Resource recycling method and application of spinel type positive electrode material of waste secondary battery
By pretreating and electrochemically reacting the positive electrode materials of waste secondary batteries, spinel oxide materials that can be used for AEMWE anodes were prepared, solving the problems of high recycling energy consumption and expensive catalysts, and achieving efficient hydrogen production and environmentally friendly reuse.
Patent Information
- Application Number
- CN202510909937.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-02
- Publication Date
- 2025-10-17
AI Technical Summary
The existing methods for recycling waste secondary battery positive electrode materials have high energy consumption and low reuse rates. AEMWE anode catalysts are expensive and scarce, resulting in high costs and low efficiency for hydrogen production by electrolysis of water.
By pre-treating the positive electrode material carrier and the negative electrode foil, a secondary battery is assembled using a metal salt solution electrolyte for electrochemical reaction, followed by high-temperature cleaning and stripping to obtain the positive electrode spinel oxide material for the anode of an anion exchange membrane electrolytic cell.
It reduces the cost of AEMWE hydrogen production, improves the anode catalytic activity and hydrogen production efficiency, realizes the resource utilization of waste battery materials, and has good economic and ecological value.
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Figure CN120810048A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical fields of new energy, new materials, secondary batteries and water electrolysis hydrogen production, in particular to a method for recycling and application of waste secondary battery spinel positive electrode material resources. BACKGROUND
[0002] At present, the secondary battery market is huge and has high penetration rate. Due to safety and technical reasons, secondary batteries need to be replaced after a certain period of use, and the increasing harmless treatment of waste secondary batteries and their materials has caused great environmental pressure.
[0003] In the field of water electrolysis hydrogen production, anion exchange membrane electrolysis cell (AEMWE) is one of the most potential technologies for water electrolysis hydrogen production because of its low cost of alkaline electrolysis cell (AWE) and high efficiency of proton exchange membrane electrolysis cell (PEMWE). AEMWE is mainly composed of anion exchange membrane (AEM) and two pieces of catalyst-loaded electrode and gas diffusion layer (Gas diffusion layer), and generally uses pure water or low-concentration alkaline solution as electrolyte. When water is electrolyzed, water is split into H2 and OH - by external power supply. OH - is mass transferred to the anode through AEM. The anode oxygen evolution reaction (OER) of AEMWE involves the transformation of multiple complex intermediates and four-electron-proton coupling, and the kinetic process is slow, which needs to cross the reaction barrier with very high overpotential, directly limiting the hydrogen production efficiency. AEMWE usually uses noble metal-based catalyst (such as IrO2 and RuO2) at the anode, which has the problems of high price and resource scarcity.
[0004] Spinel oxide in waste secondary battery is a candidate catalyst for AEMWE anode, and stress can be built in the spinel oxide during the charging and discharging process of the battery, and the material size is reduced, but the waste secondary battery material recycling method in the prior art mainly adopts fire method, wet method and direct recycling method, wherein, the fire metallurgy and wet metallurgy are widely used in the industrial field, and the technical route is mature, for the fire metallurgy, mainly involving high-temperature process for recycling Co, Ni, Li and other metals, the processing capacity is large, but the selectivity is low, and the energy consumption is large. For wet metallurgy, it uses strong acid, strong base and other solvents to recover the required metal, and the metal recovery rate is high, but the complex process and environmental pollution hinder its application. The direct recycling method repairs the structure of the cathode material, and directly supplements the active material to the cathode material to realize the secondary utilization of the cathode material, but the direct recycling method usually needs to accurately control the chemical reaction conditions such as temperature, pressure, reaction time and the like, which has high technical requirements and increases the operation difficulty, in addition, since the process may involve the use of expensive chemicals and strict process control, which may lead to increased recycling cost and affect economic benefits. It can be seen that the recycling method in the prior art has the problems of large energy consumption and low positive material recycling rate. SUMMARY
[0005] Therefore, it is necessary to provide a waste secondary battery spinel type positive material recycling method. The waste secondary battery spinel type positive material recycling method can reasonably utilize the positive material of the waste secondary battery, can produce good economic and ecological value, can reduce the cost of AEMWE hydrogen production, and can improve the hydrogen production efficiency.
