WO2024051095A1 - Recycling method for waste prussian sodium battery positive electrode material, and use - Google Patents

Recycling method for waste prussian sodium battery positive electrode material, and use Download PDF

Info

Publication number
WO2024051095A1
WO2024051095A1 PCT/CN2023/077130 CN2023077130W WO2024051095A1 WO 2024051095 A1 WO2024051095 A1 WO 2024051095A1 CN 2023077130 W CN2023077130 W CN 2023077130W WO 2024051095 A1 WO2024051095 A1 WO 2024051095A1
Authority
WO
WIPO (PCT)
Prior art keywords
sodium
prussian
positive electrode
transition metal
cathode material
Prior art date
Application number
PCT/CN2023/077130
Other languages
French (fr)
Chinese (zh)
Inventor
谢英豪
李爱霞
余海军
李长东
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司 filed Critical 广东邦普循环科技有限公司
Publication of WO2024051095A1 publication Critical patent/WO2024051095A1/en

Links

Classifications

    • 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
    • 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

  • Embodiments of the present application relate to the field of battery materials, such as a recycling method and application of waste Prussian sodium battery cathode materials.
  • Prussian sodium-like cathode material is a type of sodium-ion battery cathode material with an open frame structure. It is a metal-organic frame structure material. The metal and ferricyanide in its lattice are arranged according to Fe—C ⁇ N—M to form a three-dimensional structure. In the skeleton, Fe and metal M 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 the following advantages: (1) The rigid framework structure and open large pores and sites of the Prussian sodium-like cathode material can ensure that sodium ions with a larger ionic radius can be reversibly deintercalated during the charge and discharge process. It will not change the structure of the cathode material; (2) The Prussian sodium-like cathode material is based on the double-electron redox mechanism, and its theoretical capacity is as high as 170mAh/g; (3) The Prussian sodium-like cathode material has a simple synthesis process, low toxicity and low cost. Suitable for mass production.
  • the embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials.
  • This method precipitates and separates the transition metals in the Prussian sodium cathode materials through acid dissolution and simultaneously destroys the original complexation of each group in the material. , so that [Fe(CN) 6 ] 4- stably exists in the liquid phase, and the liquid phase can further obtain pure sodium ferrocyanide through heating/crystallization or extraction.
  • This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode material.
  • a method for recycling used Prussian sodium battery cathode materials including the following steps:
  • the transition metal elements in the Prussian sodium cathode material can be completely separated and processed through a specific organic acid reaction system, and at the same time, it can also ensure that [Fe(CN) 6 ] 4- will not occur in the material.
  • the cyanide breaks down and reacts with sodium ions to exist stably in the liquid phase.
  • This liquid phase can be obtained through subsequent treatment to pure sodium ferrocyanide, which can be further used to prepare new Prussian sodium cathode materials.
  • the recycling method described in this application has simple operation steps, low requirements for reaction reagents, conditions and equipment, and the purity and yield of the obtained materials are high, making it very suitable for industrial-scale treatment of used batteries.
  • the Prussian-based sodium cathode material includes manganese-based Prussian-based derivative sodium cathode material, nickel-based Prussian-based derivative sodium cathode material, cobalt-based Prussian-based derivative sodium cathode material, copper-based Prussian-based derivative sodium cathode material , at least one of the zinc-based Prussian derivative sodium cathode materials.
  • the organic acid is at least one of oxalic acid and acetic acid.
  • the transition metal precipitate is further prepared by calcination to prepare a transition metal oxide.
  • the transition metal precipitate is manganese metal precipitate, which is calcined at 220-280°C to prepare manganous oxide.
  • the transition metal element in the material is manganese
  • the resulting precipitate is manganese oxalate.
  • This material can be calcined at a specific temperature to directly generate manganous oxide. After further acid dissolution, it can be used to prepare Prussian sodium Synthetic manganese sources are used in cathode materials and other products.
  • Another object of this application is to provide a preparation method of Prussian sodium cathode material, which includes the following steps:
  • step (1) also includes removal of organic acids in the filtrate, and the removal of organic acids is performed by heating or extraction.
  • the filtrate obtained by the recycling method of waste Prussian sodium battery cathode materials described in this application only contains sodium ions, [Fe(CN) 6 ] 4- and organic acids, and organic acids can generally be heated It can be removed by volatilization (applicable to small molecular organic acids that can volatilize at 150°C) or extraction without leaving any residue.
  • the liquid phase can be directly dried by heating or crystallized to obtain high-purity sodium ferrocyanide powder.
  • This product can be further directly mixed with Transition metal salts are directly combined to prepare Prussian sodium cathode materials.
  • the transition metal salt is prepared from transition metal precipitation obtained by the recycling method of used Prussian sodium battery cathode materials described in this application.
  • the organic acid precipitate obtained through the recovery method described in this application can be simply oxidized and converted to obtain pure transition metal salts, and the Prussian sodium cathode material can be obtained by using this salt and the sodium ferrocyanide powder mentioned above. Realize the integrated process of recycling waste lithium-ion battery materials and implement it with high economical and cost-effectiveness.
  • the transition metal salt may also be a new salt.
  • the beneficial effect of the embodiments of the present application is that the embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials.
  • This method precipitates and separates the transition metals in the Prussian sodium battery cathode materials through acid dissolution and simultaneously destroys the materials.
  • the original complexation of each group makes [Fe(CN) 6 ] 4- stably exist in the liquid phase.
  • the liquid phase can be heated/crystallized or extracted to further obtain pure sodium ferrocyanide.
  • This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode material.
  • This application also provides a method for preparing a Prussian sodium cathode material.
  • This method uses the liquid phase obtained by the recovery method described in this application to further purify it to obtain sodium ferrocyanide. This material can be directly transferred to new materials or the results obtained in this application. Transition metal salts obtained by metal precipitation and refining are used to prepare Prussian sodium cathode materials.
  • the preparation method has low raw material cost and is cost-effective to implement.
  • Figure 1 is a scanning electron microscope image of the Prussian sodium cathode material obtained in Example 1 of the present application.
  • Figure 2 is the charge and discharge curve of the Prussian sodium cathode material obtained in Example 1 of the present application.
  • step (2) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • step (2) Calculate the manganese acetate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolve the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • step (2) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
  • Example 1 The only difference between this comparative example and Example 1 is that the molar ratio of Prussian sodium cathode material:oxalic acid in step (2) is 12:1.
  • Example 1 The only difference between this comparative example and Example 1 is that the Prussian sodium normal The electrode material was soaked in the oxalic acid solution for 48 hours. In step (3), the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was measured to be 2.61:1, [Fe(CN) 6 ] 4- The recovery rate is low and cannot meet the recycling requirements.
  • Example 1 The only difference between this comparative example and Example 1 is that the temperature at which the Prussian sodium cathode material separated in step (2) was immersed in the oxalic acid solution was 100°C.
  • step (3) the sodium ions and [ The molar ratio of Fe(CN) 6 ] 4- is 2.92:1, and the recovery rate of [Fe(CN) 6 ] 4- is low and cannot meet the recovery requirements.
  • the products of each example are processed at a rate of 0.1C
  • the first discharge specific capacity reached 147 ⁇ 155mAh/g, which is equivalent to or even slightly better than the 146mAh/g of the product of Comparative Example 1; the capacity retention rate of the products of each embodiment can still reach 94 ⁇ 95% after 150 cycles at 1C rate, which is the same as the 146mAh/g of the product of Comparative Example 1.
  • the products in Comparative Example 1 are the same, indicating that the manganese-based Prussian sodium cathode material recovered and prepared by the recycling method described in this application has excellent electrochemical properties and can completely replace commercial similar products prepared with new materials in the existing market.

