WO2024060505A1 - Recovery method for prussian positive electrode material and manganese-based prussian white positive electrode material prepared thereby - Google Patents

Recovery method for prussian positive electrode material and manganese-based prussian white positive electrode material prepared thereby Download PDF

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WO2024060505A1
WO2024060505A1 PCT/CN2023/077145 CN2023077145W WO2024060505A1 WO 2024060505 A1 WO2024060505 A1 WO 2024060505A1 CN 2023077145 W CN2023077145 W CN 2023077145W WO 2024060505 A1 WO2024060505 A1 WO 2024060505A1
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prussian
recycling
manganese
solution
positive electrode
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PCT/CN2023/077145
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Chinese (zh)
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李爱霞
余海军
谢英豪
李长东
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024060505A1 publication Critical patent/WO2024060505A1/en

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C3/00—Cyanogen; Compounds thereof
    • C01C3/08—Simple or complex cyanides of metals
    • C01C3/12—Simple or complex iron cyanides
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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 embodiments of the present application relate to the technical field of battery recycling, such as a recycling method of Prussian-type cathode materials and the prepared manganese-based Prussian white cathode materials.
  • the Prussian cathode material is a type of sodium-ion battery cathode material with an open frame structure. It is specifically a metal-organic frame structure material.
  • the metal and ferricyanide in the crystal lattice are arranged in a three-dimensional arrangement of Fe—C ⁇ N—M.
  • iron ions and metal M ions are arranged in a cube shape, and C ⁇ N roots are located on the edges of the cube.
  • This type of material belongs to the cubic crystal system, with a particle size of about 20 to 50nm, and has three-dimensional sodium ion intercalation and extraction channels.
  • This type of material has three main advantages as a cathode material for sodium-ion batteries: (1) The rigid framework structure and open large pores and sites ensure that sodium ions with larger ionic radius can be reversibly intercalated and detached without disturbing the material structure. Change; (2) Because of the two-electron redox reaction, the theoretical capacity of Prussian-based sodium cathode materials is as high as 170mAh/g; (3) The synthesis process of Prussian-based cathode materials is generally simple, low-toxic, and has low preparation and raw material costs. Suitable for mass production.
  • the embodiments of this application provide a method for recycling Prussian cathode materials.
  • This method mainly separates iron ions from the system through azeotropic treatment, and then re-complexes the separated cyanide with The metal ions in the separation system are complexed and finally converted into Prussian-like materials, achieving safe and effective recovery of each ion in the waste material.
  • a method for recycling Prussian cathode materials including the following steps:
  • the Prussian-type cathode material is first soaked in a strong acidic solution, and the reaction is carried out under boiling conditions to cause the metal ions such as manganese ions and sodium ions in the material to precipitate, and at the same time, the Prussian-type cathode material is [Fe(CN) 6 ] 4-
  • the stable structure is also destroyed and ferrous ions and cyanide are precipitated.
  • oxygen and a specific weakly acidic environment cause the ferrous ions precipitated in the solution to be oxidized and hydrolyzed and form hydroxide in one step.
  • Iron is separated from the solution system; further, when the pH of the solution after separation and precipitation is adjusted to 6 to 10, the metal ions and cyanide in the solution complex to form metal cyanate, and finally a complexing agent and a soluble metal salt are introduced. After co-precipitation, high-purity Prussian-type materials can be regenerated.
  • the recovery method has simple operation steps, high yield and high purity of the final product, which is safe and non-toxic. Depending on the actual situation, the recycled product can be further used to prepare high-performance Prussian-type cathodes. Material.
  • the Prussian cathode material is Na 2 Mn [Fe(CN) 6 ] cathode material.
  • the soluble metal salt in step (3) is a soluble manganese salt.
  • the complexing agent and the soluble manganese salt are mixed before being added to the treatment solution B.
  • Premixing the complexing agent and the soluble manganese salt can effectively reduce the reaction rate during the coprecipitation reaction, reduce the content of coordinated water and interstitial water, thereby improving the dispersibility and quality of the resulting material, and ultimately improving the gram capacity and electrochemical cycle stability of the product.
  • the treatment solution B after the pH of the treatment solution B is adjusted, before adding the complexing agent and the soluble metal salt, the treatment solution B also undergoes the following treatment: detecting the concentration of metal cyanate in the treatment solution B and adjusting it to 0.3 to 1 mol. /L.
  • the amount of soluble metal salt to be added can be effectively known to avoid adding too much or too little, resulting in waste of raw materials or the production of by-products.
  • the complexing agent in step (3) is at least one of maleic acid, lycic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), sodium citrate, and ammonia.
  • the concentration of the complexing agent in step (3) is 0.4-15 mol/L.
  • the temperature during the co-precipitation reaction in step (3) is 30 to 90°C, and the time is 1 to 5 hours.
  • the Prussian material obtained in step (3) is also aged and dried.
  • the aging time is 3 to 48 hours; the temperature during drying is 60 to 100°C, and the aging time is 4 to 12 hours.
  • the embodiment of the present application provides a manganese-based Prussian white cathode material, which is recovered and prepared by the recovery method of the Prussian-type cathode material described in the present application.
  • waste manganese-based Prussian white cathode materials are recycled, it is only necessary to use soluble manganese salts and re-complexed manganese cyanate to carry out a co-precipitation reaction in the above-mentioned recycling method to directly obtain manganese-based Prussian white cathode materials with moderate particle size, good dispersibility and high electrochemical activity.