[0006] An embodiment of the present application provides a waste secondary battery spinel type positive material recycling method.
[0007] A waste secondary battery spinel type positive material recycling method, comprising the following steps:
[0008] The positive material carrier and the negative foil material are pretreated respectively;
[0009] The first metal salt is dissolved in the first solvent to obtain a metal salt ion electrolyte;
[0010] The second metal salt is dissolved in the second solvent to obtain a metal salt ion solution, the pretreated positive material carrier is added to the metal salt ion solution, and after sufficient soaking, a positive precursor material with metal salt ions is obtained. The positive precursor material is heat treated to obtain a positive material;
[0011] The negative foil material, the positive material and the metal salt ion electrolyte are assembled to form a secondary battery, and the secondary battery is subjected to electrochemical reaction under a predetermined intensity of current;
[0012] Disassembling the secondary battery to obtain the positive electrode material after electrochemical treatment, using a third solvent to clean the obtained positive electrode material at high temperature, first drying treatment;
[0013] Peeling the positive electrode material to separate the positive electrode material carrier to obtain a positive electrode spinel oxide material, second drying treatment.
[0014] In some embodiments, the positive electrode material carrier is pretreated by one or both of acid-base treatment or heat treatment.
[0015] In some embodiments, the positive electrode material carrier includes one or more of carbon cloth, carbon paper, aluminum foil, and stainless steel mesh.
[0016] In some embodiments, the negative electrode foil material is pretreated by one or more of acid-base treatment, heat treatment, and polishing treatment.
[0017] In some embodiments, the negative electrode foil material includes one or more of Zn foil, Al foil, hard carbon, soft carbon, graphite, graphene, MnO2, and Prussian blue.
[0018] In some embodiments, the first metal salt includes one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, iron perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, iron nitrate, aluminum nitrate, zinc acetate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, iron chloride, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, potassium hydroxide, and sodium hydroxide.
[0019] In some embodiments, the first solvent includes one or more of propylene carbonate, ethylene carbonate, tetrahydrofuran, nitrogen dimethylformamide, and pure water.
[0020] In some embodiments, the concentration of metal ions in the metal salt ion electrolyte is controlled to be 0.1 mol / L to 10 mol / L.
[0021] In some embodiments, the second metal salt includes one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, iron perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, iron nitrate, aluminum nitrate, zinc acetate, cobalt nitrate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, iron chloride, cobalt chloride, lithium carbonate, lithium acetate, zinc acetate, and cobalt acetate.
[0022] In some embodiments, the second solvent includes one or more of ethanol, pure water, acetone, and nitrogen dimethylformamide.
[0023] In some embodiments, the concentration of the metal ions in the metal salt ion solution is 0.1 mol / L to 10 mol / L.
[0024] In some embodiments, when the positive electrode precursor material is subjected to the heat treatment, the heat treatment temperature is 100 ℃ to 600 ℃, the heat treatment time is 0.5 h to 6 h, and the heat treatment times is 1 to 6.
[0025] In some embodiments, the secondary battery comprises one or more of a button cell, a soft-packaged battery, a primary battery, and a jelly-roll battery.
[0026] In some embodiments, the current of the predetermined intensity is controlled to be 1 μA to 10 A.
[0027] In some embodiments, the electrochemical reaction time is 1 h to 24 h.
[0028] In some embodiments, the third solvent used in the high-temperature cleaning comprises one or more of pure water, ethanol, acetone, and n-hexane.
[0029] In some embodiments, the high-temperature cleaning is performed 1 to 10 times.
[0030] In some embodiments, the temperature of the high-temperature cleaning is controlled to be 40 ℃ to 120 ℃.
[0031] In some embodiments, the peeling method used when the positive electrode material is peeled off to separate the positive electrode material carrier to obtain the positive electrode spinel oxide material comprises one or more of ultrasonic peeling, stirring peeling, and differential centrifugation.