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Toxicology (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)
  • Primary Cells (AREA)

Abstract

The present application relates to the field of battery materials. Disclosed are a recycling method for a waste Prussian sodium battery positive electrode material, and a use. The recycling method in the present application comprises the following steps: (1) disassembling a waste sodium ion battery, separating a Prussian sodium positive electrode material on a positive electrode sheet from a current collector, and carrying out washing and sieving; and (2) soaking the separated Prussian sodium positive electrode material in an organic acid solution for 2-24 h at 20-60°C, and filtering to obtain a transition metal precipitate and a filtrate containing sodium ions and [Fe(CN)6]4-, wherein the molar ratio of the separated Prussian sodium positive electrode material to an organic acid in the organic acid solution is (7-10):1. According to the solution, the operation steps are simple, it is not needed to introduce a reagent having high toxicity or causing a violent reaction, and the transition metal ions, sodium ions, and ferrocyanide in the Prussian sodium positive electrode material can be simultaneously recycled and separated. The present application further discloses a method for preparing a Prussian sodium positive electrode material from a product obtained by the recycling method.

Description

一种废旧普鲁士类钠电池正极材料的回收方法及应用A recycling method and application of waste Prussian sodium battery cathode materials 技术领域Technical field
本申请实施例涉及电池材料领域，例如一种废旧普鲁士类钠电池正极材料的回收方法及应用。Embodiments of the present application relate to the field of battery materials, such as a recycling method and application of waste Prussian sodium battery cathode materials.
背景技术Background technique
普鲁士类钠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，它属于金属-有机物框架结构材料，其晶格中金属与铁氰根按Fe—C≡N—M排列形成三维结构骨架，Fe和金属M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。这类材料具有以下优势：(1)普鲁士类钠正极材料的刚性的框架结构和开放性的大孔隙、位点可保证其在充放电过程中离子半径较大的钠离子可实现可逆脱嵌，也不会改变正极材料结构；(2)普鲁士类钠正极材料基于双电子的氧化还原机理，其理论容量高达170mAh/g；(3)普鲁士类钠正极材料合成过程简单，低毒且成本低，适于大规模生产。Prussian sodium-like cathode material is a type of sodium-ion battery cathode material with an open frame structure. It is a metal-organic frame structure material. The metal and ferricyanide in its lattice are arranged according to Fe—C≡N—M to form a three-dimensional structure. In the skeleton, Fe and metal M 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 the following advantages: (1) The rigid framework structure and open large pores and sites of the Prussian sodium-like cathode material can ensure that sodium ions with a larger ionic radius can be reversibly deintercalated during the charge and discharge process. It will not change the structure of the cathode material; (2) The Prussian sodium-like cathode material is based on the double-electron redox mechanism, and its theoretical capacity is as high as 170mAh/g; (3) The Prussian sodium-like cathode material has a simple synthesis process, low toxicity and low cost. Suitable for mass production.
然而，随着普鲁士类正极材料逐渐走向产业化，这种材料使用废弃后如何与传统钠电正极材料一样进行回收及再利用的问题也开始困扰着人们，而该材料中含有的[Fe(CN)6]4-有少量毒性，因此也比传统材料更有处理难度。However, as Prussian cathode materials gradually move towards industrialization, the problem of how to recycle and reuse this material after it is discarded like traditional sodium cathode materials has also begun to trouble people, and the [Fe(CN) contained in this material ) 6 ] 4- Has a small amount of toxicity and is therefore more difficult to handle than traditional materials.
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.
本申请实施例提供了一种废旧普鲁士类钠电池正极材料的回收方法，该方法通过酸溶将普鲁士类钠正极材料中的过渡金属进行沉淀分离并同时破坏材料中各基团原本的络合作用，使得[Fe(CN)6]4-稳定存在在液相，该液相经加热/结晶或萃取可进一步获得纯净的亚铁氰化钠。该方案操作步骤简单，无需引入高毒或反应剧烈的试剂，可同时回收并分离出普鲁士类钠正极材料中的过渡金属离子、钠离子以及亚铁氰根。The embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials. This method precipitates and separates the transition metals in the Prussian sodium cathode materials through acid dissolution and simultaneously destroys the original complexation of each group in the material. , so that [Fe(CN) 6 ] 4- stably exists in the liquid phase, and the liquid phase can further obtain pure sodium ferrocyanide through heating/crystallization or extraction. This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode 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:
一种废旧普鲁士类钠电池正极材料的回收方法，包括以下步骤： A method for recycling used Prussian sodium battery cathode materials, including the following steps:
(1)拆解废旧钠离子电池，将正极极片上的普鲁士类钠正极材料与集流体分离并进行洗涤、过筛处理；(1) Disassemble the used sodium ion battery, separate the Prussian sodium positive electrode material on the positive electrode sheet from the current collector, and wash and screen it;
(2)将分离后的普鲁士类钠正极材料置于有机酸溶液中于20～60℃浸泡2～24h，过滤，得过渡金属沉淀以及含钠离子和[Fe(CN)6]4-的滤液；所述分离后的普鲁士类钠正极材料与有机酸溶液中的有机酸的摩尔比为(7～10)：1。(2) Soak the separated Prussian sodium cathode material in an organic acid solution at 20 to 60°C for 2 to 24 hours, and filter to obtain transition metal precipitates and a filtrate containing sodium ions and [Fe(CN) 6 ] 4- ; The molar ratio of the separated Prussian sodium cathode material to the organic acid in the organic acid solution is (7-10):1.