  • the material preparation operation steps are simple, the waste material recycling rate is high, the economic benefits are high, and the performance quality of the output material is comparable to the existing commercially available manganese-based Prussian white cathode materials.
  • the beneficial effect of the embodiments of the present application is that the embodiments of the present application provide a method for recycling Prussian-type cathode materials.
  • This method reacts the waste Prussian-type cathode materials under boiling conditions to precipitate ferrous ions and cyanide, and then oxidizes them.
  • the ferric hydroxide is separated and recovered by hydrolysis; further, by adjusting the recovery liquid, the metal ions and cyanide contained in the liquid are complexed to regenerate metal cyanate, and finally the complexing agent and soluble metal salt are introduced for co-precipitation, and then the metal hydroxide can be regenerated. High-purity Prussian-like materials are generated.
  • the recovery method has simple operation steps.
  • the final product has high yield and purity, is safe and non-toxic, and the obtained Prussian-like materials, especially the manganese-based Prussian white cathode material prepared by using soluble manganese salts, have moderate particles. It has high dispersion and electrochemical activity, which is comparable to existing commercial products.
  • Figure 1 is a scanning electron microscope image of the manganese-based Prussian white cathode material recovered and prepared by the Prussian-type cathode material recovery method described in Example 1 of the present application.
  • Figure 2 is an XRD pattern of the manganese-based Prussian white cathode material recovered and prepared by the Prussian-type cathode material recovery method described in Example 1 of the present application.
  • step (3) of the recycling method is: adjusting the pH of the treatment solution B to 8 and stabilizing it , use ICP to detect the concentration of manganese cyanate in the solution to be 0.312mol/L, transfer it to the reaction kettle, Add 200L precursor solution and mix, carry out co-precipitation reaction at 70°C for 1 to 5 hours until complete, age for 48 hours, filter, and dry at 100°C for 10 hours to obtain the manganese-based Prussian white cathode material; the precursor solution is lemon Aqueous solution of acid and manganese sulfate, the concentrations of citric acid and manganese sulfate are both 1mol/L.
  • step (3) of the recycling method is: (3) Adjust the pH of the treatment solution B to 10 and stabilize, use ICP to detect the concentration of manganese cyanate in the solution to be 0.305mol/L, transfer it to the reaction kettle, directly add 100L of 2mol/L complexing agent citric acid and 100L of 2mol/L manganese sulfate solution and mix, in The coprecipitation reaction is carried out at 70°C for 1 to 5 hours until complete, aged for 48 hours, filtered, and dried at 100°C for 10 hours to obtain the manganese-based Prussian white cathode material.
  • a method for recycling Prussian cathode materials including the following steps:
  • a method for recycling Prussian cathode materials including the following steps:
  • the discharge specific capacity of the product is also equivalent to commercial materials, indicating that the recycling method of Prussian-type cathode materials described in this application can not only effectively solve the recycling problem of existing discarded Prussian-type cathode materials, but also The performance of the products prepared by further processing of the recycled materials is equivalent to that of commercial products, and can completely replace the production and use of existing commercial manganese-rich manganese-based Prussian white cathode materials.

Abstract

A recovery method for a Prussian positive electrode material and a manganese-based Prussian white positive electrode material prepared by using the method, which belong to the technical field of battery recovery. The recovery method for a Prussian positive electrode material comprises: soaking a waste Prussian positive electrode material in an acidic solution, reacting same under boiling conditions to precipitate out ferrous ions and cyanogen, and then obtaining ferric hydroxide and a recovery solution by means of an oxidative hydrolysis effect; and furthermore, adjusting the pH value of the recovery solution, such that the metal ions and the cyanogen in the recovery solution are subjected to a complexing reaction to regenerate metal cyanate, adding a complexing agent and a soluble metal salt for co-precipitation, and regenerating a high-purity Prussian material. The recovery method has simple operation steps; and the final product has a high yield and a high purity, and is safe and non-toxic.

Description

一种普鲁士类正极材料的回收方法及其制备的锰基普鲁士白正极材料A method for recycling Prussian-type cathode materials and the prepared manganese-based Prussian white cathode material 技术领域Technical field
本申请实施例涉及电池回收技术领域，例如一种普鲁士类正极材料的回收方法及其制备的锰基普鲁士白正极材料。The embodiments of the present application relate to the technical field of battery recycling, such as a recycling method of Prussian-type cathode materials and the prepared manganese-based Prussian white cathode materials.
