WO2017215283A1 - Method for recycling lithium in lithium iron phosphate by means of electrochemical process - Google Patents
Method for recycling lithium in lithium iron phosphate by means of electrochemical process Download PDFInfo
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- WO2017215283A1 WO2017215283A1 PCT/CN2017/074132 CN2017074132W WO2017215283A1 WO 2017215283 A1 WO2017215283 A1 WO 2017215283A1 CN 2017074132 W CN2017074132 W CN 2017074132W WO 2017215283 A1 WO2017215283 A1 WO 2017215283A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Definitions
- the invention relates to a method for recovering lithium in lithium iron phosphate by electrochemical method, and belongs to the technical field of energy materials.
- Lithium batteries including lithium-ion batteries and lithium metal batteries.
- Lithium-ion batteries generally use a lithium-containing compound as a positive electrode and a carbon material as a negative electrode.
- the lithium metal battery is a battery using a lithium compound as a positive electrode, a lithium metal or a lithium alloy as a negative electrode material, and a nonaqueous electrolyte solution.
- Lithium iron phosphate lithium iron phosphate (LiFePO 4 )
- LiFePO 4 lithium iron phosphate
- LiFePO 4 is a newly developed lithium ion battery electrode material, mainly used in power lithium ion batteries. It is used as a positive electrode active material and has a large discharge capacity, low price, no toxicity, no Causes environmental pollution and other advantages.
- lithium batteries With the wide application of lithium batteries, lithium batteries have entered a large number of failure and recycling stages. How to recycle lithium batteries and recycle resources has become a common concern in society.
- the recycling of lithium batteries can not only solve a series of environmental problems caused by used batteries, but also recycle the non-ferrous metals in the batteries, which can effectively alleviate the shortage of resources.
- Patent 2012800276260 discloses a method for recovering lithium by electrochemical method, and recovering lithium in waste cathode raw material by electrochemical method.
- the method uses unqualified cathode material as raw material, and only targets lithium manganese oxide LixMyMnzO 4 (where M represents Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Si, Mg, and Zn, x is 1.33 to 2, y is 0 to 0.5, and z is 1 to 1.67).
- the raw material is subjected to pulping and coating to form a positive electrode sheet, and a non-aqueous solution in which a lithium salt is dissolved is used as an electrolyte, and the electrode plate is a lithium plate or a copper plate which forms a mesh form.
- a non-aqueous solution in which a lithium salt is dissolved is used as an electrolyte
- the electrode plate is a lithium plate or a copper plate which forms a mesh form.
- Patent 201310105752.X discloses a method for electrochemically recovering lithium, using FePO 4 material as a negative electrode, and a lithium-containing solution (a near-neutral solution in which a lithium iron ion battery lithium iron phosphate positive electrode material is dissolved and treated by acid) is electrolysis.
- the liquid and the inert electrode are positive electrodes, and the Li 1-x FePO 4 material formed by lithium is directly recovered from the solution by electrochemical method, and the formed Li 1-x FePO 4 material is newly prepared to form a new LiFePO 4 material.
- the method is to recover lithium by using an acid-dissolved solution of a lithium-ion battery lithium iron phosphate cathode material as an electrolyte, and the recovered lithium enters the iron phosphate to form lithium iron phosphate, which is high in one fell swoop. Novelty, but this method can only be recycled for low-value ionic solutions. Moreover, the final product recovered by this method is lithium iron phosphate.
- the technical problem to be solved by the present invention is to provide a method for recovering lithium in lithium iron phosphate, which directly recovers lithium in lithium iron phosphate by an electrochemical method.
- the method for recovering lithium in lithium iron phosphate by electrochemical method of the invention using lithium iron phosphate as a positive electrode, metal or carbon as a negative electrode, and using an aqueous solution as an electrolyte, applying a potential to move lithium ions in lithium iron phosphate into an aqueous electrolyte solution A lithium-containing solution is formed.
- the source of the lithium iron phosphate is a positive electrode scrap produced in a lithium battery production process, a positive electrode waste generated in a lithium battery production process, a waste generated in a lithium iron phosphate production process, or a positive electrode disassembled after a lithium battery is disassembled.
- the material of the metal or carbon electrode is platinum, nickel, copper, ruthenium, titanium or carbon.
- the aqueous solution electrolyte is a lithium hydroxide solution, a sodium chloride solution, a lithium sulfate solution or a lithium nitrate solution.