相关技术中，对传统的钠离子正极材料进行回收时，常采用无机酸或强碱进行过渡元素的分离，然而当回收对象替换成普鲁士类钠正极材料时，由于该材料的络合结构，若要单独分离出过渡金属元素，需考虑材料中[Fe(CN)6]4-的稳定性，若分离条件不当，不仅可能造成[Fe(CN)6]4-的析出，甚至可能发生破氰反应，使得氰根析出产生毒性影响。因此，在本申请技术方案中，通过特定的有机酸反应体系可使得普鲁士类钠正极材料中的过渡金属元素完全分离处理，同时也可保障材料中[Fe(CN)6]4-不会发生破氰反应并和钠离子稳定存在于液相当中，该液相经过后续处理可以获得纯净的亚铁氰化钠，该物质可进一步用于制备新的普鲁士类钠正极材料。同时，经过实验申请人发现，在分离过程中，若有机酸溶液的引入量过多或过少，亦或是浸泡时间/温度条件选择不当，均无法使[Fe(CN)6]4-稳定存留在液相当中或者过渡金属元素完全分离。In related technologies, when recycling traditional sodium ion cathode materials, inorganic acids or strong bases are often used to separate transition elements. However, when the recycling object is replaced with a Prussian sodium cathode material, due to the complex structure of the material, if To separate transition metal elements individually, the stability of [Fe(CN) 6 ] 4- in the material needs to be considered. If the separation conditions are improper, not only may [Fe(CN) 6 ] 4- precipitate, but cyanide breakdown may even occur. The reaction causes cyanide to precipitate and cause toxic effects. Therefore, in the technical solution of this application, the transition metal elements in the Prussian sodium cathode material can be completely separated and processed through a specific organic acid reaction system, and at the same time, it can also ensure that [Fe(CN) 6 ] 4- will not occur in the material. The cyanide breaks down and reacts with sodium ions to exist stably in the liquid phase. This liquid phase can be obtained through subsequent treatment to pure sodium ferrocyanide, which can be further used to prepare new Prussian sodium cathode materials. At the same time, the applicant found through experiments that during the separation process, if the amount of organic acid solution is introduced too much or too little, or the soaking time/temperature conditions are improperly selected, [Fe(CN) 6 ] 4- cannot be stabilized. Remain in the liquid phase or the transition metal elements are completely separated.
本申请所述回收方法操作步骤简单，对于反应的试剂、条件及设备要求低，所得材料的纯度及产率较高，非常适用于工业化废旧电池规模处理。The recycling method described in this application has simple operation steps, low requirements for reaction reagents, conditions and equipment, and the purity and yield of the obtained materials are high, making it very suitable for industrial-scale treatment of used batteries.
优选地，所述普鲁士类钠正极材料包括锰基普鲁士类衍生物钠正极材料、镍基普鲁士类衍生物钠正极材料、钴基普鲁士类衍生物钠正极材料、铜基普鲁士类衍生物钠正极材料、锌基普鲁士类衍生物钠正极材料中的至少一种。Preferably, the Prussian-based sodium cathode material includes manganese-based Prussian-based derivative sodium cathode material, nickel-based Prussian-based derivative sodium cathode material, cobalt-based Prussian-based derivative sodium cathode material, copper-based Prussian-based derivative sodium cathode material , at least one of the zinc-based Prussian derivative sodium cathode materials.
优选地，所述有机酸为草酸、乙酸中的至少一种。Preferably, the organic acid is at least one of oxalic acid and acetic acid.
优选地，所述过渡金属沉淀进一步通过煅烧制备过渡金属氧化物。Preferably, the transition metal precipitate is further prepared by calcination to prepare a transition metal oxide.
更优选地，所述过渡金属沉淀为锰金属沉淀，经220～280℃条件下煅烧制备得到氧化亚锰。More preferably, the transition metal precipitate is manganese metal precipitate, which is calcined at 220-280°C to prepare manganous oxide.
经过有机酸浸泡后，若材料中的过渡金属元素为锰，则生成的沉淀为草酸锰，该物质在特定温度下煅烧可直接生成氧化亚锰，经过进一步酸溶解后可作为制备诸如普鲁士类钠正极材料等产品合成的锰源使用。After soaking with organic acid, if the transition metal element in the material is manganese, the resulting precipitate is manganese oxalate. This material can be calcined at a specific temperature to directly generate manganous oxide. After further acid dissolution, it can be used to prepare Prussian sodium Synthetic manganese sources are used in cathode materials and other products.
本申请的另一目的在于提供一种普鲁士类钠正极材料的制备方法，包括以下步骤： Another object of this application is to provide a preparation method of Prussian sodium cathode material, which includes the following steps:
(1)将本申请所述废旧普鲁士类钠电池正极材料的回收方法所得滤液进行钠离子和[Fe(CN)6]4-浓度的检测，并向滤液中引入钠离子使滤液中钠离子和[Fe(CN)6]4-的摩尔比为(4～6)：1，干燥或结晶处理，得亚铁氰化钠粉末；(1) The filtrate obtained from the recycling method of used Prussian sodium battery cathode materials described in this application is tested for sodium ions and [Fe(CN) 6 ] 4- concentrations, and sodium ions are introduced into the filtrate to make the sodium ions and The molar ratio of [Fe(CN) 6 ] 4- is (4~6):1, and it is dried or crystallized to obtain sodium ferrocyanide powder;
(2)将过渡金属盐与步骤(1)所得亚铁氰化钠粉末混合制备普鲁士类钠正极材料。(2) Mix the transition metal salt with the sodium ferrocyanide powder obtained in step (1) to prepare a Prussian sodium cathode material.
优选地，所述步骤(1)中还包括了滤液中有机酸的去除，所述有机酸的去除采用加热法或萃取法进行。Preferably, step (1) also includes removal of organic acids in the filtrate, and the removal of organic acids is performed by heating or extraction.
本申请所述废旧普鲁士类钠电池正极材料的回收方法所得滤液中由于过渡金属元素的完全分离，仅仅含有钠离子、[Fe(CN)6]4-以及有机酸，而有机酸一般可采用加热挥发(适用于150℃下可挥发的小分子有机酸)或萃取进行去除且不会发生残留。去除有机酸后，根据亚铁氰化钠的理论摩尔比进行适当补钠后，所述液相可直接通过加热干燥或结晶处理获得高纯度的亚铁氰化钠粉末，该产品进一步可直接与过渡金属盐直接化合制备普鲁士类钠正极材料。Due to the complete separation of transition metal elements, the filtrate obtained by the recycling method of waste Prussian sodium battery cathode materials described in this application only contains sodium ions, [Fe(CN) 6 ] 4- and organic acids, and organic acids can generally be heated It can be removed by volatilization (applicable to small molecular organic acids that can volatilize at 150°C) or extraction without leaving any residue. After removing the organic acid and appropriately adding sodium according to the theoretical molar ratio of sodium ferrocyanide, the liquid phase can be directly dried by heating or crystallized to obtain high-purity sodium ferrocyanide powder. This product can be further directly mixed with Transition metal salts are directly combined to prepare Prussian sodium cathode materials.
优选地，所述过渡金属盐由本申请所述废旧普鲁士类钠电池正极材料的回收方法得到的过渡金属沉淀制备得到。Preferably, the transition metal salt is prepared from transition metal precipitation obtained by the recycling method of used Prussian sodium battery cathode materials described in this application.