背景技术Background technique
普鲁士类正极材料是一类具有开放式框架结构的钠离子电池正极材料，具体属于金属-有机物框架结构材料，其晶格中的金属与铁氰根按Fe—C≡N—M的排列形成三维结构骨架，铁离子和金属M离子按立方体状排列，C≡N根位于立方体的棱上。这类材料属于立方晶系，粒子尺寸约为20～50nm，其拥有三维的钠离子嵌脱通道。这类材料作为钠离子电池正极材料的优势主要有三点：(1)刚性的框架结构和开放性的大孔隙、位点保证离子半径较大的钠离子可以可逆的嵌脱而不会使材料结构改变；(2)因为具有双电子的氧化还原反应，普鲁士类钠正极材料的理论容量高达170mAh/g；(3)普鲁士类正极材料的合成过程一般比较简单，低毒且制备及原料成本低，适于大规模生产。The Prussian cathode material is a type of sodium-ion battery cathode material with an open frame structure. It is specifically a metal-organic frame structure material. The metal and ferricyanide in the crystal lattice are arranged in a three-dimensional arrangement of Fe—C≡N—M. In the structural skeleton, iron ions and metal M ions are arranged in a cube shape, and C≡N roots are located on the edges of the cube. This type of material belongs to the cubic crystal system, with a particle size of about 20 to 50nm, and has three-dimensional sodium ion intercalation and extraction channels. This type of material has three main advantages as a cathode material for sodium-ion batteries: (1) The rigid framework structure and open large pores and sites ensure that sodium ions with larger ionic radius can be reversibly intercalated and detached without disturbing the material structure. Change; (2) Because of the two-electron redox reaction, the theoretical capacity of Prussian-based sodium cathode materials is as high as 170mAh/g; (3) The synthesis process of Prussian-based cathode materials is generally simple, low-toxic, and has low preparation and raw material costs. Suitable for mass production.
然而，随着普鲁士类正极材料逐渐走向产业化，其产生的大量废弃材料也成为了一个需要解决的问题，主要是由于普鲁士类钠正极材料的结构与常规正极材料不同，回收方法也不尽相同，而该材料中含有[Fe(CN)6]4-具有一定的低毒性，若处理不当可能会造成环境污染。However, as Prussian-type cathode materials gradually move towards industrialization, the large amount of waste materials they generate has become a problem that needs to be solved. This is mainly because the structure of Prussian-type sodium cathode materials is different from conventional cathode materials, and the recycling methods are also different. , and the material contains [Fe(CN) 6 ] 4- , which has a certain low toxicity and may cause environmental pollution if not handled properly.
发明内容Contents of the invention
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。The following is an overview of the topics described in detail in this article. This summary is not intended to limit the scope of the claims.
基于相关技术存在的缺陷，本申请实施例提供了普鲁士类正极材料的的回收方法，该方法主要通过共沸处理首先将铁离子分离出体系，随后重新以络合作用将分离出来的氰根与分离体系中的金属离子进行络合并最终转换为普鲁士类材料，实现废弃材料各离子的安全有效回收。Based on the shortcomings of related technologies, the embodiments of this application provide a method for recycling Prussian cathode materials. This method mainly separates iron ions from the system through azeotropic treatment, and then re-complexes the separated cyanide with The metal ions in the separation system are complexed and finally converted into Prussian-like materials, achieving safe and effective recovery of each ion in the waste material.
本申请实施例采取的技术方案为：The technical solutions adopted in the embodiments of this application are:
一种普鲁士类正极材料的回收方法，包括以下步骤：A method for recycling Prussian cathode materials, including the following steps:
(1)将废旧电池上分离的普鲁士类正极材料浸泡在pH＜2.5的酸性溶液中， 在沸腾条件下反应0.5～2h，得处理溶液A；(1) Soak the Prussian cathode material separated from the used battery in an acidic solution with pH < 2.5. React under boiling conditions for 0.5 to 2 hours to obtain treatment solution A;
(2)在处理溶液A中通入氧气并调节溶液pH为2.7～4发生沉淀反应至完全，过滤，得氢氧化铁沉淀及处理溶液B；(2) Pour oxygen into the treatment solution A and adjust the pH of the solution to 2.7-4 to cause the precipitation reaction to be complete, then filter to obtain iron hydroxide precipitation and treatment solution B;
(3)调节处理溶液B的pH至6～10并稳定，加入络合剂及可溶性金属盐进行共沉淀反应至完全，过滤，得普鲁士类材料。(3) Adjust the pH of treatment solution B to 6 to 10 and stabilize it, add complexing agent and soluble metal salt to carry out co-precipitation reaction until it is complete, and filter to obtain Prussian material.
本申请所述普鲁士类正极材料的回收方法中，首先将普鲁士类正极材料浸泡在强酸性溶液中，在沸腾条件下进行反应使得材料中的锰离子、钠离子等金属离子析出，同时材料中的[Fe(CN)6]4-稳定结构也被破坏并析出亚铁离子和氰根，此时通过氧气和特定弱酸性的环境使得溶液中析出的亚铁离子发生氧化和水解并一步形成氢氧化铁分离出溶液体系；进一步的，当分离沉淀后的溶液调节pH至6～10时，溶液中的金属离子和氰根发生络合作用生成金属氰酸根，最终引入络合剂及可溶性金属盐进行共沉淀后，可重新生成高纯度的普鲁士类材料，所述回收方法操作步骤简单，最终产品产率高且纯度高，安全无毒，根据实际情况可选择将回收产物进一步制备高性能普鲁士类正极材料。In the recycling method of the Prussian-type cathode material described in this application, the Prussian-type cathode material is first soaked in a strong acidic solution, and the reaction is carried out under boiling conditions to cause the metal ions such as manganese ions and sodium ions in the material to precipitate, and at the same time, the Prussian-type cathode material is [Fe(CN) 6 ] 4- The stable structure is also destroyed and ferrous ions and cyanide are precipitated. At this time, oxygen and a specific weakly acidic environment cause the ferrous ions precipitated in the solution to be oxidized and hydrolyzed and form hydroxide in one step. Iron is separated from the solution system; further, when the pH of the solution after separation and precipitation is adjusted to 6 to 10, the metal ions and cyanide in the solution complex to form metal cyanate, and finally a complexing agent and a soluble metal salt are introduced. After co-precipitation, high-purity Prussian-type materials can be regenerated. The recovery method has simple operation steps, high yield and high purity of the final product, which is safe and non-toxic. Depending on the actual situation, the recycled product can be further used to prepare high-performance Prussian-type cathodes. Material.