- the aqueous solution electrolyte has a concentration of 0.01 to 1 mol/L, preferably 0.025 to 0.8 mol/L.
- a potential of 0.1 to 5.0 V is applied, and the time for applying the potential is 0.5 to 8 hours. More preferably, a potential of 0.1 to 4.4 V is applied, and the time for applying the potential is 1.5 to 5 hours.
- a lithium-containing solution can be prepared as a lithium salt.
- the lithium salt prepared is lithium carbonate, lithium chloride or lithium hydroxide.
- the invention directly moves lithium ions from the lithium iron phosphate into the electrolyte by electrochemical method, and extracts lithium from the lithium iron phosphate at one time to form a lithium solution, and the migration rate is high, and can reach more than 90%. Even as high as 99%. Since only lithium can be removed at a certain potential, it is not sensitive to other ions such as iron ions, has high selectivity, and achieves a low impurity content in the solution, which is favorable for obtaining a lithium salt of adjustable grade. By the method of the present invention, lithium element in lithium iron phosphate can be recovered simply and efficiently. In addition, the present invention can also recover lithium in other positive electrode materials, except that the obtained lithium solution has more impurities, and the later purification process is complicated, thereby causing high cost.
- the method for recovering lithium in lithium iron phosphate by electrochemical method of the invention using lithium iron phosphate as a positive electrode, metal or carbon as a negative electrode, and using an aqueous solution as an electrolyte, applying a potential to move lithium ions in lithium iron phosphate into an aqueous electrolyte solution A lithium-containing solution is formed.
- the recovered lithium iron phosphate is derived from the positive electrode scrap produced in the production process of the lithium battery which is ubiquitous on the market, the positive electrode waste generated in the production process of the lithium battery, the waste generated in the production process of the lithium iron phosphate or the lithium battery. Disassembled positive electrode.
- the material of the metal or carbon electrode is platinum, nickel, copper, ruthenium, titanium or carbon.
- the aqueous solution of the present invention is an aqueous electrolyte solution.
- the aqueous solution electrolyte is a lithium hydroxide solution, a sodium chloride solution, a lithium sulfate solution or a lithium nitrate solution.
- the aqueous solution electrolyte has a concentration of 0.01 to 1 mol/L, preferably 0.025 to 0.8 mol/L.
- a potential of 0.1 to 5.0 V is applied, and the time for applying the potential is 0.5 to 8 hours. More preferably, a potential of 0.1 to 4.4 V is applied, and the time for applying the potential is 1.5 to 5 hours.
- a lithium-containing solution can be prepared as a lithium salt.
- a commonly used method for preparing a lithium salt from a lithium-containing solution is suitable for use in the present invention.
- the prepared lithium salt is lithium carbonate, lithium chloride or lithium hydroxide.
- the preparation method is a prior art in the art, for example, lithium carbonate is prepared by the following method: a lithium-containing solution is concentrated to a solution having a Li 2 O content of 30 to 35 g/L, and 280 to 285 g/L of Na 2 is added thereto. CO 3 , the excess coefficient is 105%, the precipitation of lithium carbonate is obtained, and the precipitation is completed and aged for 20 minutes.
- the solid-liquid separation is carried out to obtain the crude lithium carbonate, and the crude lithium carbonate is stirred with deionized water at a solid-liquid ratio of 1:3.
- a lithium carbonate product having a purity of a battery grade is obtained.
- Step 1 The lithium iron phosphate material is used as the positive electrode sheet, the sodium chloride aqueous solution is used as the electrolyte, and the graphite is used as the negative electrode, and 0.1 V potential is applied to the electrolytic cell for electrochemical recovery, wherein the concentration of the sodium chloride solution is 0.025 mol/L for 2 h, the lithium ions in the positive electrode sheet were moved into the electrolyte solution to form a lithium-containing solution. A lithium-containing solution is obtained. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 95.3%, and the lithium content in the lithium-containing solution was measured to be 1.1 g/L (calculated as Li 2 O).
- Step 2 The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 33 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
- Step 1 The lithium iron phosphate material is used as a positive electrode sheet, the lithium sulfate aqueous solution is used as an electrolyte solution, and the copper piece is used as a negative electrode, and an electric potential of 0.3 V is applied to the electrolytic cell for electrochemical recovery, wherein the concentration of the lithium sulfate solution is 0.5 mol/L and a time of 1.5 h, the lithium ions in the positive electrode sheet were moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 99.1%, and the lithium content in the lithium-containing solution was measured to be 1.1 g/L (calculated as Li 2 O).