经过本申请所述回收方法得到的有机酸沉淀可经过简单的氧化及转化即可获得纯净的过渡金属盐，而采用该盐与上文所述亚铁氰化钠粉末进行普鲁士类钠正极材料可实现废旧锂离子电池材料的回收再造一体化工艺流程，实施经济性价比高。此外，需要说明的是，基于实际需要，所述过渡金属盐也可是新盐。The organic acid precipitate obtained through the recovery method described in this application can be simply oxidized and converted to obtain pure transition metal salts, and the Prussian sodium cathode material can be obtained by using this salt and the sodium ferrocyanide powder mentioned above. Realize the integrated process of recycling waste lithium-ion battery materials and implement it with high economical and cost-effectiveness. In addition, it should be noted that based on actual needs, the transition metal salt may also be a new salt.
本申请实施例的有益效果在于，本申请实施例提供了一种废旧普鲁士类钠电池正极材料的回收方法，该方法通过酸溶将普鲁士类钠正极材料中的过渡金属进行沉淀分离并同时破坏材料中各基团原本的络合作用，使得[Fe(CN)6]4-稳定存在在液相，该液相经加热/结晶或萃取可进一步获得纯净的亚铁氰化钠。该方案操作步骤简单，无需引入高毒或反应剧烈的试剂，可同时回收并分离出普鲁士类钠正极材料中的过渡金属离子、钠离子以及亚铁氰根。本申请还提供了一种普鲁士类钠正极材料的制备方法，该方法应用本申请所述回收方法得到的液相进一步纯化得到亚铁氰化钠，该物质可直接与新料或本申请所得过渡金属沉淀提炼得到的过渡金属盐制备普鲁士类钠正极材料，所述制备方法原料成本低廉，实施性价比高。The beneficial effect of the embodiments of the present application is that the embodiments of the present application provide a method for recycling waste Prussian sodium battery cathode materials. This method precipitates and separates the transition metals in the Prussian sodium battery cathode materials through acid dissolution and simultaneously destroys the materials. The original complexation of each group makes [Fe(CN) 6 ] 4- stably exist in the liquid phase. The liquid phase can be heated/crystallized or extracted to further obtain pure sodium ferrocyanide. This solution has simple operation steps and does not require the introduction of highly toxic or violently reactive reagents. It can simultaneously recover and separate transition metal ions, sodium ions and ferrocyanide in the Prussian sodium cathode material. This application also provides a method for preparing a Prussian sodium cathode material. This method uses the liquid phase obtained by the recovery method described in this application to further purify it to obtain sodium ferrocyanide. This material can be directly transferred to new materials or the results obtained in this application. Transition metal salts obtained by metal precipitation and refining are used to prepare Prussian sodium cathode materials. The preparation method has low raw material cost and is cost-effective to implement.
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 after reading and understanding the drawings and detailed description.
附图说明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所得普鲁士类钠正极材料的扫描电镜图。Figure 1 is a scanning electron microscope image of the Prussian sodium cathode material obtained in Example 1 of the present application.
图2为本申请实施例1所得普鲁士类钠正极材料的充放电曲线。Figure 2 is the charge and discharge curve of the Prussian sodium cathode material obtained 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及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 embodiments and comparative examples. The purpose is to understand the content of the present application in detail, but not 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
本申请所述废旧普鲁士类钠电池正极材料的回收方法及应用的一种实施例，包括以下步骤：An embodiment of the recycling method and application of waste Prussian sodium battery cathode materials described in this application includes the following steps:
(1)拆解正极材料为Na2MnFe(CN)6的废旧钠离子电池，将正极极片上的普鲁士类钠正极材料从集流体机械刮落浆料，并进行简单过筛、洗涤处理；(1) Dismantle the used sodium-ion battery whose positive electrode material is Na 2 MnFe(CN) 6 , scrape off the slurry of the Prussian-like sodium positive electrode material on the positive electrode sheet from the current collector machine, and perform simple sieving and washing;
(2)将分离后的普鲁士类钠正极材料按质量预估摩尔量，并按照摩尔比普鲁士类钠正极材料：草酸＝10:1，置于1mol/L草酸溶液中于25℃浸泡12h，期间蓝色的普鲁士类钠正极材料逐渐溶解，并生成白色沉淀，过滤，得草酸锰沉淀以及含钠离子和[Fe(CN)6]4-的滤液；(2) Estimate the molar mass of the separated Prussian sodium cathode material according to the mass, and according to the molar ratio of the Prussian sodium cathode material: oxalic acid = 10:1, place it in a 1 mol/L oxalic acid solution and soak it at 25°C for 12 hours. The blue Prussian sodium cathode material gradually dissolves and forms a white precipitate, which is filtered to obtain manganese oxalate precipitate and a filtrate containing sodium ions and [Fe(CN) 6 ] 4- ;
(3)将所得滤液进行钠离子和[Fe(CN)6]4-浓度的检测，得知滤液中钠离子和[Fe(CN)6]4-的摩尔比为1.87：1，向滤液中加入氯化钠使滤液中钠离子和[Fe(CN)6]4-的摩尔比为4：1，随后将所得液相在120℃、惰性气氛下进行蒸发结晶处理，得亚铁氰化钠粉末；(3) The obtained filtrate was tested for the concentration of sodium ions and [Fe(CN) 6 ] 4- . It was found that the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was 1.87:1. Sodium chloride is added to make the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate 4:1, and then the resulting liquid phase is evaporated and crystallized at 120°C under an inert atmosphere to obtain sodium ferrocyanide. powder;
(4)将步骤(2)所得草酸锰沉淀在250℃、氧气气氛下煅烧6h，得氧化亚锰，随后将氧化亚锰置入1mol/L稀盐酸中溶解，得氯化亚锰溶液；(4) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
(5)将氯化亚锰溶液与柠檬酸钠按摩尔比1:4用去离子水混合，配制Mn2+ 浓度为0.15mol/L的混合液I，随后将步骤(3)所得亚铁氰化钠粉末用水溶解并配制成浓度[Fe(CN)6]4-为0.75mol/L的混合液II，将混合液I和II混合并在65℃下保温12h，得到锰基普鲁士类钠正极材料，将所得产品进行扫描电镜观察，如图1所示，该产品的尺寸约为200～800nm，呈立方体形状。(5) Mix manganous chloride solution and sodium citrate with deionized water at a molar ratio of 1:4 to prepare Mn 2+ Mixed liquid I with a concentration of 0.15 mol/L, and then dissolve the sodium ferrocyanide powder obtained in step (3) with water and prepare a mixed liquid II with a concentration of [Fe(CN) 6 ] 4- of 0.75 mol/L. Mix the mixture I and II and keep it at 65°C for 12 hours to obtain a manganese-based Prussian sodium cathode material. The obtained product is observed under a scanning electron microscope. As shown in Figure 1, the size of the product is about 200~800nm and is in the shape of a cube. .
