c) with an auxiliary agent to obtain a second liquid phase;
    e)调节步骤d)所提供的第二液相中Li元素、Fe元素、P元素、C元素的含量,得到第三液相;e) Adjust the content of Li element, Fe element, P element, and C element in the second liquid phase provided in step d) to obtain a third liquid phase;
    f)脱除步骤e)所提供的第三液相的溶剂,得到磷酸铁锂前驱体;f) removing the solvent in the third liquid phase provided in step e) to obtain a lithium iron phosphate precursor;
    g)将步骤f)所提供的磷酸铁锂前驱体在还原环境下煅烧,得到磷酸铁锂正极材料。g) The lithium iron phosphate precursor provided in step f) is calcined under a reducing environment to obtain a lithium iron phosphate cathode material.
  2. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤a)中,所述电芯材料包括未去除电池壳体的电芯、去除电池壳体的电芯、以及将去除电池壳体的电芯进行拆解得到的正极极片中的至少一种;The method for recovering a lithium iron phosphate positive electrode material according to claim 1, wherein in step a), the cell material includes a cell without removing the battery case, and a cell with the battery case removed And at least one of the positive pole pieces obtained by disassembling the battery core with the battery case removed;
    所述电芯材料中含有电解液。The battery material contains an electrolyte.
  3. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤a)中的所述酸溶液为无机强酸和/或有机强酸的水溶液;The method for recovering and preparing lithium iron phosphate cathode material according to claim 1, wherein the acid solution in step a) is an aqueous solution of a strong inorganic acid and/or a strong organic acid;
    所述酸溶液的摩尔浓度为0.5M~10M,优选的,所述酸溶液的摩尔浓度为1M~6M。The molar concentration of the acid solution is 0.5M-10M, preferably, the molar concentration of the acid solution is 1M-6M.
  4. 如权利要求3所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述无机强酸选自盐酸、硝酸、硫酸、高氯酸、氯酸中的一种或多种的组合;所述有机强酸选自2,4,6-三硝基苯酚、2,4,6-三硝基苯甲酸、三氟乙酸、三氯乙酸、甲磺酸、苯磺酸、KMD酸中的一种或多种的组合。The method for recovering a lithium iron phosphate cathode material according to claim 3, wherein the strong inorganic acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, and chloric acid; The organic strong acid is selected from one of 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid, and KMD acid Or a combination of multiple.
  5. 如权利要求1~4任一权利要求所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤a)中,所述酸溶液具有氧化性;The method for recovering and preparing a lithium iron phosphate cathode material according to any one of claims 1 to 4, characterized in that, in the step a), the acid solution is oxidative;
    和/或,所述酸溶液中含有过氧化氢,优选的,过氧化氢在所述酸溶液中的摩尔浓度为0.5M~10M,优选为1M~6M。And/or, the acid solution contains hydrogen peroxide. Preferably, the molar concentration of hydrogen peroxide in the acid solution is 0.5M-10M, preferably 1M-6M.
  6. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤a)中,所述第一液相中Fe 2+的浓度≤50ppm。 The method for recovering a lithium iron phosphate positive electrode material according to claim 1, wherein in the step a), the concentration of Fe 2+ in the first liquid phase is ≤50ppm.
  7. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤a)中,所述电芯材料与所述酸溶液接触的温度为10℃~60℃,优选为15℃~40℃,更优选为 20℃~35℃。The method for recovering a lithium iron phosphate cathode material according to claim 1, characterized in that, in the step a), the temperature at which the cell material is in contact with the acid solution is 10°C to 60°C, preferably It is 15°C to 40°C, and more preferably 20°C to 35°C.
  8. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤a)中,所述电芯材料与所述酸溶液接触的时间为0.5h~5h,优选为1h~3h。The method for recovering a lithium iron phosphate cathode material according to claim 1, wherein in step a), the contact time between the battery material and the acid solution is 0.5h-5h, preferably 1h~3h.
  9. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤c)中,所述第二含锂溶液的Al元素含量不高于30ppm。The method for recovering a lithium iron phosphate positive electrode material according to claim 1, wherein in step c), the Al element content of the second lithium-containing solution is not higher than 30 ppm.