- Step 2 The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 33 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
- Step 1 Lithium iron phosphate was used as the positive electrode sheet, lithium sulfate aqueous solution was used as the electrolyte, copper plate was used as the negative electrode, and 1.2 V potential was applied to the electrolytic cell for electrochemical recovery, wherein the electrolyte concentration was 0.8 mol/ L, the time is 5h, and the lithium ions in the positive electrode sheet are moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, the lithium removal rate was 99.6%, and the lithium content in the lithium-containing solution was measured to be 1.5 g/L (calculated as Li 2 O).
- Step 2 The lithium-containing solution obtained in the step 1 was concentrated to a solution having a Li 2 O content of 30 g/L, and 285 g/L of Na 2 CO 3 was added thereto, and the excess coefficient was 105% to obtain lithium carbonate precipitation, and the precipitation was completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
- Step 1 Lithium iron phosphate was used as the positive electrode sheet, lithium sulfate aqueous solution was used as the electrolyte, copper plate was used as the negative electrode, and an electric potential of 4.4 V was applied to the electrolytic cell for electrochemical recovery, wherein the electrolyte concentration was 0.8 mol/ L, the time is 2h, and the lithium ions in the positive electrode sheet are moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 95.3%, and the lithium content in the lithium-containing solution was measured to be 1.5 g/L (calculated as Li 2 O).
- Step 2 The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 30 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
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Abstract
Description
本发明涉及电化学法回收磷酸铁锂中的锂的方法，属于能源材料技术领域。The invention relates to a method for recovering lithium in lithium iron phosphate by electrochemical method, and belongs to the technical field of energy materials.
锂电池，包括锂离子电池和锂金属电池。锂离子电池通常以含锂的化合物作正极，以碳素材料为负极。而锂金属电池是由锂的化合物作正极、锂金属或锂合金为负极材料、使用非水电解质溶液的电池。Lithium batteries, including lithium-ion batteries and lithium metal batteries. Lithium-ion batteries generally use a lithium-containing compound as a positive electrode and a carbon material as a negative electrode. The lithium metal battery is a battery using a lithium compound as a positive electrode, a lithium metal or a lithium alloy as a negative electrode material, and a nonaqueous electrolyte solution.
磷酸铁锂，即磷酸亚铁锂(LiFePO4)作为近来新开发的锂离子电池电极材料，主要用于动力锂离子电池，作为正极活性物质使用，具有放电容量大，价格低廉，无毒性，不造成环境污染等优点。Lithium iron phosphate, lithium iron phosphate (LiFePO 4 ), is a newly developed lithium ion battery electrode material, mainly used in power lithium ion batteries. It is used as a positive electrode active material and has a large discharge capacity, low price, no toxicity, no Causes environmental pollution and other advantages.
随着锂电池的广泛应用，锂电池已大量进入失效、回收阶段，如何回收锂电池和资源化循环利用已成为社会普遍关注的问题。回收处理锂电池不仅可以解决废旧电池所带来的一系列环境问题，而且对电池中有色金属进行了回收利用，能有效缓解资源的紧缺。With the wide application of lithium batteries, lithium batteries have entered a large number of failure and recycling stages. How to recycle lithium batteries and recycle resources has become a common concern in society. The recycling of lithium batteries can not only solve a series of environmental problems caused by used batteries, but also recycle the non-ferrous metals in the batteries, which can effectively alleviate the shortage of resources.
专利2012800276260公开了利用电化学法的锂的回收方法，利用电化学法回收废旧正极原材料中的锂，该方法选用不合格的正极材料作为原料，且只针对锂锰氧化物LixMyMnzO4(其中M代表Ti、V、Cr、Fe、Co、Ni、Cu、Zr、Nb、Mo、Si、Mg及Zn，x为1.33至2，y为0至0.5，z为1至1.67)。将这种原料经过制浆、涂布后形成正极片，以溶解了锂盐的非水溶液做电解质，电极板为形成网形态的锂板或铜板。采用该方法，可回收正极材料中的锂，其回收率高，使用的化学物质的消耗量少，具有卓越的经济性。但该项专利回收所采用的原料并不是锂离子电池中的正极片为原料。Patent 2012800276260 discloses a method for recovering lithium by electrochemical method, and recovering lithium in waste cathode raw material by electrochemical method. The method uses unqualified cathode material as raw material, and only targets lithium manganese oxide LixMyMnzO 4 (where M represents Ti, V, Cr, Fe, Co, Ni, Cu, Zr, Nb, Mo, Si, Mg, and Zn, x is 1.33 to 2, y is 0 to 0.5, and z is 1 to 1.67). The raw material is subjected to pulping and coating to form a positive electrode sheet, and a non-aqueous solution in which a lithium salt is dissolved is used as an electrolyte, and the electrode plate is a lithium plate or a copper plate which forms a mesh form. According to this method, lithium in the positive electrode material can be recovered, and the recovery rate is high, the consumption of the chemical substance used is small, and the economy is excellent. However, the raw materials used in the patent recovery are not the positive electrode sheets in the lithium ion battery.