实施例2Example 2
本申请所述废旧普鲁士类钠电池正极材料的回收方法及应用的一种实施例，包括以下步骤：An embodiment of the recycling method and application of waste Prussian sodium battery cathode materials described in this application includes the following steps:
(1)拆解正极材料为Na2MnFe(CN)6的废旧钠离子电池，将正极极片上的普鲁士类钠正极材料从集流体机械刮落浆料，并进行简单过筛、洗涤处理；(1) Dismantle the used sodium-ion battery whose positive electrode material is Na 2 MnFe(CN) 6 , scrape off the slurry of the Prussian-like sodium positive electrode material on the positive electrode sheet from the current collector machine, and perform simple sieving and washing;
(2)将分离后的普鲁士类钠正极材料按质量预估摩尔量，并按照摩尔比普鲁士类钠正极材料：乙酸＝7:1，置于1mol/L草酸溶液中于60℃浸泡2h，期间蓝色的普鲁士类钠正极材料逐渐溶解，并生成白色沉淀，过滤，得草酸锰沉淀以及含钠离子和[Fe(CN)6]4-的滤液；(2) Estimate the molar mass of the separated Prussian sodium cathode material according to the mass, and use the molar ratio of the Prussian sodium cathode material: acetic acid = 7:1, and place it in a 1 mol/L oxalic acid solution and soak it at 60°C for 2 hours. The blue Prussian sodium cathode material gradually dissolves and forms a white precipitate, which is filtered to obtain manganese oxalate precipitate and a filtrate containing sodium ions and [Fe(CN) 6 ] 4- ;
(3)将所得滤液进行钠离子和[Fe(CN)6]4-浓度的检测，得知滤液中钠离子和[Fe(CN)6]4-的摩尔比为1.74：1，向滤液中加入氯化钠使滤液中钠离子和[Fe(CN)6]4-的摩尔比为4：1，随后将所得液相在120℃、惰性气氛下进行蒸发结晶处理，得亚铁氰化钠粉末；(3) The obtained filtrate was tested for the concentration of sodium ions and [Fe(CN) 6 ] 4- . It was found that the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was 1.74:1. Sodium chloride is added to make the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate 4:1, and then the resulting liquid phase is evaporated and crystallized at 120°C under an inert atmosphere to obtain sodium ferrocyanide. powder;
(4)将步骤(2)所得乙酸锰沉淀在250℃、氧气气氛下煅烧6h，得氧化亚锰，随后将氧化亚锰置入1mol/L稀盐酸中溶解，得氯化亚锰溶液；(4) Calculate the manganese acetate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolve the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
(5)将氯化亚锰溶液与柠檬酸钠按摩尔比1:4用去离子水混合，配制Mn2+浓度为0.15mol/L的混合液I，随后将步骤(3)所得亚铁氰化钠粉末用水溶解并配制成浓度[Fe(CN)6]4-为0.75mol/L的混合液II，将混合液I和II混合并在65℃下保温12h，得到锰基普鲁士类钠正极材料。(5) Mix the manganous chloride solution and sodium citrate in a molar ratio of 1:4 with deionized water to prepare a mixed solution I with a Mn 2+ concentration of 0.15 mol/L, and then add the ferrocyanide obtained in step (3) Dissolve the sodium powder with water and prepare a mixed solution II with a concentration [Fe(CN) 6 ] 4- of 0.75 mol/L. Mix the mixed solutions I and II and keep them at 65°C for 12 hours to obtain a manganese-based Prussian sodium cathode. Material.
实施例3Example 3
本申请所述废旧普鲁士类钠电池正极材料的回收方法及应用的一种实施例，包括以下步骤：An embodiment of the recycling method and application of waste Prussian sodium battery cathode materials described in this application includes the following steps:
(1)拆解正极材料为Na2MnFe(CN)6的废旧钠离子电池，将正极极片上的普鲁士类钠正极材料从集流体机械刮落浆料，并进行简单过筛、洗涤处理； (1) Dismantle the used sodium-ion battery whose positive electrode material is Na 2 MnFe(CN) 6 , scrape off the slurry of the Prussian-like sodium positive electrode material on the positive electrode sheet from the current collector machine, and perform simple sieving and washing;
(2)将分离后的普鲁士类钠正极材料按质量预估摩尔量，并按照摩尔比普鲁士类钠正极材料：草酸＝10:1，置于1mol/L草酸溶液中于20℃浸泡24h，期间蓝色的普鲁士类钠正极材料逐渐溶解，并生成白色沉淀，过滤，得草酸锰沉淀以及含钠离子和[Fe(CN)6]4-的滤液；(2) Estimate the molar mass of the separated Prussian sodium cathode material according to the mass, and according to the molar ratio of the Prussian sodium cathode material: oxalic acid = 10:1, place it in a 1 mol/L oxalic acid solution and soak it at 20°C for 24 hours. The blue Prussian sodium cathode material gradually dissolves and forms a white precipitate, which is filtered to obtain manganese oxalate precipitate and a filtrate containing sodium ions and [Fe(CN) 6 ] 4- ;
(3)将所得滤液进行钠离子和[Fe(CN)6]4-浓度的检测，得知滤液中钠离子和[Fe(CN)6]4-的摩尔比为1.85：1，向滤液中加入氯化钠使滤液中钠离子和[Fe(CN)6]4-的摩尔比为6：1，随后将所得液相在120℃、惰性气氛下进行蒸发结晶处理，得亚铁氰化钠粉末；(3) The obtained filtrate was tested for the concentration of sodium ions and [Fe(CN) 6 ] 4- . It was found that the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was 1.85:1. Sodium chloride is added to make the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate 6:1, and then the resulting liquid phase is evaporated and crystallized at 120°C under an inert atmosphere to obtain sodium ferrocyanide. powder;
(4)将步骤(2)所得草酸锰沉淀在250℃、氧气气氛下煅烧6h，得氧化亚锰，随后将氧化亚锰置入1mol/L稀盐酸中溶解，得氯化亚锰溶液；(4) Calcining the manganese oxalate precipitate obtained in step (2) for 6 hours at 250°C in an oxygen atmosphere to obtain manganous oxide, and then dissolving the manganous oxide in 1 mol/L dilute hydrochloric acid to obtain a manganous chloride solution;
(5)将氯化亚锰溶液与柠檬酸钠按摩尔比1:4用去离子水混合，配制Mn2+浓度为0.15mol/L的混合液I，随后将步骤(3)所得亚铁氰化钠粉末用水溶解并配制成[Fe(CN)6]4-浓度为0.75mol/L的混合液II，将混合液I和II混合并在65℃下保温12h，得到锰基普鲁士类钠正极材料。(5) Mix the manganous chloride solution and sodium citrate in a molar ratio of 1:4 with deionized water to prepare a mixed solution I with a Mn 2+ concentration of 0.15 mol/L, and then add the ferrocyanide obtained in step (3) Dissolve the sodium powder with water and prepare [Fe(CN) 6 ] 4- mixed solution II with a concentration of 0.75 mol/L. Mix the mixed solutions I and II and keep them at 65°C for 12 hours to obtain a manganese-based Prussian sodium cathode. Material.
对比例1Comparative example 1