  10. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤The method for recovering and preparing lithium iron phosphate cathode material according to claim 1, wherein in the step
    a)中,所述第一液相的pH值<1;In a), the pH value of the first liquid phase is <1;
    在所述步骤b)中,调节步骤a)所提供的第一液相的pH值至1~3,固液分离得到所述第一沉淀和所述第一含锂溶液,优选的,调节pH值至1.5~2.5;In step b), adjust the pH value of the first liquid phase provided in step a) to 1 to 3, solid-liquid separation to obtain the first precipitate and the first lithium-containing solution, preferably, adjust the pH Value to 1.5~2.5;
    在所述步骤c)中,调节步骤b)所提供的第一含锂溶液的pH值至4~11,固液分离得到所述第二含锂溶液和所述第二沉淀,优选的,调节pH值至6~10。In the step c), adjust the pH value of the first lithium-containing solution provided in step b) to 4 to 11, solid-liquid separation to obtain the second lithium-containing solution and the second precipitate, preferably, adjust The pH value is from 6 to 10.
  11. 如权利要求1或10所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤b)和/或所述步骤c)中,使用无机碱和/或有机碱调节pH值;The method for recovering a lithium iron phosphate cathode material according to claim 1 or 10, characterized in that, in the step b) and/or the step c), an inorganic base and/or an organic base is used to adjust the pH value ;
    优选的,所述无机碱选自氨水、氢氧化钠、氢氧化钾中的一种或多种的组合,所述有机碱选自甲胺、乙胺、乙醇胺、乙二胺、二甲胺、三甲胺、三乙胺、丙胺、异丙胺、1,3-丙二胺、三丙胺、丁胺、异丁胺、叔丁胺、己胺、辛胺、环己胺中的一种或多种的组合。Preferably, the inorganic base is selected from one or a combination of ammonia, sodium hydroxide, and potassium hydroxide, and the organic base is selected from methylamine, ethylamine, ethanolamine, ethylenediamine, dimethylamine, A combination of one or more of trimethylamine, triethylamine, propylamine, isopropylamine, 1,3-propanediamine, tripropylamine, butylamine, isobutylamine, tert-butylamine, hexylamine, octylamine, cyclohexylamine .
  12. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤d)中,所述助剂包括酸、分散剂、表面活性剂、螯合剂中的一种或多种的组合;The method for recovering a lithium iron phosphate positive electrode material according to claim 1, wherein in step d), the auxiliary agent includes one or more of acid, dispersant, surfactant, chelating agent Combinations of species
    所述助剂中的酸选自无机酸和/或有机酸,所述无机酸优选为无机强酸,更优选为盐酸、硝酸、硫酸、高氯酸、氯酸中的一种或多种的组合,所述有机酸优选为有机强酸,更优选为2,4,6-三硝基苯酚、2,4,6-三硝基苯甲酸、三氟乙酸、三氯乙酸、甲磺酸、苯磺酸、KMD酸中的一种或多种的组合;The acid in the auxiliary agent is selected from an inorganic acid and/or an organic acid, the inorganic acid is preferably a strong inorganic acid, and more preferably a combination of one or more of hydrochloric acid, nitric acid, sulfuric acid, perchloric acid, and chloric acid , The organic acid is preferably a strong organic acid, more preferably 2,4,6-trinitrophenol, 2,4,6-trinitrobenzoic acid, trifluoroacetic acid, trichloroacetic acid, methanesulfonic acid, benzenesulfonic acid One or more combinations of acid and KMD acid;
    所述分散剂选自水、乙醇、丙酮、丙醇、异丙醇、甲醇、正丁醇、乙腈、四氢呋喃、乙醚二氯甲烷、氯仿、二甲基亚砜、二甲基甲酰胺中的一种或多种的组合;The dispersant is selected from the group consisting of water, ethanol, acetone, propanol, isopropanol, methanol, n-butanol, acetonitrile, tetrahydrofuran, diethyl ether methylene chloride, chloroform, dimethyl sulfoxide, and dimethyl formamide One or more combinations;
    所述表面活性剂选自十六烷基三甲基溴化铵、十六烷基三甲基氯化铵、十二烷基硫酸钠、十二烷基苯磺酸钠、聚乙二醇、聚氧化乙烯、聚丙烯酰胺或羧甲基纤维素、聚乙烯吡咯烷酮、乙烯-丙烯酸共聚物、乙烯-醋酸乙烯共聚物中的一种或多种的组合;The surfactant is selected from cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, One or more combinations of polyethylene oxide, polyacrylamide or carboxymethyl cellulose, polyvinylpyrrolidone, ethylene-acrylic acid copolymer, ethylene-vinyl acetate copolymer;
    所述螯合剂选自次氨基三乙酸、1,2-环己二胺四乙酸、乙二胺四乙酸、柠檬酸、苹果酸、草酸、乙酸、水杨酸中的一种或多种的组合。The chelating agent is selected from one or more combinations of nitrilotriacetic acid, 1,2-cyclohexanediaminetetraacetic acid, ethylenediaminetetraacetic acid, citric acid, malic acid, oxalic acid, acetic acid, and salicylic acid .