专利201310105752.X公开了一种电化学回收锂的方法，以FePO4材料为负极，含锂的溶液(废旧锂离子电池磷酸铁锂正极材料经酸溶解并处理后的近中性溶液)为电解液，惰性电极为正极，通过电化学方法直接从溶液中回收锂形成的Li1-xFePO4材料，并将形成的Li1-xFePO4材料重新制备生成新的LiFePO4材料。该方法是将废旧的锂离子电池磷酸铁锂正极材料经过酸溶解后的溶液作为电解液进行回收锂，而回收的锂进入到磷酸铁中形成了磷酸铁锂，一举双得，有很高的新颖性，但是此方法只能针对价值不高的离子溶液进行回收。而且通过此方法回收的最终产品为磷酸铁锂。 Patent 201310105752.X discloses a method for electrochemically recovering lithium, using FePO 4 material as a negative electrode, and a lithium-containing solution (a near-neutral solution in which a lithium iron ion battery lithium iron phosphate positive electrode material is dissolved and treated by acid) is electrolysis. The liquid and the inert electrode are positive electrodes, and the Li 1-x FePO 4 material formed by lithium is directly recovered from the solution by electrochemical method, and the formed Li 1-x FePO 4 material is newly prepared to form a new LiFePO 4 material. The method is to recover lithium by using an acid-dissolved solution of a lithium-ion battery lithium iron phosphate cathode material as an electrolyte, and the recovered lithium enters the iron phosphate to form lithium iron phosphate, which is high in one fell swoop. Novelty, but this method can only be recycled for low-value ionic solutions. Moreover, the final product recovered by this method is lithium iron phosphate.
发明内容Summary of the invention
本发明解决的技术问题是提供回收磷酸铁锂中的锂的方法，采用电化学法直接回收磷酸铁锂中的锂。The technical problem to be solved by the present invention is to provide a method for recovering lithium in lithium iron phosphate, which directly recovers lithium in lithium iron phosphate by an electrochemical method.
本发明电化学法回收磷酸铁锂中的锂的方法，将磷酸铁锂作为正极，金属或碳类作为负极，水性溶液作为电解质，施加电势，使磷酸铁锂中的锂离子迁入电解质水溶液中形成含锂溶液。The method for recovering lithium in lithium iron phosphate by electrochemical method of the invention, using lithium iron phosphate as a positive electrode, metal or carbon as a negative electrode, and using an aqueous solution as an electrolyte, applying a potential to move lithium ions in lithium iron phosphate into an aqueous electrolyte solution A lithium-containing solution is formed.
其中，所述磷酸铁锂的来源为锂电池生产过程中产生的正极边角料、锂电池生产过程中产生的正极废料、磷酸铁锂生产过程中产生的废料或锂电池拆解后的正极。Wherein, the source of the lithium iron phosphate is a positive electrode scrap produced in a lithium battery production process, a positive electrode waste generated in a lithium battery production process, a waste generated in a lithium iron phosphate production process, or a positive electrode disassembled after a lithium battery is disassembled.
所述金属或碳类电极的材料为铂、镍、铜、钌、钛或碳。The material of the metal or carbon electrode is platinum, nickel, copper, ruthenium, titanium or carbon.
所述水性溶液电解质为氢氧化锂溶液、氯化钠溶液、硫酸锂溶液或硝酸锂溶液。The aqueous solution electrolyte is a lithium hydroxide solution, a sodium chloride solution, a lithium sulfate solution or a lithium nitrate solution.
进一步的，所述水性溶液电解质浓度为0.01～1mol/L，优选为0.025～0.8mol/L。Further, the aqueous solution electrolyte has a concentration of 0.01 to 1 mol/L, preferably 0.025 to 0.8 mol/L.