优选地，所述普鲁士类正极材料为Na2Mn[Fe(CN)6]正极材料。Preferably, the Prussian cathode material is Na 2 Mn [Fe(CN) 6 ] cathode material.
由于铁和锰均是电池正极材料领域中常用的两种互补元素，当材料中的铁元素被析出，在优选条件下锰元素可以有效和余下的氰根进行高活性络合生成[Mn(CN)6]4-。Since both iron and manganese are two complementary elements commonly used in the field of battery cathode materials, when the iron element in the material is precipitated, the manganese element can effectively complex with the remaining cyanide ions under optimal conditions to form [Mn(CN ) 6 ] 4- .
更优选地，所述步骤(3)中的可溶性金属盐为可溶性锰盐。More preferably, the soluble metal salt in step (3) is a soluble manganese salt.
当处理溶液B中的活性离子为[Mn(CN)6]4-时，引入可溶性锰盐与络合剂进行共沉淀反应可生成高活性的富锰锰基普鲁士白正极材料，该材料不仅颗粒均匀分散，同时具有较高的电化学活性，与现有市售的商业材料相媲美，生产性价比较高。When the active ions in treatment solution B are [Mn(CN) 6 ] 4- , introducing soluble manganese salts and complexing agents for co-precipitation reaction can generate highly active manganese-rich manganese-based Prussian white cathode materials, which are not only particles It is uniformly dispersed and has high electrochemical activity, which is comparable to existing commercial materials and has high production cost performance.
优选地，所述络合剂和可溶性锰盐在加入处理溶液B前先进行混合处理。Preferably, the complexing agent and the soluble manganese salt are mixed before being added to the treatment solution B.
将络合剂及可溶性锰盐预先混合，可以有效降低在共沉淀反应时的反应速率，降低配位水和间隙水含量，从而提升所得材料的分散性和品质，最终提升产品的克容量和电化学循环稳定性。Premixing the complexing agent and the soluble manganese salt can effectively reduce the reaction rate during the coprecipitation reaction, reduce the content of coordinated water and interstitial water, thereby improving the dispersibility and quality of the resulting material, and ultimately improving the gram capacity and electrochemical cycle stability of the product.
优选地，所述步骤(3)中处理溶液B在pH调节后，在加入络合剂和可溶性金属盐前，还经过以下处理：检测处理溶液B中金属氰酸根的浓度并调节为0.3～1mol/L。 Preferably, in step (3), after the pH of the treatment solution B is adjusted, before adding the complexing agent and the soluble metal salt, the treatment solution B also undergoes the following treatment: detecting the concentration of metal cyanate in the treatment solution B and adjusting it to 0.3 to 1 mol. /L.
通过金属氰酸根的浓度检测及调节，可以有效知晓可溶性金属盐的添加量，避免添加过多或过少，造成原料的浪费或副产物的产生。By detecting and adjusting the concentration of metal cyanate, the amount of soluble metal salt to be added can be effectively known to avoid adding too much or too little, resulting in waste of raw materials or the production of by-products.
优选地，所述步骤(3)中络合剂为马来酸、枸杞酸、柠檬酸、乙二胺四乙酸(EDTA)、柠檬酸钠、氨水中的至少一种。Preferably, the complexing agent in step (3) is at least one of maleic acid, lycic acid, citric acid, ethylenediaminetetraacetic acid (EDTA), sodium citrate, and ammonia.
优选地，所述步骤(3)中络合剂的浓度为0.4～15mol/L。Preferably, the concentration of the complexing agent in step (3) is 0.4-15 mol/L.
优选地，所述步骤(3)中共沉淀反应时温度为30～90℃，时间为1～5h。Preferably, the temperature during the co-precipitation reaction in step (3) is 30 to 90°C, and the time is 1 to 5 hours.
优选地，所述步骤(3)所得普鲁士类材料还经过陈化和干燥处理。Preferably, the Prussian material obtained in step (3) is also aged and dried.
更优选地，所述陈化的时间为3～48h；干燥时的温度为60～100℃，时间为4～12h。More preferably, the aging time is 3 to 48 hours; the temperature during drying is 60 to 100°C, and the aging time is 4 to 12 hours.
本申请实施例提供一种锰基普鲁士白正极材料，由本申请所述普鲁士类正极材料的回收方法回收制备得到。The embodiment of the present application provides a manganese-based Prussian white cathode material, which is recovered and prepared by the recovery method of the Prussian-type cathode material described in the present application.
当采用锰基普鲁士类正极材料废料进行回收处理时，只需在上述回收方法中采用可溶性锰盐与重新络合的锰氰酸根进行共沉淀反应，即可直接获得颗粒尺寸适中，分散性好且电化学活性高的锰基普鲁士白正极材料，所述材料制备操作步骤简单，废弃材料回收利用率高，经济效益高，产出材料的性能品质可媲美现有市售的锰基普鲁士白正极材料。When waste manganese-based Prussian white cathode materials are recycled, it is only necessary to use soluble manganese salts and re-complexed manganese cyanate to carry out a co-precipitation reaction in the above-mentioned recycling method to directly obtain manganese-based Prussian white cathode materials with moderate particle size, good dispersibility and high electrochemical activity. The material preparation operation steps are simple, the waste material recycling rate is high, the economic benefits are high, and the performance quality of the output material is comparable to the existing commercially available manganese-based Prussian white cathode materials.