[0032] In some embodiments, the peeling time is 1 h to 24 h.
[0033] In some embodiments, the drying method used in the first drying treatment and the second drying treatment, respectively, independently comprises one or more of vacuum drying, high-temperature drying, air-blowing drying, and freeze-drying.
[0034] In some embodiments, the time used in the first drying treatment and the time used in the second drying treatment, respectively, independently is 1 h to 24 h.
[0035] An embodiment of the present application further provides an anion exchange membrane electrolytic cell.
[0036] An anion exchange membrane electrolytic cell comprises an anion exchange membrane, a catalytic electrode and a gas diffusion layer, wherein the anion exchange membrane is prepared by dropping and coating one of carbon paper, carbon cloth, titanium foil, foamed nickel and stainless steel mesh with a positive electrode spinel oxide material obtained by the waste secondary battery spinel positive electrode material resource recycling method in any of the above embodiments and a membrane solution.
[0037] The waste secondary battery spinel positive electrode material resource recycling method can reasonably utilize the positive electrode material of the waste secondary battery, solve the waste battery material recycling problem, produce good economic and ecological value, and the recovered positive electrode spinel oxide material can be used for the metal-based catalyst of the anode of an anion exchange membrane electrolytic cell (AEMWE), which can reduce the cost of the AEMWE and improve the hydrogen production efficiency. Specifically, in the waste secondary battery spinel positive electrode material resource recycling method, a negative electrode foil material, a positive electrode material after heat treatment and a metal salt ion electrolyte are assembled to form a secondary battery, and the secondary battery is subjected to an electrochemical reaction under a predetermined strength of current, so that strain can be generated in the positive electrode material, the size can be reduced, and the recovered positive electrode spinel oxide material can effectively improve the oxygen evolution reaction activity of the anode of the AEMWE. BRIEF DESCRIPTION OF DRAWINGS
[0038] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed in the embodiment description will be briefly introduced. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.
[0039] In order to more completely understand the present application and its beneficial effects, the following will be described with reference to the drawings. In the following description, the same reference numerals represent the same parts.
[0040] Figure 1 The waste secondary battery spinel positive electrode material resource recycling method flowchart of an embodiment of the present application;
[0041] Figure 2 The X-ray diffraction pattern of the positive electrode spinel oxide material described in embodiment 1 of the present application, wherein the abscissa is 2theta and the ordinate is intensity;
[0042] Figure 3 The anion exchange membrane electrolytic cell current density comparison schematic diagram described in embodiment 2 and comparative example 1 of the present application, wherein the ordinate is current density. DETAILED DESCRIPTION
[0043] In order to make the above objectives, characteristics and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application are described in detail below with reference to the drawings. In the following description, a large number of specific details are set forth in order to facilitate a thorough understanding of the present application. However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without departing from the spirit of the present application, so the present application is not limited to the specific embodiments disclosed below.
[0044] In this application, when referring to a numerical interval (i.e. a numerical range), the distribution of the optional numbers in the numerical interval is considered to be continuous and includes both numerical endpoints (i.e. the minimum and maximum values) of the numerical interval and every number between the two numerical endpoints, unless otherwise specified. When a numerical interval refers only to integers within the numerical interval, unless otherwise specified, the two endpoint integers of the numerical range and every integer between the two endpoints are equivalent to directly listing each integer. When multiple numerical ranges are provided to describe a feature or characteristic, these numerical ranges can be combined. In other words, unless otherwise specified, the numerical ranges disclosed in this application should be understood to include any and all sub-ranges encompassed therein. The "numbers" in the numerical interval can be any quantitative value, such as a number, a percentage, a ratio, etc. The "numerical interval" is intended to broadly include quantitative intervals such as percentage intervals, ratio intervals, and value intervals.
[0045] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.
[0046] The embodiment of the present application provides a resource recycling method for waste secondary battery spinel type cathode material, so as to solve at least one of the following problems in the prior art: (1) the traditional technology has the problem of large energy consumption and low recycling rate of the secondary battery cathode material; (2) AEMWE uses noble metal catalyst (such as IrO2 and RuO2) and high-quality anion exchange membrane and its supporting materials, which have the problems of high price and resource scarcity. The resource recycling method for waste secondary battery spinel type cathode material will be described below with reference to the accompanying drawings.