作为优选方案，施加0.1～5.0V的电势，施加电势的时间为0.5～8h。更优选施加0.1～4.4V的电势，施加电势的时间为1.5～5h。As a preferred embodiment, a potential of 0.1 to 5.0 V is applied, and the time for applying the potential is 0.5 to 8 hours. More preferably, a potential of 0.1 to 4.4 V is applied, and the time for applying the potential is 1.5 to 5 hours.
本发明回收磷酸铁锂中的锂的方法，可以将含锂溶液制备成锂盐。优选的，制备得到的锂盐为碳酸锂、氯化锂或氢氧化锂。In the method for recovering lithium in lithium iron phosphate according to the present invention, a lithium-containing solution can be prepared as a lithium salt. Preferably, the lithium salt prepared is lithium carbonate, lithium chloride or lithium hydroxide.
本发明通过电化学方法使锂离子从磷酸铁锂中直接迁入到电解液中，一次性将锂从磷酸铁锂中提取出来，形成锂溶液，其迁出率高，能达到90％以上，甚至高达99％。由于在一定的电势下只能迁出锂，对铁离子等其他离子都不敏感，具有高的选择性，实现在溶液中杂质含量较低，有利于得到品级可调的锂盐。通过本发明方法，能简单、高效的回收磷酸铁锂中的锂元素。此外，本发明也可回收其他正极材料中的锂，只是其得到的锂溶液杂质较多，后期提纯工艺复杂，从而造成成本较高。The invention directly moves lithium ions from the lithium iron phosphate into the electrolyte by electrochemical method, and extracts lithium from the lithium iron phosphate at one time to form a lithium solution, and the migration rate is high, and can reach more than 90%. Even as high as 99%. Since only lithium can be removed at a certain potential, it is not sensitive to other ions such as iron ions, has high selectivity, and achieves a low impurity content in the solution, which is favorable for obtaining a lithium salt of adjustable grade. By the method of the present invention, lithium element in lithium iron phosphate can be recovered simply and efficiently. In addition, the present invention can also recover lithium in other positive electrode materials, except that the obtained lithium solution has more impurities, and the later purification process is complicated, thereby causing high cost.
本发明电化学法回收磷酸铁锂中的锂的方法，将磷酸铁锂作为正极，金属或碳类作为负极，水性溶液作为电解质，施加电势，使磷酸铁锂中的锂离子迁入电解质水溶液中形成含锂溶液。The method for recovering lithium in lithium iron phosphate by electrochemical method of the invention, using lithium iron phosphate as a positive electrode, metal or carbon as a negative electrode, and using an aqueous solution as an electrolyte, applying a potential to move lithium ions in lithium iron phosphate into an aqueous electrolyte solution A lithium-containing solution is formed.
本发明的方法，回收的磷酸亚铁锂来源于市面上普遍存在的锂电池生产过程中产生的正极边角料、锂电池生产过程中产生的正极废料、磷酸铁锂生产过程中产生的废料或锂电池拆解后的正极。In the method of the invention, the recovered lithium iron phosphate is derived from the positive electrode scrap produced in the production process of the lithium battery which is ubiquitous on the market, the positive electrode waste generated in the production process of the lithium battery, the waste generated in the production process of the lithium iron phosphate or the lithium battery. Disassembled positive electrode.
所述金属或碳类电极的材料为铂、镍、铜、钌、钛或碳。 The material of the metal or carbon electrode is platinum, nickel, copper, ruthenium, titanium or carbon.
本发明所述的水性溶液即为电解质水溶液。所述水性溶液电解质为氢氧化锂溶液、氯化钠溶液、硫酸锂溶液或硝酸锂溶液。The aqueous solution of the present invention is an aqueous electrolyte solution. The aqueous solution electrolyte is a lithium hydroxide solution, a sodium chloride solution, a lithium sulfate solution or a lithium nitrate solution.
进一步的，所述水性溶液电解质浓度为0.01～1mol/L，优选为0.025～0.8mol/L。Further, the aqueous solution electrolyte has a concentration of 0.01 to 1 mol/L, preferably 0.025 to 0.8 mol/L.
作为优选方案，施加0.1～5.0V的电势，施加电势的时间为0.5～8h。更优选施加0.1～4.4V的电势，施加电势的时间为1.5～5h。As a preferred embodiment, a potential of 0.1 to 5.0 V is applied, and the time for applying the potential is 0.5 to 8 hours. More preferably, a potential of 0.1 to 4.4 V is applied, and the time for applying the potential is 1.5 to 5 hours.