  13. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤e)中,通过ICP、化学滴定、液相色谱、沉淀法、碳硫分析法中的一种或者多种的组合确定体系中的元素含量;The method for recovering and preparing a lithium iron phosphate cathode material according to claim 1, wherein in step e), one of ICP, chemical titration, liquid chromatography, precipitation method, carbon sulfur analysis method is used Or a combination of multiples to determine the element content in the system;
    所述第三液相中Li元素、Fe元素、P元素、C元素的摩尔比为(1~1.5):(0.95~1.05):(0.95~1.05):(0.5~4)。The molar ratio of Li element, Fe element, P element, and C element in the third liquid phase is (1 to 1.5): (0.95 to 1.05): (0.95 to 1.05): (0.5 to 4).
  14. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤e)中,通过锂源调节第二液相中Li元素的含量,所述锂源选自碳酸锂、磷酸二氢锂、磷酸锂、醋酸锂、氢氧化锂、草酸锂、硝酸锂中的一种或多种的组合;The method for recovering a lithium iron phosphate cathode material according to claim 1, wherein in step e), the content of Li element in the second liquid phase is adjusted by a lithium source, and the lithium source is selected from lithium carbonate , A combination of one or more of lithium dihydrogen phosphate, lithium phosphate, lithium acetate, lithium hydroxide, lithium oxalate, lithium nitrate;
    通过铁源调节第二液相中Fe元素的含量,所述铁源选自三氧化二铁、四氧化三铁、磷酸铁、硝酸铁、氯化铁、硝酸亚铁、氯化亚铁、醋酸铁、碳酸铁、碳酸亚铁、乙酰丙酮铁中的一种或多种的组合;至少部分的步骤b)中所提供的第一沉淀作为铁源调节第二液相中Fe元素的含量;The content of Fe in the second liquid phase is adjusted by an iron source selected from the group consisting of ferric oxide, ferric oxide, ferric phosphate, ferric nitrate, ferric chloride, ferrous nitrate, ferrous chloride, and acetic acid A combination of one or more of iron, iron carbonate, ferrous carbonate, and iron acetylacetonate; at least part of the first precipitate provided in step b) is used as an iron source to adjust the content of Fe element in the second liquid phase;
    通过磷源调节第二液相中P元素的含量,所述磷源选自磷酸二氢铵、磷酸二氢锂、磷酸铁、磷酸中的一种或多种的组合;Adjusting the content of P element in the second liquid phase by a phosphorus source selected from one or more of ammonium dihydrogen phosphate, lithium dihydrogen phosphate, iron phosphate, phosphoric acid;
    通过碳源调节第二液相中C元素的含量,所述碳源选自石墨、导电碳、乙炔黑、导电炭黑、碳纤维、碳纳米管、纳米碳微球、葡萄糖、蔗糖、果糖、聚丙烯腈中的一种或多种的组合,所述碳源优选为可溶性碳源。The content of element C in the second liquid phase is adjusted by a carbon source selected from graphite, conductive carbon, acetylene black, conductive carbon black, carbon fiber, carbon nanotubes, nanocarbon microspheres, glucose, sucrose, fructose, poly In one or a combination of acrylonitrile, the carbon source is preferably a soluble carbon source.