[0047] The resource recycling method for waste secondary battery spinel type cathode material provided by the embodiment of the present application is exemplarily shown in Figure 1 Figure 1 A flowchart of a method for recycling waste secondary battery spinel-type cathode material according to an embodiment of the present application is shown. The method for recycling waste secondary battery spinel-type cathode material can be used for recycling secondary battery cathode material. The spinel-type cathode material obtained by the method for recycling waste secondary battery spinel-type cathode material can be used for an anode of an anion exchange membrane electrolysis cell.
[0048] To more clearly illustrate the structure of the method for recycling waste secondary battery spinel-type cathode material, the method for recycling waste secondary battery spinel-type cathode material will be described below in conjunction with the accompanying drawings.
[0049] It should be noted that, unless otherwise specified, each reaction step can be performed in the order described herein or can not be performed in the order described herein. For example, each reaction step can include other steps therebetween, and the order of the reaction steps can be appropriately changed. This can be determined by a person skilled in the art based on common knowledge and experience. Preferably, the reaction method herein is performed in sequence.
[0050] Exemplarily, a method for recycling waste secondary battery spinel-type cathode material includes the following steps:
[0051] A method for recycling waste secondary battery spinel-type cathode material is shown in Figure 1 and includes the following steps:
[0052] S10, respectively pretreating a cathode material carrier and a negative electrode foil material.
[0053] S20, dissolving a first metal salt in a first solvent to obtain a metal salt ion electrolyte.
[0054] S30, dissolving a second metal salt in a second solvent to obtain a metal salt ion solution, adding the pretreated cathode material carrier to the metal salt ion solution, and obtaining a cathode precursor material with metal salt ions after sufficient soaking. The cathode precursor material is subjected to heat treatment to obtain a cathode material.
[0055] S40, assembling the negative electrode foil material, the cathode material, and the metal salt ion electrolyte to form a secondary battery, and performing electrochemical reaction on the secondary battery under a predetermined intensity of current.
[0056] S50, disassembling the secondary battery to obtain the cathode material after electrochemical treatment, using a third solvent to perform high-temperature cleaning on the obtained cathode material, and performing first drying treatment.
[0057] S60, peeling off the cathode material to separate the cathode material carrier to obtain a cathode spinel oxide material, and performing second drying treatment.
[0058] The present application can solve the problems of the existing hydrogen storage energy technology, such as the limitation of materials, high cost, low catalytic activity of relatively cheap anode materials, and poor stability, and the economic and environmental problems of recycling old materials due to the high replacement rate of secondary batteries.
[0059] In some embodiments, the pretreatment of the positive material carrier includes one or both of an acid-base treatment method or a heat treatment method.
[0060] In some embodiments, the positive material carrier includes one or more of carbon cloth, carbon paper, aluminum foil, and stainless steel mesh.
[0061] In some embodiments, the pretreatment of the negative foil material includes one or more of an acid-base treatment method, a heat treatment method, and a polishing treatment method.
[0062] In some embodiments, the acid-base treatment method includes acid treatment and / or base treatment, wherein the acid treatment includes one or more of hydrochloric acid, nitric acid, and sulfuric acid, and the concentration of the acid is 1 mol / L to 10 mol / L. The base treatment includes one or more of potassium hydroxide and sodium hydroxide, and the concentration of the base is 1 mol / L to 10 mol / L.
[0063] In some embodiments, the heat treatment for the pretreatment of the positive material carrier and / or the pretreatment of the negative foil material has a temperature of 100 ℃ to 600 ℃, a time of 0.5 h to 6 h, and a number of 1 to 6.
[0064] In some embodiments, the polishing treatment method for the pretreatment of the negative foil material includes plasma polishing, sandpaper polishing, and polishing.