本申请实施例的有益效果在于，本申请实施例提供了一种普鲁士类正极材料的回收方法，该方法将废旧普鲁士类正极材料在沸腾条件下进行反应析出亚铁离子和氰根，随后通过氧化水解作用分离回收氢氧化铁；进一步的，通过调节回收液使其含有的金属离子和氰根发生络合作用重新生成金属氰酸根，最终引入络合剂及可溶性金属盐进行共沉淀后，可重新生成高纯度的普鲁士类材料，所述回收方法操作步骤简单，最终产品产率高且纯度高，安全无毒，所得普鲁士类材料尤其是选用可溶性锰盐制备的锰基普鲁士白正极材料颗粒适中，分散性及电化学活性高，可媲美现有市售产品。The beneficial effect of the embodiments of the present application is that the embodiments of the present application provide a method for recycling Prussian-type cathode materials. This method reacts the waste Prussian-type cathode materials under boiling conditions to precipitate ferrous ions and cyanide, and then oxidizes them. The ferric hydroxide is separated and recovered by hydrolysis; further, by adjusting the recovery liquid, the metal ions and cyanide contained in the liquid are complexed to regenerate metal cyanate, and finally the complexing agent and soluble metal salt are introduced for co-precipitation, and then the metal hydroxide can be regenerated. High-purity Prussian-like materials are generated. The recovery method has simple operation steps. The final product has high yield and purity, is safe and non-toxic, and the obtained Prussian-like materials, especially the manganese-based Prussian white cathode material prepared by using soluble manganese salts, have moderate particles. It has high dispersion and electrochemical activity, which is comparable to existing commercial products.
在阅读并理解了附图和详细描述后，可以明白其他方面。Other aspects will be apparent upon reading and understanding the drawings and detailed description.
附图说明BRIEF DESCRIPTION OF THE DRAWINGS
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。 The accompanying drawings are used to provide a further understanding of the technical solutions herein, and constitute a part of the specification. Together with the embodiments of the present application, they are used to explain the technical solutions herein, and do not constitute a limitation of the technical solutions herein.
图1为本申请实施例1所述普鲁士类正极材料的回收方法回收制备的锰基普鲁士白正极材料的扫描电镜图。Figure 1 is a scanning electron microscope image of the manganese-based Prussian white cathode material recovered and prepared by the Prussian-type cathode material recovery method described in Example 1 of the present application.
图2为本申请实施例1所述普鲁士类正极材料的回收方法回收制备的锰基普鲁士白正极材料的XRD图。Figure 2 is an XRD pattern of the manganese-based Prussian white cathode material recovered and prepared by the Prussian-type cathode material recovery method described in Example 1 of the present application.
具体实施方式Detailed ways
为了更好地说明本申请的目的、技术方案和优点，下面将结合具体实施例/对比例对本申请作进一步说明，其目的在于详细地理解本申请的内容，而不是对本申请的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本申请的保护范围。本申请实施、对比例所设计的实验试剂、原料及仪器，除非特别说明，均为常用的普通试剂、原料及仪器。In order to better explain the purpose, technical solutions and advantages of the present application, the present application will be further described below in conjunction with specific examples/comparative examples. The purpose is to understand the content of the present application in detail, rather than to limit the present application. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of this application. The experimental reagents, raw materials and instruments designed for the implementation and comparative examples of this application are all commonly used common reagents, raw materials and instruments unless otherwise specified.
实施例1Example 1
本申请所述普鲁士类正极材料的回收方法的一种实施例，包括以下步骤：An embodiment of the recycling method of Prussian cathode materials described in this application includes the following steps:
(1)将废旧锰基普鲁士白钠Na2Mn[Fe(CN)6]电池上分离的正极材料刮下，收集80kg浸泡在100L的pH＜2.5的3mol/L硫酸溶液中，在沸腾条件下反应1h，得处理溶液A；(1) Scrape off the separated positive electrode material from the waste manganese-based Prussian white sodium Na 2 Mn [Fe(CN) 6 ] battery, collect 80kg and soak it in 100L of 3mol/L sulfuric acid solution with pH < 2.5, under boiling conditions After 1 hour of reaction, solution A is obtained;
(2)在处理溶液A中通入氧气并用水调节溶液pH为3.5发生沉淀反应至完全，过滤红色的沉淀，得氢氧化铁沉淀及余下的处理溶液B；(2) Pour oxygen into the treatment solution A and adjust the pH of the solution to 3.5 with water to cause the precipitation reaction to be complete. Filter the red precipitate to obtain iron hydroxide precipitate and the remaining treatment solution B;
(3)调节处理溶液B的pH至8并稳定，采用ICP检测溶液中锰氰酸根的浓度为0.312mol/L，转移至反应釜中，直接加入100L的2mol/L络合剂柠檬酸及100L的2mol/L硫酸锰溶液混合，在70℃下进行共沉淀反应1～5h至完全，陈化48h，过滤，在100℃下干燥10h，即得锰基普鲁士白正极材料。将所得材料进行扫描电镜观察，如图1所示，可以看出该材料颗粒均匀分散，尺寸适中，没有明显团聚；进一步进行XRD测试，结果如图2所示，该材料纯度较高，无明显杂质特征峰。(3) Adjust the pH of treatment solution B to 8 and stabilize it. Use ICP to detect the concentration of manganese cyanate in the solution to 0.312mol/L. Transfer it to the reaction kettle and directly add 100L of 2mol/L complexing agent citric acid and 100L Mix 2 mol/L manganese sulfate solution, carry out co-precipitation reaction at 70°C for 1 to 5 hours until complete, age for 48 hours, filter, and dry at 100°C for 10 hours to obtain manganese-based Prussian white cathode material. The obtained material was observed with a scanning electron microscope, as shown in Figure 1. It can be seen that the material particles are evenly dispersed, of moderate size, and have no obvious agglomeration. Further XRD testing was performed, and the results are shown in Figure 2. The material has high purity and no obvious agglomeration. Impurity characteristic peaks.