本发明回收磷酸铁锂中的锂的方法，可以将含锂溶液制备成锂盐。常用的从含锂溶液中制备得到锂盐的方法均适用于本发明，优选的，制备得到的锂盐为碳酸锂、氯化锂或氢氧化锂。其制备方法为本领域现有技术，例如，采用如下方法制备得到碳酸锂：将含锂溶液浓缩至Li2O含量为30～35g/L的溶液，向其中加入280～285g/L的Na2CO3，过量系数为105％，得到碳酸锂沉淀，沉淀完成后陈化20min，进行固液分离得到碳酸锂粗品，将碳酸锂粗品以固液比为1:3用去离子水搅洗两次，得到纯度为电池级的碳酸锂产品。In the method for recovering lithium in lithium iron phosphate according to the present invention, a lithium-containing solution can be prepared as a lithium salt. A commonly used method for preparing a lithium salt from a lithium-containing solution is suitable for use in the present invention. Preferably, the prepared lithium salt is lithium carbonate, lithium chloride or lithium hydroxide. The preparation method is a prior art in the art, for example, lithium carbonate is prepared by the following method: a lithium-containing solution is concentrated to a solution having a Li 2 O content of 30 to 35 g/L, and 280 to 285 g/L of Na 2 is added thereto. CO 3 , the excess coefficient is 105%, the precipitation of lithium carbonate is obtained, and the precipitation is completed and aged for 20 minutes. The solid-liquid separation is carried out to obtain the crude lithium carbonate, and the crude lithium carbonate is stirred with deionized water at a solid-liquid ratio of 1:3. A lithium carbonate product having a purity of a battery grade is obtained.
下面结合实施例对本发明的具体实施方式做进一步的描述，并不因此将本发明限制在所述的实施例范围之中。The embodiments of the present invention are further described in conjunction with the embodiments, and are not intended to limit the invention.
实施例1Example 1
步骤1：以磷酸亚铁锂材料为正极片，以氯化钠水溶液为电解液，以石墨为负极，在电解槽中对其施加0.1V电势进行电化学回收，其中氯化钠溶液的浓度为0.025mol/L，时间为2h，使正极片中的锂离子迁入电解质溶液中形成含锂溶液。得到含锂溶液。实验结束后检测正极片中的锂含量，锂的迁出率能达到95.3％，检测含锂溶液中的锂含量，为1.1g/L(以Li2O计)。Step 1: The lithium iron phosphate material is used as the positive electrode sheet, the sodium chloride aqueous solution is used as the electrolyte, and the graphite is used as the negative electrode, and 0.1 V potential is applied to the electrolytic cell for electrochemical recovery, wherein the concentration of the sodium chloride solution is 0.025 mol/L for 2 h, the lithium ions in the positive electrode sheet were moved into the electrolyte solution to form a lithium-containing solution. A lithium-containing solution is obtained. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 95.3%, and the lithium content in the lithium-containing solution was measured to be 1.1 g/L (calculated as Li 2 O).
步骤2：将步骤1中所得的含锂溶液浓缩至Li2O含量为33g/L的溶液，向其中加入280g/L的Na2CO3，过量系数为105％，得到碳酸锂沉淀，沉淀完成后陈化20min，进行固液分离得到碳酸锂粗品，将碳酸锂粗品以固液比为1:3用去离子水搅洗两次，得到纯度为电池级的碳酸锂产品。Step 2: The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 33 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
实施例2Example 2
步骤1：以磷酸亚铁锂材料为正极片，以硫酸锂水溶液为电解液，以铜片为负极，在电解槽中对其施加0.3V的电势进行电化学回收，其中硫酸锂溶液的浓度为0.5mol/L,时间为1.5h，使正极片中的锂离子迁入电解质溶液中形成含锂溶液。实验结束后检测正极片中的锂含量，锂的迁出率能达到99.1％，检测含锂溶液中的锂含量，为1.1g/L (以Li2O计)。Step 1: The lithium iron phosphate material is used as a positive electrode sheet, the lithium sulfate aqueous solution is used as an electrolyte solution, and the copper piece is used as a negative electrode, and an electric potential of 0.3 V is applied to the electrolytic cell for electrochemical recovery, wherein the concentration of the lithium sulfate solution is 0.5 mol/L and a time of 1.5 h, the lithium ions in the positive electrode sheet were moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 99.1%, and the lithium content in the lithium-containing solution was measured to be 1.1 g/L (calculated as Li 2 O).