购置分析级氯化亚锰、柠檬酸钠和亚铁氰化钠，按照摩尔比氯化亚锰：柠檬酸钠＝1:4用去离子水混合，配置Mn2+浓度为0.15mol/L的混合液I，将亚铁氰化钠溶解于去离子水中配置成[Fe(CN)6]4-浓度为0.75mol/L的混合液II，将混合液I和II混合并在65℃下保温12h，得到锰基普鲁士类钠正极材料。Purchase analytical grade manganous chloride, sodium citrate and sodium ferrocyanide, mix them with deionized water according to the molar ratio of manganous chloride: sodium citrate = 1:4, and prepare a Mn 2+ concentration of 0.15mol/L Mixed solution I, dissolve sodium ferrocyanide in deionized water to prepare [Fe(CN) 6 ] 4- mixed solution II with a concentration of 0.75 mol/L, mix mixed solutions I and II and keep them warm at 65°C After 12 hours, the manganese-based Prussian sodium cathode material was obtained.
对比例2Comparative example 2
本对比例与实施例1的差别仅在于，步骤(2)所述普鲁士类钠正极材料：草酸的摩尔比为12:1。The only difference between this comparative example and Example 1 is that the molar ratio of Prussian sodium cathode material:oxalic acid in step (2) is 12:1.
此时，观察到步骤(2)所述草酸溶液中仍然有大量未溶解的普鲁士类钠正极材料，达不到回收要求，说明该所述条件下草酸的添加量不足，难以实现普鲁士类钠正极材料的充分回收。At this time, it was observed that there was still a large amount of undissolved Prussian sodium cathode material in the oxalic acid solution described in step (2), which could not meet the recovery requirements, indicating that the amount of oxalic acid added under the conditions was insufficient and it was difficult to realize the Prussian sodium cathode material. Full recycling of materials.
对比例3Comparative example 3
本对比例与实施例1的差别仅在于，步骤(2)所述分离后的普鲁士类钠正 极材料在草酸溶液中浸泡的时间为48h，步骤(3)中测得滤液中钠离子和[Fe(CN)6]4-的摩尔比为2.61：1，[Fe(CN)6]4-的回收率较低，达不到回收要求。The only difference between this comparative example and Example 1 is that the Prussian sodium normal The electrode material was soaked in the oxalic acid solution for 48 hours. In step (3), the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate was measured to be 2.61:1, [Fe(CN) 6 ] 4- The recovery rate is low and cannot meet the recycling requirements.
经分析，主要是因为当普鲁士类钠正极材料在草酸溶液中浸泡时间过长，溶液中的[Fe(CN)6]4-分解或者重新形成沉淀，导致回收率的降低。After analysis, the main reason is that when the Prussian sodium cathode material is soaked in oxalic acid solution for too long, [Fe(CN) 6 ] 4- in the solution decomposes or re-forms as a precipitate, resulting in a decrease in recovery rate.
对比例4Comparative example 4
本对比例与实施例1的差别仅在于，步骤(2)所述分离后的普鲁士类钠正极材料在草酸溶液中浸泡的温度为100℃，步骤(3)中测得滤液中钠离子和[Fe(CN)6]4-的摩尔比为2.92：1，[Fe(CN)6]4-的回收率较低，达不到回收要求。The only difference between this comparative example and Example 1 is that the temperature at which the Prussian sodium cathode material separated in step (2) was immersed in the oxalic acid solution was 100°C. In step (3), the sodium ions and [ The molar ratio of Fe(CN) 6 ] 4- is 2.92:1, and the recovery rate of [Fe(CN) 6 ] 4- is low and cannot meet the recovery requirements.
经分析，主要是因为普鲁士类钠正极材料在草酸溶液中的浸泡温度过高，溶液中的[Fe(CN)6]4-在酸性和高温条件下不稳定，导致[Fe(CN)6]4-分解。After analysis, the main reason is that the immersion temperature of the Prussian sodium cathode material in the oxalic acid solution is too high, and [Fe(CN) 6 ] 4- in the solution is unstable under acidic and high-temperature conditions, resulting in [Fe(CN) 6 ] 4- Decomposition.
效果例1Effect example 1
为了验证本申请所述回收方法制备得到的锰基普鲁士类钠正极材料的性能，对各材料进行粒径D50的测试，随后将各实施例方法制备的产品作为正极，以金属钠为负极，玻璃纤维为隔膜，六氟磷酸钠的EC/DEC溶液为电解液于手套箱中装配钠离子半电池，并在2～4V的工作电压，不同电流密度下进行充放电测试，同时以商业购置新料制备的对比例1产品作为对照样品并进行相同测试，结果如表1所示，其中实施例1所得产品组装电池测试时的充放电曲线如图2所示。In order to verify the performance of the manganese-based Prussian sodium cathode material prepared by the recycling method described in this application, the particle size D50 of each material was tested, and then the product prepared by the method of each embodiment was used as the cathode, with metallic sodium as the negative electrode, and glass The fiber is used as the separator, and the EC/DEC solution of sodium hexafluorophosphate is used as the electrolyte. A sodium ion half-cell is assembled in a glove box, and charge and discharge tests are conducted at a working voltage of 2 to 4V and different current densities. At the same time, new materials are purchased commercially. The prepared product of Comparative Example 1 was used as a control sample and subjected to the same test. The results are shown in Table 1. The charge and discharge curves of the product obtained in Example 1 when assembled into a battery test are shown in Figure 2.
表1
Table 1
从各实施例和对比例2～4所述回收方法可以看出，本申请所述废旧普鲁士类钠电池正极材料的回收方法可以充分有效地回收电池中的过渡金属离子和[Fe(CN)6]4-并重新制备锰基普鲁士类钠正极材料，而对这些材料的颗粒粒径尺寸与采用新料直接制备的对比例1产品无太大差距，同时，各实施例产品在0.1C倍率下的首次放电比容量达到了147～155mAh/g，与对比例1产品的146mAh/g相当甚至略优；各实施例产品经过1C倍率150次循环后容量保持率依然可达到94～95％，与对比例1产品相同，说明本申请所述回收方法回收制备的锰基普鲁士类钠正极材料电化学性能优异，完全可以代替现有市场采用新料制备的商业同类产品。It can be seen from the recovery methods described in each embodiment and Comparative Examples 2 to 4 that the recovery method of used Prussian sodium battery cathode materials described in this application can fully and effectively recover transition metal ions and [Fe(CN) 6 in the battery. ] 4- And prepare the manganese-based Prussian sodium cathode material again, and the particle size of these materials is not much different from the Comparative Example 1 product directly prepared using new materials. At the same time, the products of each example are processed at a rate of 0.1C The first discharge specific capacity reached 147~155mAh/g, which is equivalent to or even slightly better than the 146mAh/g of the product of Comparative Example 1; the capacity retention rate of the products of each embodiment can still reach 94~95% after 150 cycles at 1C rate, which is the same as the 146mAh/g of the product of Comparative Example 1. The products in Comparative Example 1 are the same, indicating that the manganese-based Prussian sodium cathode material recovered and prepared by the recycling method described in this application has excellent electrochemical properties and can completely replace commercial similar products prepared with new materials in the existing market.
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 (8)