实施例2Example 2
本申请所述普鲁士类正极材料的回收方法的一种实施例，本实施例与实施例1的差别仅在于，所述回收方法的步骤(3)为：调节处理溶液B的pH至8并稳定，采用ICP检测溶液中锰氰酸根的浓度为0.312mol/L，转移至反应釜中， 加入200L前驱体溶液混合，在70℃下进行共沉淀反应1～5h至完全，陈化48h，过滤，在100℃下干燥10h，即得锰基普鲁士白正极材料；所述前驱体溶液为柠檬酸和硫酸锰的水溶液，柠檬酸和硫酸锰的浓度均为1mol/L。An embodiment of the recycling method of the Prussian cathode material described in this application. The only difference between this embodiment and Embodiment 1 is that step (3) of the recycling method is: adjusting the pH of the treatment solution B to 8 and stabilizing it , use ICP to detect the concentration of manganese cyanate in the solution to be 0.312mol/L, transfer it to the reaction kettle, Add 200L precursor solution and mix, carry out co-precipitation reaction at 70°C for 1 to 5 hours until complete, age for 48 hours, filter, and dry at 100°C for 10 hours to obtain the manganese-based Prussian white cathode material; the precursor solution is lemon Aqueous solution of acid and manganese sulfate, the concentrations of citric acid and manganese sulfate are both 1mol/L.
实施例3Example 3
本申请所述普鲁士类正极材料的回收方法的一种实施例，本实施例与实施例1的差别仅在于，所述回收方法的步骤(3)为：(3)调节处理溶液B的pH至10并稳定，采用ICP检测溶液中锰氰酸根的浓度为0.305mol/L，转移至反应釜中，直接加入100L的2mol/L络合剂柠檬酸及100L的2mol/L硫酸锰溶液混合，在70℃下进行共沉淀反应1～5h至完全，陈化48h，过滤，在100℃下干燥10h，即得锰基普鲁士白正极材料。An embodiment of the recycling method of the Prussian cathode material described in this application. The only difference between this embodiment and Embodiment 1 is that step (3) of the recycling method is: (3) Adjust the pH of the treatment solution B to 10 and stabilize, use ICP to detect the concentration of manganese cyanate in the solution to be 0.305mol/L, transfer it to the reaction kettle, directly add 100L of 2mol/L complexing agent citric acid and 100L of 2mol/L manganese sulfate solution and mix, in The coprecipitation reaction is carried out at 70°C for 1 to 5 hours until complete, aged for 48 hours, filtered, and dried at 100°C for 10 hours to obtain the manganese-based Prussian white cathode material.
对比例1Comparative Example 1
一种普鲁士类正极材料的回收方法，包括以下步骤：A method for recycling Prussian cathode materials, including the following steps:
(1)将废旧锰基普鲁士白钠Na2Mn[Fe(CN)6]电池上分离的正极材料刮下，收集80kg浸泡在100L的pH＜2.5的3mol/L硫酸溶液中，在沸腾条件下反应1h，得处理溶液A；(1) Scrape off the separated positive electrode material from the waste manganese-based Prussian white sodium Na 2 Mn [Fe(CN) 6 ] battery, collect 80kg and soak it in 100L of 3mol/L sulfuric acid solution with pH < 2.5, under boiling conditions After 1 hour of reaction, solution A is obtained;
(2)在处理溶液A中通入氧气并用水调节溶液pH为6发生沉淀反应至完全，此时观察到先生成红色沉淀，再生成褐色沉淀，过滤沉淀后，得氢氧化铁和羟基氧化锰的混合沉淀以及余下的处理溶液B；(2) Pour oxygen into the treatment solution A and adjust the solution pH to 6 with water to allow the precipitation reaction to complete. At this time, it is observed that a red precipitate is formed first, and then a brown precipitate is formed. After filtering the precipitate, ferric hydroxide and manganese oxyhydroxide are obtained. The mixed precipitation and the remaining treatment solution B;
(3)调节处理溶液B的pH至8并稳定，采用ICP检测溶液中锰氰酸根的浓度为0.109mol/L，含量过少，无法再进一步用于合成锰基普鲁士白正极材料。(3) Adjust the pH of treatment solution B to 8 and stabilize it. Use ICP to detect the concentration of manganese cyanate in the solution to be 0.109 mol/L. The content is too small and cannot be further used to synthesize manganese-based Prussian white cathode materials.