[0065] In some embodiments, the negative foil material includes one or more of Zn foil, Al foil, hard carbon, soft carbon, graphite, graphene, MnO2, and Prussian blue.
[0066] In some embodiments, the first metal salt includes one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, iron perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, iron nitrate, aluminum nitrate, zinc acetate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, iron chloride, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, potassium hydroxide, and sodium hydroxide.
[0067] In some embodiments, the first solvent includes one or more of propylene carbonate, ethylene carbonate, tetrahydrofuran, dimethylformamide, and pure water.
[0068] In some embodiments, the concentration of metal ions in the metal salt ionic electrolyte is controlled to be between 0.1 mol / L and 10 mol / L.
[0069] In some embodiments, the second metal salt comprises one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, iron perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, iron nitrate, aluminum nitrate, zinc acetate, cobalt nitrate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, iron chloride, cobalt chloride, lithium carbonate, lithium acetate, zinc acetate, cobalt acetate.
[0070] In some embodiments, the second solvent comprises one or more of ethanol, pure water, acetone, and dimethylformamide.
[0071] In some embodiments, the concentration of metal ions in the metal salt ionic solution is between 0.1 mol / L and 10 mol / L. The concentration of metal ions in the metal salt ionic solution includes, but is not limited to, 0.1 mol / L, 0.5 mol / L, 1 mol / L, 2 mol / L, 3 mol / L, 5 mol / L, 6 mol / L, 8 mol / L, 10 mol / L, or a range between any two of the foregoing.
[0072] In some embodiments, when the positive electrode precursor material is subjected to heat treatment, the heat treatment temperature is between 100 °C and 600 °C, the heat treatment time is between 0.5 h and 6 h, and the heat treatment number is between 1 and 6. The heat treatment temperature includes, but is not limited to, 100 °C, 200 °C, 300 °C, 400 °C, 500 °C, 600 °C, or a range between any two of the foregoing. The heat treatment time includes, but is not limited to, 0.5 h, 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, or a range between any two of the foregoing. The heat treatment number includes, but is not limited to, 1, 2, 3, 4, 5, 6, or a range between any two of the foregoing.
[0073] In some embodiments, the secondary battery comprises one or more of a button cell, a soft-pack battery, a primary battery, and a jelly-roll battery.
[0074] In some embodiments, the predetermined intensity of the current is controlled to be between 1 μA and 10 A. The predetermined intensity of the current includes, but is not limited to, 1 μA, 100 μA, 500 μA, 1 mA, 10 mA, 100 mA, 1 A, or a range between any two of the foregoing.
[0075] In some embodiments, the electrochemical reaction time is 1 h to 24 h. The electrochemical reaction time includes, but is not limited to, 1 h, 2 h, 5 h, 10 h, 15 h, 20 h, 24 h, or a range between any two of the foregoing.
[0076] In some embodiments, the third solvent in the high-temperature cleaning includes one or more of pure water, ethanol, acetone, and n-hexane.
[0077] In some embodiments, the high-temperature cleaning is performed 1 to 10 times. The number of times of the high-temperature cleaning includes, but is not limited to, 1 time, 2 times, 3 times, 4 times, 5 times, 6 times, 8 times, 10 times, or a range between any two of the foregoing.
[0078] In some embodiments, the high-temperature cleaning is performed at a temperature of 40 ℃ to 120 ℃. The temperature of the high-temperature cleaning includes, but is not limited to, 40 ℃, 50 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, or a range between any two of the foregoing.
[0079] In some embodiments, the peeling method for peeling the positive electrode material to separate the positive electrode material carrier to obtain the positive electrode spinel oxide material includes one or more of ultrasonic peeling, stirring peeling, and differential centrifugation.
[0080] In some embodiments, the peeling time is 1 h to 24 h. The peeling time includes, but is not limited to, 1 h, 2 h, 5 h, 10 h, 15 h, 20 h, 24 h, or a range between any two of the foregoing.
[0081] In some embodiments, the drying method during the first drying process and the second drying process, respectively, independently includes one or more of vacuum drying, high-temperature drying, air blowing drying, and freeze drying.