  1. 一种废旧普鲁士类钠电池正极材料的回收方法，其包括以下步骤：A method for recycling used Prussian sodium battery cathode materials, which includes the following steps:
    (1)拆解废旧钠离子电池，将正极极片上的普鲁士类钠正极材料与集流体分离并进行洗涤、过筛处理；(1) Disassemble the used sodium ion battery, separate the Prussian sodium positive electrode material on the positive electrode sheet from the current collector, and wash and screen it;
    (2)将分离后的普鲁士类钠正极材料置于有机酸溶液中于20～60℃浸泡2～24h，过滤，得过渡金属沉淀以及含钠离子和[Fe(CN)6]4-的滤液；所述分离后的普鲁士类钠正极材料与有机酸溶液中的有机酸的摩尔比为(7～10)：1。(2) Soak the separated Prussian sodium cathode material in an organic acid solution at 20 to 60°C for 2 to 24 hours, and filter to obtain transition metal precipitates and a filtrate containing sodium ions and [Fe(CN) 6 ] 4- ; The molar ratio of the separated Prussian sodium cathode material to the organic acid in the organic acid solution is (7-10):1.
  2. 如权利要求1所述废旧普鲁士类钠电池正极材料的回收方法，其中，所述普鲁士类钠正极材料包括锰基普鲁士类衍生物钠正极材料、镍基普鲁士类衍生物钠正极材料、钴基普鲁士类衍生物钠正极材料、铜基普鲁士类衍生物钠正极材料、锌基普鲁士类衍生物钠正极材料中的至少一种。The recycling method of waste Prussian-based sodium battery cathode materials according to claim 1, wherein the Prussian-based sodium cathode materials include manganese-based Prussian-based derivative sodium cathode materials, nickel-based Prussian-based derivative sodium cathode materials, cobalt-based Prussian-based derivative sodium cathode materials At least one of a derivative sodium cathode material, a copper-based Prussian derivative sodium cathode material, and a zinc-based Prussian derivative sodium cathode material.
  3. 如权利要求1所述废旧普鲁士类钠电池正极材料的回收方法，其中，所述有机酸为草酸、乙酸中的至少一种。The method for recycling waste Prussian sodium battery cathode materials according to claim 1, wherein the organic acid is at least one of oxalic acid and acetic acid.
  4. 如权利要求1所述废旧普鲁士类钠电池正极材料的回收方法，其中，所述过渡金属沉淀还通过煅烧制备过渡金属氧化物。The method for recycling waste Prussian sodium battery cathode materials according to claim 1, wherein the transition metal precipitation is further prepared by calcining the transition metal oxide.
  5. 如权利要求4所述废旧普鲁士类钠电池正极材料的回收方法，其中，所述过渡金属沉淀为锰金属沉淀，经220～280℃条件下煅烧制备得到氧化亚锰。The method for recycling waste Prussian sodium battery cathode materials according to claim 4, wherein the transition metal precipitate is manganese metal precipitate, and manganous oxide is prepared by calcining at 220-280°C.
  6. 一种普鲁士类钠正极材料的制备方法，其包括以下步骤：A preparation method of Prussian sodium cathode material, which includes the following steps:
    (1)将权利要求1～5任一项所述废旧普鲁士类钠电池正极材料的回收方法所得滤液进行钠离子和[Fe(CN)6]4-浓度的检测，并向滤液中引入钠离子使滤液中钠离子和[Fe(CN)6]4-的摩尔比为(4～6)：1，干燥或结晶处理，得亚铁氰化钠粉末；(1) The filtrate obtained by the recycling method of used Prussian sodium battery cathode materials according to any one of claims 1 to 5 is subjected to detection of sodium ion and [Fe(CN) 6 ] 4 - concentrations, and sodium ions are introduced into the filtrate Make the molar ratio of sodium ions and [Fe(CN) 6 ] 4- in the filtrate to (4~6):1, dry or crystallize to obtain sodium ferrocyanide powder;
    (2)将过渡金属盐与步骤(1)所得亚铁氰化钠粉末混合制备普鲁士类钠正极材料。(2) Mix the transition metal salt with the sodium ferrocyanide powder obtained in step (1) to prepare a Prussian sodium cathode material.
  7. 如权利要求6所述普鲁士类钠正极材料的制备方法，其中，所述步骤(1)中还包括了滤液中有机酸的去除，所述有机酸的去除采用加热法或萃取法进行。 The preparation method of Prussian sodium cathode material according to claim 6, wherein the step (1) also includes the removal of organic acid in the filtrate, and the removal of the organic acid is carried out by heating method or extraction method.
  8. 如权利要求6所述普鲁士类钠正极材料的制备方法，其中，所述过渡金属盐由本申请所述废旧普鲁士类钠电池正极材料的回收方法得到的过渡金属沉淀制备得到。 The method for preparing a Prussian-based sodium cathode material according to claim 6, wherein the transition metal salt is prepared from transition metal precipitation obtained by the recycling method of used Prussian-based sodium battery cathode materials described in this application.
PCT/CN2023/077130 2022-09-05 2023-02-20 Recycling method for waste prussian sodium battery positive electrode material, and use WO2024051095A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202211087961.1 2022-09-05
CN202211087961.1A CN115472943B (en) 2022-09-05 2022-09-05 Recovery method and application of waste Prussian sodium battery anode material