步骤2：将步骤1中所得的含锂溶液浓缩至Li2O含量为33g/L的溶液，向其中加入280g/L的Na2CO3，过量系数为105％，得到碳酸锂沉淀，沉淀完成后陈化20min，进行固液分离得到碳酸锂粗品，将碳酸锂粗品以固液比为1:3用去离子水搅洗两次，得到纯度为电池级的碳酸锂产品。Step 2: The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 33 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
实施例3Example 3
步骤1：以磷酸亚铁锂为正极片，以硫酸锂水溶液为电解液，以铜片为负极，在电解槽中对其施加1.2V的电势进行电化学回收，其中电解液浓度为0.8mol/L，时间为5h，使正极片中的锂离子迁入电解质溶液中形成含锂溶液。实验结束后检测正极片中的锂含量，锂的迁出率能达到99.6％，检测含锂溶液中的锂含量，为1.5g/L(以Li2O计)。Step 1: Lithium iron phosphate was used as the positive electrode sheet, lithium sulfate aqueous solution was used as the electrolyte, copper plate was used as the negative electrode, and 1.2 V potential was applied to the electrolytic cell for electrochemical recovery, wherein the electrolyte concentration was 0.8 mol/ L, the time is 5h, and the lithium ions in the positive electrode sheet are moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, the lithium removal rate was 99.6%, and the lithium content in the lithium-containing solution was measured to be 1.5 g/L (calculated as Li 2 O).
步骤2：将步骤1中所得的含锂溶液浓缩至Li2O含量为30g/L的溶液，向其中加入285g/L的Na2CO3，过量系数为105％，得到碳酸锂沉淀，沉淀完成后陈化20min，进行固液分离得到碳酸锂粗品，将碳酸锂粗品以固液比为1:3用去离子水搅洗两次，得到纯度为电池级的碳酸锂产品。Step 2: The lithium-containing solution obtained in the step 1 was concentrated to a solution having a Li 2 O content of 30 g/L, and 285 g/L of Na 2 CO 3 was added thereto, and the excess coefficient was 105% to obtain lithium carbonate precipitation, and the precipitation was completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
实施例4Example 4
步骤1：以磷酸亚铁锂为正极片，以硫酸锂水溶液为电解液，以铜片为负极，在电解槽中对其施加4.4V的电势进行电化学回收，其中电解液浓度为0.8mol/L，时间为2h，使正极片中的锂离子迁入电解质溶液中形成含锂溶液。实验结束后检测正极片中的锂含量，锂的迁出率能达到95.3％，检测含锂溶液中的锂含量，为1.5g/L(以Li2O计)。Step 1: Lithium iron phosphate was used as the positive electrode sheet, lithium sulfate aqueous solution was used as the electrolyte, copper plate was used as the negative electrode, and an electric potential of 4.4 V was applied to the electrolytic cell for electrochemical recovery, wherein the electrolyte concentration was 0.8 mol/ L, the time is 2h, and the lithium ions in the positive electrode sheet are moved into the electrolyte solution to form a lithium-containing solution. After the end of the experiment, the lithium content in the positive electrode sheet was measured, and the lithium removal rate was 95.3%, and the lithium content in the lithium-containing solution was measured to be 1.5 g/L (calculated as Li 2 O).
步骤2：将步骤1中所得的含锂溶液浓缩至Li2O含量为30g/L的溶液，向其中加入280g/L的Na2CO3，过量系数为105％，得到碳酸锂沉淀，沉淀完成后陈化20min，进行固液分离得到碳酸锂粗品，将碳酸锂粗品以固液比为1:3用去离子水搅洗两次，得到纯度为电池级的碳酸锂产品。 Step 2: The lithium-containing solution obtained in the step 1 is concentrated to a solution having a Li 2 O content of 30 g/L, and 280 g/L of Na 2 CO 3 is added thereto, and the excess coefficient is 105% to obtain lithium carbonate precipitation, and the precipitation is completed. After aging for 20 min, solid-liquid separation was carried out to obtain a crude lithium carbonate product, and the crude lithium carbonate was stirred twice with a solid-liquid ratio of 1:3 with deionized water to obtain a lithium carbonate product having a purity of a battery grade.
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