[0082] In some embodiments, the time during the first drying process and the time during the second drying process, respectively, independently is 1 h to 24 h. The time during the first drying process includes, but is not limited to, 1 h, 2 h, 5 h, 10 h, 15 h, 20 h, 24 h, or a range between any two of the foregoing. The time during the second drying process includes, but is not limited to, 1 h, 2 h, 5 h, 10 h, 15 h, 20 h, 24 h, or a range between any two of the foregoing.
[0083] An embodiment of the present application further provides an anion exchange membrane electrolytic cell.
[0084] An anion exchange membrane electrolytic cell comprises an anion exchange membrane, a catalytic electrode and a gas diffusion layer, wherein the anion exchange membrane is prepared by dropping and coating one of carbon paper, carbon cloth, titanium foil, foamed nickel and stainless steel mesh with a positive electrode spinel oxide material obtained by the method for recycling waste secondary battery spinel positive electrode material and a membrane solution.
[0085] The method for recycling waste secondary battery spinel positive electrode material can reasonably recycle the positive electrode material of the secondary battery, and the recycled material can be used in a new anion exchange membrane electrolytic cell, thereby generating good economic and ecological values. Using the common secondary battery positive electrode as the anode of the electrolytic cell can achieve high hydrogen production efficiency and reduce the cost of the electrolytic cell, and protect the ecological environment. The present application can solve the problems of the existing water electrolysis hydrogen storage technology, such as the limitation of materials, high cost, low catalytic activity of relatively inexpensive anode materials, poor stability and the like, and the economic and environmental problems of recycling old materials due to the high replacement rate of secondary batteries.
[0086] Embodiment 1
[0087] A method for recycling waste secondary battery spinel positive electrode material, characterized in that it comprises the following steps:
[0088] (1) A method for recycling waste secondary battery spinel positive electrode material, comprising the following steps:
[0089] S11, the positive electrode material carrier and the negative electrode foil material are pretreated with potassium hydroxide with a concentration of 1 mol / L. The positive electrode material carrier includes carbon cloth. The negative electrode foil material includes Zn foil.
[0090] S21, dissolve the first metal salt zinc perchlorate in the first solvent zinc perchlorate to obtain a metal salt ion electrolyte. The concentration of metal ions in the metal salt ion electrolyte is controlled to be 1 mol / L.
[0091] S31, dissolve the second metal salt zinc perchlorate in the second solvent acetone to obtain a metal salt ion solution. The concentration of metal ions in the metal salt ion solution is 1 mol / L. The pretreated positive electrode material carrier is added to the metal salt ion solution, and after sufficient soaking, a positive electrode precursor material with metal salt ions is obtained. The positive electrode precursor material is heat treated, the heat treatment temperature is 250 DEG C, the heat treatment time is 2 h, and the heat treatment number is 1 time, to obtain a positive electrode material.
[0092] S41, the negative electrode foil material, the positive electrode material after heat treatment and the metal salt ion electrolyte are assembled to form a button cell, and the button cell is subjected to electrochemical reaction at a current of 1 A for 2 h.
[0093] S51, the secondary battery is disassembled to obtain the positive electrode material after electrochemical treatment, the obtained positive electrode material is subjected to high-temperature cleaning using a third solvent, acetone, at a temperature of 100 DEG C, and high-temperature drying for 2 h.
[0094] S61, the positive electrode material is stripped by stirring for 2 h to separate the positive electrode material carrier to obtain the positive electrode spinel oxide material, and the positive electrode spinel oxide material is subjected to high-temperature drying for 2 h. Referring to Figure 2 , Figure 2 X-ray diffraction pattern of the positive electrode spinel oxide material obtained in Example 1.
[0095] Example 2
[0096] This example provides an anion exchange membrane electrolytic cell.
[0097] An anion exchange membrane electrolytic cell, comprising an anion exchange membrane, a catalytic electrode and a gas diffusion layer, wherein the anion exchange membrane is prepared by dropping and coating a carbon paper after mixing an active material and a membrane solution.