对比例2Comparative example 2
一种普鲁士类正极材料的回收方法，包括以下步骤：A method for recycling Prussian cathode materials, including the following steps:
(1)将废旧锰基普鲁士白钠Na2Mn[Fe(CN)6]电池上分离的正极材料刮下，收集80kg浸泡在100L的pH＜2.5的3mol/L硫酸溶液中，在沸腾条件下反应1h，得处理溶液A；(1) Scrape off the separated positive electrode material from the waste manganese-based Prussian white sodium Na 2 Mn [Fe(CN) 6 ] battery, collect 80kg and soak it in 100L of 3mol/L sulfuric acid solution with pH < 2.5, under boiling conditions After 1 hour of reaction, solution A is obtained;
(2)在处理溶液A中通入氧气并用水调节溶液pH为3.5发生沉淀反应至完全，过滤红色沉淀后，得氢氧化铁沉淀以及余下的处理溶液B； (2) Pour oxygen into the treatment solution A and adjust the pH of the solution to 3.5 with water to cause the precipitation reaction to be complete. After filtering the red precipitate, the iron hydroxide precipitate and the remaining treatment solution B are obtained;
(3)调节处理溶液B的pH至11并稳定，采用ICP检测溶液中锰氰酸根的浓度为0.11mol/L，含量过少，无法再进一步用于合成锰基普鲁士白正极材料。效果例(3) Adjust the pH of treatment solution B to 11 and stabilize it. Use ICP to detect the concentration of manganese cyanate in the solution to be 0.11 mol/L. The content is too small and cannot be further used to synthesize manganese-based Prussian white cathode materials. Effect example
为了验证本申请所述普鲁士类正极材料回收制备的锰基普鲁士白正极材料的性质和性能，将各实施例产品进行粒径分布(D10、D50、D90)、比表面积、振实密度的测试，同时以该材料作为钠离子电池正极材料制备正极极片，采用商用钠电隔膜和钠片共同制备钠离子半电池，在2～4V的工作电压下，以0.2C的倍率进行充放电测试并记录其放电比容量，同时以市售富锰锰基普鲁士白正极材料作为对照样品与各实施例产品进行相同处理和测试进行比较，测试结果如表1所示。In order to verify the properties and performance of the manganese-based Prussian white cathode material prepared by recycling the Prussian cathode material described in this application, the products of each example were tested for particle size distribution (D10, D50, D90), specific surface area, and tap density. At the same time, this material was used as the cathode material of the sodium-ion battery to prepare the cathode plate. Commercial sodium electrolytic separators and sodium sheets were used to prepare the sodium-ion half-battery. Under the working voltage of 2 to 4V, the charge and discharge test was performed at a rate of 0.2C and recorded. The discharge specific capacity was compared with the commercially available manganese-rich manganese-based Prussian white cathode material as a control sample and the products of each embodiment through the same treatment and testing. The test results are shown in Table 1.
表1
Table 1
从表1可以看出，各实施例所述回收方法重新制备的产品的粒径分布及均匀度与现有市售的商业富锰锰基普鲁士白正极材料几乎一致，比表面积和振实密度也较为相似，在电化学性能方面，所述产品的放电比容量也与商业材料相当，说明本申请所述普鲁士类正极材料的回收方法不仅可有效解决现有废弃普鲁士类正极材料的回收问题，同时回收得到的材料进一步加工制备的产品其性能与商业产品相当，完全可以代替现有商业富锰锰基普鲁士白正极材料生产和使用。It can be seen from Table 1 that the particle size distribution and uniformity of the products re-prepared by the recycling method described in each embodiment are almost the same as those of the commercially available commercial manganese-rich manganese-based Prussian white cathode materials, and the specific surface area and tap density are also the same. Relatively similar, in terms of electrochemical performance, the discharge specific capacity of the product is also equivalent to commercial materials, indicating that the recycling method of Prussian-type cathode materials described in this application can not only effectively solve the recycling problem of existing discarded Prussian-type cathode materials, but also The performance of the products prepared by further processing of the recycled materials is equivalent to that of commercial products, and can completely replace the production and use of existing commercial manganese-rich manganese-based Prussian white cathode materials.
最后所应当说明的是，以上实施例仅用以说明本申请的技术方案而非对本申请保护范围的限制，尽管参照较佳实施例对本申请作了详细说明，本领域的普通技术人员应当理解，可以对本申请的技术方案进行修改或者等同替换，而不脱离本申请技术方案的实质和范围。 Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application and do not limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present application may be modified or equivalently substituted without departing from the essence and scope of the technical solution of the present application.

Claims (10)

  1. 一种普鲁士类正极材料的回收方法，其包括以下步骤：A method for recycling Prussian cathode materials, which includes the following steps:
    (1)将废旧电池上分离的普鲁士类正极材料浸泡在pH＜2.5的酸性溶液中，在沸腾条件下反应0.5～2h，得处理溶液A；(1) Soak the Prussian cathode material separated from the used battery in an acidic solution with pH < 2.5, and react under boiling conditions for 0.5 to 2 hours to obtain treatment solution A;
    (2)在处理溶液A中通入氧气并调节溶液pH为2.7～4发生沉淀反应至完全，过滤，得氢氧化铁沉淀及处理溶液B；(2) Pour oxygen into the treatment solution A and adjust the pH of the solution to 2.7-4 to cause the precipitation reaction to be complete, then filter to obtain iron hydroxide precipitation and treatment solution B;
    (3)调节处理溶液B的pH至6～10并稳定，加入络合剂及可溶性金属盐进行共沉淀反应至完全，过滤，得普鲁士类材料。(3) Adjust the pH of treatment solution B to 6 to 10 and stabilize it, add complexing agent and soluble metal salt to carry out co-precipitation reaction until it is complete, and filter to obtain Prussian material.