  15. 如权利要求1或14所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤e)中,通过加入碳源调节第二液相中C元素的含量,至少部分的碳源为所述步骤a)中所述不溶物经筛分得到。The method for recovering a lithium iron phosphate cathode material according to claim 1 or 14, wherein in step e), the content of C element in the second liquid phase is adjusted by adding a carbon source, at least part of the carbon The source is obtained by sieving the insoluble matter in step a).
  16. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤f)中,所述脱除溶剂的方法选自常压干燥、减压干燥、喷雾干燥、沸腾干燥、冷冻干燥中的一种或多种的组合。The method for recovering a lithium iron phosphate cathode material according to claim 1, wherein in step f), the method for removing the solvent is selected from normal pressure drying, reduced pressure drying, spray drying, and boiling drying , One or a combination of freeze-drying.
  17. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,所述步骤g)中,提供所述还原环境的物质选自还原性气体和/或还原性液体,优选选自氢气、一氧化碳、乙炔、甲醇、乙醇、甲烷、乙烷中的一种或多种的组合;The method for recovering a lithium iron phosphate cathode material according to claim 1, wherein in step g), the substance providing the reducing environment is selected from reducing gas and/or reducing liquid, preferably selected from One or more combinations of hydrogen, carbon monoxide, acetylene, methanol, ethanol, methane, and ethane;
    所述煅烧温度为500℃~700℃;The calcination temperature is 500°C to 700°C;
    所述煅烧时间为10min~300min。The calcination time is 10 min to 300 min.
  18. 如权利要求1所述的回收制备磷酸铁锂正极材料的方法,其特征在于,在所述步骤g)提供的磷酸铁锂正极材料中,Cu、Al杂质离子含量之和<200ppm。The method for recovering and preparing lithium iron phosphate cathode material according to claim 1, wherein in the lithium iron phosphate cathode material provided in step g), the sum of Cu and Al impurity ion contents is less than 200 ppm.
  19. 一种回收制备的磷酸铁锂正极材料,通过权利要求1~18中任一权利要求所述的方法制备。A recovered lithium iron phosphate cathode material prepared by the method of any one of claims 1-18.
  20. 如权利要求19所述回收制备的磷酸铁锂正极材料,其特征在于,在所述回收制备的磷酸铁锂正极材料中,Cu、Al杂质离子含量之和<200ppm。The lithium iron phosphate cathode material recovered and prepared according to claim 19, characterized in that, in the lithium iron phosphate cathode material recovered and prepared, the sum of Cu and Al impurity ion contents is less than 200 ppm.
  21. 一种锂离子电池,包括如权利要求19或20中任一权利要求所述的回收制备的磷酸铁锂正极材料。A lithium ion battery, comprising the lithium iron phosphate cathode material recovered and prepared according to any one of claims 19 or 20.
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CN115448285A (en) * 2022-10-26 2022-12-09 华鼎国联四川电池材料有限公司 Method for preparing lithium iron phosphate by taking recycled lithium phosphate as raw material
CN115566307A (en) * 2022-11-15 2023-01-03 湖南五创循环科技有限公司 Method for recovering high-purity lithium oxalate and high-purity lithium hydroxide from disassembled black powder of waste lithium battery and/or waste cathode powder of lithium battery
CN115566307B (en) * 2022-11-15 2023-03-24 湖南五创循环科技有限公司 Method for recovering high-purity lithium oxalate and high-purity lithium hydroxide from waste lithium battery
CN115744940A (en) * 2022-11-15 2023-03-07 四川长虹格润环保科技股份有限公司 Method for recovering valuable metals from waste lithium iron phosphate positive electrode powder
CN115784191A (en) * 2022-12-12 2023-03-14 厦门厦钨新能源材料股份有限公司 Method for recycling lithium iron phosphate from waste lithium iron phosphate anode material
CN117303330A (en) * 2023-09-20 2023-12-29 百杰瑞(荆门)新材料有限公司 Method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste
CN117303330B (en) * 2023-09-20 2024-03-19 百杰瑞(荆门)新材料有限公司 Method for preparing battery grade lithium dihydrogen phosphate by recycling lithium iron phosphate waste

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