[0098] Comparative Example 1
[0099] This comparative example provides an anion exchange membrane electrolytic cell.
[0100] This comparative example 1 is basically the same as Example 1, except that the positive electrode spinel oxide material prepared in Example 1 is not contained in Comparative Example 1.
[0101] An anion exchange membrane electrolytic cell, comprising an anion exchange membrane, a catalytic electrode and a gas diffusion layer, wherein the anion exchange membrane is prepared by dropping and coating a carbon paper after mixing a membrane solution.
[0102] The anion exchange membrane electrolytic cells of Example 2 and Comparative Example 1 are subjected to current density test. The test results are shown in Figure 3 .
[0103] According to the d-band center theory, different d-band centers can affect the efficiency of the oxygen evolution reaction in the anode. The d-band center of the material can be effectively adjusted by the coordination of ions and the stress effect, thereby improving the efficiency of the oxygen evolution reaction in the anode. The anion exchange membrane electrolysis cell (stress sample) in Example 2 has high cell efficiency, and can reach a current density of 250 mA / cm -2 at a overpotential of 1.9 V in 1 mol of KOH electrolyte. Compared with Comparative Example 1 (non-stress sample) which does not contain the recovered active material, the current density at the same potential is more than 2 times higher.
[0104] In the above examples, the description of each example focuses on different aspects. For parts not described in detail in a certain example, please refer to the relevant description of other examples.
[0105] Each technical feature of the above-described examples can be combined arbitrarily. In order to make the description concise, not all possible combinations of the technical features in the above examples are described. However, as long as the combination of the technical features does not exist contradictory, it should be considered as the scope of the present disclosure.
[0106] The above-described examples only express several embodiments of the present application, and the description is more specific and detailed. However, it should not be construed as limiting the scope of the present patent. It should be noted that for ordinary skilled persons in the art, without departing from the concept of the present application, a number of modifications and improvements can be made, which are within the scope of the present application. Therefore, the scope of the present patent should be subject to the appended claims.
Claims
1. A method for recycling spinel cathode materials of waste secondary batteries, characterized in that: The steps include: Pre-treating the positive electrode material carrier and the negative electrode foil material respectively; dissolving a first metal salt in a first solvent to obtain a metal salt ion electrolyte; dissolving a second metal salt in a second solvent to obtain a metal salt ion solution, adding the pretreated positive electrode material carrier to the metal salt ion solution, fully infiltrating the positive electrode precursor material to obtain a positive electrode precursor material with metal salt ions, and heat-treating the positive electrode precursor material to obtain a positive electrode material; Assembling the negative electrode foil material, the positive electrode material and the metal salt ion electrolyte to form a secondary battery, and subjecting the secondary battery to an electrochemical reaction at a current of a predetermined intensity; disassembling the secondary battery to obtain the electrochemically treated positive electrode material, performing a high-temperature cleaning on the obtained positive electrode material using a third solvent, and performing a first drying process; The positive electrode material is peeled off to separate the positive electrode material carrier to obtain a positive electrode spinel oxide material, and a second drying process is performed.
2. The method for recycling waste secondary battery spinel positive electrode materials according to claim 1, characterized in that: The method for recycling waste secondary battery spinel positive electrode materials further satisfies at least one of the following conditions: (1) Pre-treating the positive electrode material carrier includes one or both of acid-base treatment and heat treatment; (2) The positive electrode material carrier includes one or more of carbon cloth, carbon paper, aluminum foil and stainless steel mesh; (3) Pre-treating the negative electrode foil material, including one or more of an acid-base treatment method, a heat treatment method, and a polishing treatment method; (4) The negative electrode foil material includes one or more of Zn foil, Al foil, hard carbon, soft carbon, graphite, graphene, MnO2 and Prussian blue.