Publications (1)

Publication Number Publication Date
WO2024051095A1 true WO2024051095A1 (en) 2024-03-14

Family

ID=84369201

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2023/077130 WO2024051095A1 (en) 2022-09-05 2023-02-20 Recycling method for waste prussian sodium battery positive electrode material, and use

Country Status (2)

Country Link
CN (1) CN115472943B (en)
WO (1) WO2024051095A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115472943B (en) * 2022-09-05 2023-12-12 广东邦普循环科技有限公司 Recovery method and application of waste Prussian sodium battery anode material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352448A (en) * 2011-08-05 2012-02-15 南昌大学 Method for recovering rare earth from low-concentration rare earth solution through prussian blue colloidal nanoparticles
JP2014064991A (en) * 2012-09-26 2014-04-17 Sumitomo Osaka Cement Co Ltd Method for treating effluent including cesium
US20160221920A1 (en) * 2013-09-23 2016-08-04 Basf Se Process for the recovery of components forming a metal-organic framework material
KR20180026903A (en) * 2016-09-05 2018-03-14 한국원자력연구원 Method for recovering prussian blue and method for removing cesium from aqueous solution
WO2021168600A1 (en) * 2020-02-24 2021-09-02 辽宁星空钠电电池有限公司 Prussian blue sodium ion battery positive electrode material having low moisture content, preparation method therefor, and sodium ion battery
CN114497793A (en) * 2022-01-25 2022-05-13 宁波大学 Method for realizing rapid stripping of recovered electrode active material by mechanical bending mixed gas tension
CN115472943A (en) * 2022-09-05 2022-12-13 广东邦普循环科技有限公司 Recovery method and application of waste Prussian sodium battery positive electrode material

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101752302B1 (en) * 2015-10-16 2017-07-03 지엠텍(주) Method of recovery prussian blue and apparatus thereof
CN107364875A (en) * 2017-06-22 2017-11-21 全球能源互联网研究院 A kind of method and sodium-ion battery for preparing Prussian blue positive electrode
CN107699692A (en) * 2017-09-18 2018-02-16 北京理工大学 A kind of recovery and the method for regenerating waste used anode material for lithium-ion batteries
CN110474042A (en) * 2018-05-11 2019-11-19 中国科学院物理研究所 A kind of Novel Prussian blue class sode cell positive electrode and application thereof
CN114229875B (en) * 2021-10-26 2024-05-31 广东邦普循环科技有限公司 Comprehensive recovery method of waste sodium ion battery
CN115000561A (en) * 2022-06-28 2022-09-02 上海恩捷新材料科技有限公司 Recycling method of sodium ion battery positive electrode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102352448A (en) * 2011-08-05 2012-02-15 南昌大学 Method for recovering rare earth from low-concentration rare earth solution through prussian blue colloidal nanoparticles
JP2014064991A (en) * 2012-09-26 2014-04-17 Sumitomo Osaka Cement Co Ltd Method for treating effluent including cesium
US20160221920A1 (en) * 2013-09-23 2016-08-04 Basf Se Process for the recovery of components forming a metal-organic framework material
KR20180026903A (en) * 2016-09-05 2018-03-14 한국원자력연구원 Method for recovering prussian blue and method for removing cesium from aqueous solution
WO2021168600A1 (en) * 2020-02-24 2021-09-02 辽宁星空钠电电池有限公司 Prussian blue sodium ion battery positive electrode material having low moisture content, preparation method therefor, and sodium ion battery
CN114497793A (en) * 2022-01-25 2022-05-13 宁波大学 Method for realizing rapid stripping of recovered electrode active material by mechanical bending mixed gas tension
CN115472943A (en) * 2022-09-05 2022-12-13 广东邦普循环科技有限公司 Recovery method and application of waste Prussian sodium battery positive electrode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHEM, SHOUCHUN: "IMPORTANT INORGANIC CHEMICAL REACTIONS), EDITION 3", 30 April 1994, article "[121]CH3COOH", XP009555139 *

Also Published As

Publication number Publication date
CN115472943B (en) 2023-12-12
CN115472943A (en) 2022-12-13

Similar Documents

Publication Publication Date Title
JP4916094B2 (en) Precursor for positive electrode material of lithium ion secondary battery, method for producing the same, and method for producing positive electrode material using the same
CN109999750B (en) Lithium zirconate coated manganese lithium ion sieve and preparation and application thereof
EP4269336A1 (en) Method for recycling lithium iron phosphate waste and use thereof
CN108432031A (en) The LiCoO for including in used Li ion cell2Sour dissolving method
CN111048862B (en) Method for efficiently recovering lithium ion battery anode and cathode materials as supercapacitor electrode materials
WO2023155539A1 (en) Preparation method for sodium ferrovanadium phosphate material and application thereof
WO2024051095A1 (en) Recycling method for waste prussian sodium battery positive electrode material, and use
CN110013822A (en) A kind of method of waste and old lithium ion battery recycling co-production lithium adsorbent
WO2015027826A1 (en) Positive electrode material for lithium-ion battery and method for preparing same
CN108987749A (en) The method of ferric phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore
CN105695751A (en) Purification process of manganese anode slime
WO2023024593A1 (en) Method for recovering mixed waste of lithium nickel cobalt manganate and lithium iron phosphate
CN114644327A (en) Preparation method of iron phosphate and application of iron phosphate
KR101536054B1 (en) Method of recovering lithium from bittern by using electrochemisty process
CN111403842B (en) Recovery method of waste lithium battery anode material, spherical nickel oxide material and application
CN115472948A (en) Method for regenerating sodium-electricity positive electrode material by using waste lithium manganate
WO2024060505A1 (en) Recovery method for prussian positive electrode material and manganese-based prussian white positive electrode material prepared thereby
CN110137460A (en) A kind of hollow V of lithium/sodium ions to potassium ions battery3S4The preparation method of@C nano pipe negative electrode material
CN109231182A (en) The method of ammonium dihydrogen phosphate, the preparation method of iron manganese phosphate for lithium and lithium iron phosphate positive material are prepared by phosphorus ore
CN108529666A (en) Method, product and the application of lithium titanate are prepared by inorganic ti sources
CN103221557B (en) Method for producing nickel-ontaining acidic solution
CN116281917B (en) Battery-grade anhydrous ferric phosphate, preparation method and application thereof, and preparation method of lithium iron phosphate
CN116845408A (en) Method for recycling waste lithium cobaltate battery positive electrode material by using water-based eutectic solvent
CN116553502A (en) Method for effectively recycling anode material of waste lithium iron phosphate battery
Ma et al. Antisolvent crystallization from deep eutectic solvent leachates of LiNi1/3Mn1/3Co1/3O2 for recycling and direct synthesis of battery cathodes

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 23861803

Country of ref document: EP

Kind code of ref document: A1