  2. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述普鲁士类正极材料为Na2Mn[Fe(CN)6]正极材料。The recycling method of Prussian-type cathode material according to claim 1, wherein the Prussian-type cathode material is Na 2 Mn [Fe(CN) 6 ] cathode material.
  3. 如权利要求2所述普鲁士类正极材料的回收方法，其中，所述步骤(3)中的可溶性金属盐为可溶性锰盐。The method for recycling Prussian cathode materials according to claim 2, wherein the soluble metal salt in step (3) is a soluble manganese salt.
  4. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述络合剂和可溶性锰盐在加入处理溶液B前先进行混合处理。The method for recycling Prussian cathode materials according to claim 1, wherein the complexing agent and the soluble manganese salt are mixed before adding the treatment solution B.
  5. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述步骤(3)中处理溶液B在pH调节后，在加入络合剂和可溶性金属盐前，还经过以下处理：检测处理溶液B中金属氰酸根的浓度并调节为0.3～1mol/L。The method for recycling Prussian cathode materials according to claim 1, wherein in the step (3), after the pH adjustment, the treatment solution B also undergoes the following treatment before adding the complexing agent and the soluble metal salt: detecting the treatment solution The concentration of metal cyanate in B is adjusted to 0.3~1mol/L.
  6. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述步骤(3)中络合剂为马来酸、枸杞酸、柠檬酸、乙二胺四乙酸、柠檬酸钠、氨水中的至少一种。The method for recycling Prussian cathode materials according to claim 1, wherein the complexing agent in step (3) is maleic acid, lycic acid, citric acid, ethylenediaminetetraacetic acid, sodium citrate, or ammonia in water. At least one.
  7. 如权利要求6所述普鲁士类正极材料的回收方法，其中，所述步骤(3)中络合剂的浓度为0.4～15mol/L。The method for recovering Prussian cathode materials as claimed in claim 6, wherein the concentration of the complexing agent in step (3) is 0.4 to 15 mol/L.
  8. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述步骤(3)中共沉淀反应时温度为30～90℃，时间为1～5h。The method for recycling Prussian cathode materials according to claim 1, wherein the temperature during the coprecipitation reaction in step (3) is 30-90°C and the time is 1-5 hours.
  9. 如权利要求1所述普鲁士类正极材料的回收方法，其中，所述步骤(3) 所得普鲁士类材料还经过陈化和干燥处理；The method for recycling Prussian cathode materials according to claim 1, wherein the step (3) The resulting prussian material is also aged and dried;
    所述陈化的时间为3～48h；干燥时的温度为60～100℃，时间为4～12h。The aging time is 3 to 48 hours; the temperature during drying is 60 to 100°C, and the aging time is 4 to 12 hours.
  10. 一种锰基普鲁士白正极材料，其中，由权利要求1～9任一项所述普鲁士类正极材料的回收方法回收制备得到。 A manganese-based Prussian white cathode material, which is prepared by recycling the Prussian-type cathode material according to any one of claims 1 to 9.
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CN115498299A (en) * 2022-09-22 2022-12-20 广东邦普循环科技有限公司 Method for recovering Prussian positive electrode material and manganese-based Prussian white positive electrode material prepared by same

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JP2013112767A (en) * 2011-11-30 2013-06-10 Alps Electric Co Ltd Method for producing ink containing prussian blue type complex, and method for manufacturing electrochromic element using the ink
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CN112209409A (en) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery
CN112645354A (en) * 2020-12-21 2021-04-13 电子科技大学 Surface-modified sodium-manganese-iron-based Prussian blue material and preparation method and application thereof
CN115000494A (en) * 2022-06-16 2022-09-02 杨维年 Low-energy-consumption production process for sodium ion battery
CN115498299A (en) * 2022-09-22 2022-12-20 广东邦普循环科技有限公司 Method for recovering Prussian positive electrode material and manganese-based Prussian white positive electrode material prepared by same

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CN102285673A (en) * 2011-06-03 2011-12-21 佛山市邦普循环科技有限公司 Method for recovering lithium and iron from lithium iron phosphate power battery for electromobile
JP2013112767A (en) * 2011-11-30 2013-06-10 Alps Electric Co Ltd Method for producing ink containing prussian blue type complex, and method for manufacturing electrochromic element using the ink
CN110697796A (en) * 2019-10-09 2020-01-17 福建江夏学院 Green and efficient synthesis method of transition metal oxyhydroxide ultrathin nanosheets
CN112209409A (en) * 2020-09-28 2021-01-12 浙江凯恩电池有限公司 Method for rapidly preparing Prussian white serving as positive electrode material of sodium-ion battery
CN112645354A (en) * 2020-12-21 2021-04-13 电子科技大学 Surface-modified sodium-manganese-iron-based Prussian blue material and preparation method and application thereof
CN115000494A (en) * 2022-06-16 2022-09-02 杨维年 Low-energy-consumption production process for sodium ion battery
CN115498299A (en) * 2022-09-22 2022-12-20 广东邦普循环科技有限公司 Method for recovering Prussian positive electrode material and manganese-based Prussian white positive electrode material prepared by same

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