3. The method for recycling spinel cathode materials of waste secondary batteries according to claim 1, characterized in that: The method for recycling waste secondary battery spinel positive electrode materials further satisfies at least one of the following conditions: (1) the first metal salt comprises one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, ferric perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, ferric nitrate, aluminum nitrate, zinc acetate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, ferric chloride, lithium tetrafluoroborate, lithium hexafluoroarsenate, lithium hexafluorophosphate, potassium hydroxide, and sodium hydroxide; (2) The first solvent includes one or more of propylene carbonate, ethylene carbonate, tetrahydrofuran, dimethylformamide and pure water; (3) Controlling the metal ion concentration in the metal salt ion electrolyte to be 0.1 mol / L~10 mol / L.
4. The method for recycling spinel cathode materials of waste secondary batteries according to claim 1, characterized in that: The method for recycling waste secondary battery spinel positive electrode materials further satisfies at least one of the following conditions: (1) The second metal salt includes one or more of zinc perchlorate, aluminum perchlorate, lithium perchlorate, ferric perchlorate, sodium perchlorate, zinc sulfate, aluminum sulfate, sodium thiosulfate, zinc nitrate, ferric nitrate, aluminum nitrate, zinc acetate, cobalt nitrate, aluminum acetate, zinc chloride, aluminum chloride, sodium chloride, ferric chloride, cobalt chloride, lithium carbonate, lithium acetate, zinc acetate, and cobalt acetate; (2) The second solvent includes one or more of ethanol, pure water, acetone and dimethylformamide; (3) The metal ion concentration in the metal salt ion solution is 0.1 mol / L~10 mol / L.
5. The method for recycling waste secondary battery spinel cathode materials according to any one of claims 1 to 4, characterized in that: When the positive electrode precursor material is heat-treated, the heat treatment temperature is 100° C. to 600° C., the heat treatment time is 0.5 h to 6 h, and the heat treatment times are 1 to 6 times.
6. The method for recycling waste secondary battery spinel cathode materials according to any one of claims 1 to 4, characterized in that: The method for recycling waste secondary battery spinel oxide positive electrode materials further satisfies at least one of the following conditions: (1) The secondary battery includes one or more of a button battery, a soft pack battery, a primary battery, and a wound battery; (2) The current of the predetermined intensity is controlled to be 1 μA~10 A; (3) The electrochemical reaction time is 1 h~24 h.
7. The method for recycling waste secondary battery spinel cathode materials for use as anodes in anion exchange membrane electrolytic cells according to any one of claims 1 to 4, characterized in that: The method for recycling waste secondary battery spinel-type positive electrode materials for use as anion exchange membrane electrolytic cell anodes further satisfies at least one of the following conditions: (1) The third solvent during the high-temperature cleaning includes one or more of pure water, ethanol, acetone, and n-hexane; (2) The number of high-temperature cleaning is 1 to 10 times; (3) The temperature of the high-temperature cleaning is controlled to be 40°C~120°C.
8. The method for recycling waste secondary battery spinel cathode materials for use as anodes in anion exchange membrane electrolytic cells according to any one of claims 1 to 4, characterized in that: The method for recycling waste secondary battery spinel-type positive electrode materials for use as anion exchange membrane electrolytic cell anodes further satisfies at least one of the following conditions: (1) The stripping method for stripping the positive electrode material to separate the positive electrode material carrier to obtain the positive electrode spinel oxide material includes one or more of ultrasonic stripping, stirring stripping and differential centrifugation; (2) The peeling time is 1 h~24 h.
9. The method for recycling waste secondary battery spinel cathode materials for use as anodes in anion exchange membrane electrolytic cells according to any one of claims 1 to 4, characterized in that: (1) The drying methods in the first drying process and the second drying process independently include one or more of vacuum drying, high temperature drying, forced air drying, and freeze drying; (2) The time for the first drying treatment and the time for the second drying treatment are independently 1 h to 24 h.
10. An anion exchange membrane electrolytic cell, characterized in that: It includes an anion exchange membrane, a catalytic electrode and a gas diffusion layer, wherein the anion exchange membrane is prepared by mixing the spinel positive electrode material obtained by the resource recovery method of waste secondary battery spinel positive electrode material according to any one of claims 1 to 9 with a membrane solution and then drop-coating it on one of carbon paper, carbon cloth, titanium foil, foam nickel and stainless steel mesh.