CN116200600B - Method for recycling battery positive electrode material - Google Patents
Method for recycling battery positive electrode material Download PDFInfo
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- CN116200600B CN116200600B CN202211733150.4A CN202211733150A CN116200600B CN 116200600 B CN116200600 B CN 116200600B CN 202211733150 A CN202211733150 A CN 202211733150A CN 116200600 B CN116200600 B CN 116200600B
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
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- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B1/00—Preliminary treatment of ores or scrap
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- C22B1/06—Sulfating roasting
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- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/14—Agglomerating; Briquetting; Binding; Granulating
- C22B1/24—Binding; Briquetting ; Granulating
- C22B1/2406—Binding; Briquetting ; Granulating pelletizing
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
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- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- C22B47/00—Obtaining manganese
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
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Abstract
本发明提供了一种电池正极材料的回收方法，包括以下步骤：将电池正极材料经过前处理得到正极粉和集流体粗料；将集流体粗料与水混合反应后，过滤，得到第一滤渣和第一滤液；将第一滤渣与水和淀粉混合搅洗，固液分离得到集流体精料与淀粉水；将淀粉水与正极粉、硫酸钠混合焙烧，焙烧后加水混合并过滤，得到第二滤渣和第二滤液；将第二滤液与第一滤液进行碳化处理得到第一金属材料的碳酸盐沉淀。该方法通过第一段回收实现了对第一金属材料的优先提取，在二段回收时通过焙烧还原法对剩余的第一金属材料进行再次提取，通过二段回收正极材料的方法能提高金属材料的总回收率。
The present invention provides a method for recovering positive electrode materials of a battery, comprising the following steps: pre-treating the positive electrode materials of the battery to obtain positive electrode powder and a rough current collector; mixing the rough current collector with water for reaction, filtering to obtain a first filter residue and a first filtrate; mixing the first filter residue with water and starch, stirring and washing, and performing solid-liquid separation to obtain a fine current collector and starch water; mixing the starch water with positive electrode powder and sodium sulfate and roasting, adding water after roasting, mixing and filtering to obtain a second filter residue and a second filtrate; and carbonizing the second filtrate and the first filtrate to obtain a carbonate precipitate of a first metal material. The method realizes the preferential extraction of the first metal material through the first stage recovery, and the remaining first metal material is extracted again by the roasting reduction method during the second stage recovery. The method of recovering the positive electrode material through the second stage can improve the total recovery rate of the metal material.
Description
Technical Field
The invention relates to the technical field of waste battery recovery, in particular to a method for recovering a battery anode material.
Background
With the development of new energy industry, the yield and sales of lithium ion batteries increase exponentially. According to the service life of the power battery of 5-8 years, the power battery is about to retire from service on a large scale, so that battery recycling is becoming an industry hotspot. The battery recovery mainly comprises material recovery, gradient utilization, pretreatment, recycling recovery and the like, and in the recycling recovery, along with the rising of lithium salt price, the lithium recovery gradually becomes an important research direction of the recycling recovery of the battery.
At present, the recycling recovery process of the positive plate mainly comprises the following steps of crushing and sorting the positive plate, carrying out wet extraction on lithium, namely crushing and screening the positive plate to obtain positive plate powder and coarse aluminum, treating the positive plate powder through wet processes such as leaching and extraction, so as to realize recycling recovery of metals such as nickel, cobalt, manganese, lithium and the like, leaching the metals such as nickel, cobalt, manganese, lithium and the like doped or wrapped in the coarse aluminum by adopting processes such as acid washing, salt washing and the like, and leaching slag is high-purity aluminum slag. The positive plate is formed by bonding positive electrode powder and an aluminum current collector through a binder, so that the process can lead to the positive electrode powder to contain a large amount of organic matters, reduce the recovery rate of metals such as nickel, cobalt, manganese, lithium and the like, leach impurities such as aluminum and the like in coarse aluminum materials, lead to the impurity of the leached metals such as nickel, cobalt, manganese, lithium and the like, and also lead to the residue of the metals such as nickel, cobalt, manganese, lithium and the like in leached residues, thereby directly improving the complexity of the back-end process and influencing the recovery rate of metals. 2. Breaking, sorting and roasting to obtain positive plate, breaking, sieving and roasting the positive plate, and wet extracting lithium from the roasted material. The process can lead to unfired treatment of part of the crushed and screened positive plate, wherein metals such as nickel, cobalt, manganese, lithium and the like are not recovered, so that the metal recovery rate is reduced.
Disclosure of Invention
Aiming at least one part of problems of incomplete metal recovery, lower metal recovery and the like in the traditional battery anode material recovery process, the invention provides a method for recovering a battery anode material.
According to an aspect of the present invention, there is provided a method for recovering a positive electrode material of a battery, comprising the steps of:
pretreating a battery anode material to obtain anode powder and current collector coarse materials;
Mixing the current collector coarse material with water for reaction, and filtering to obtain first filter residue and first filtrate;
mixing and stirring the first filter residue, water and starch, and carrying out solid-liquid separation to obtain a current collector concentrate and starch water;
mixing and roasting the starch water, the positive electrode powder and sulfate, adding water after roasting, mixing and filtering to obtain second filter residues and second filtrate;
and carbonizing the second filtrate and the first filtrate to obtain carbonate precipitation of the first metal material.
According to the technical scheme, firstly, coarse current collector materials are mixed with water to react, the coarse current collector materials are filtered to obtain first filter residues and first filtrate, part of first metal materials enter the first filtrate along with liquid phase, separation of the coarse current collector materials and recovery of part of the first metal materials are achieved, at the moment, part of the first metal materials still exist in the first filter residues, then starch and water are mixed and stirred with the first filter residues, solid-liquid separation is conducted to obtain fine current collector materials and starch water, the fine current collector materials and the positive electrode active materials are basically and completely separated, the obtained fine current collector materials are high-purity current collector materials, recovery of the current collector materials is achieved, other positive electrode active materials enter the starch water, then starch water and positive electrode powder are mixed and roasted with sulfate, water is added to mix and filtered to obtain second filter residues and second filtrate, the first metal materials in the starch water and the positive electrode powder enter the second filtrate, and finally the first metal materials in the first filtrate and the second filtrate are extracted, and recovery of the first metal materials is achieved. Through the mode, the first section of the current collector coarse material is recycled to obtain the first filtrate, and the second section of the current collector coarse material is recycled to obtain the second filtrate, so that the total recovery rate of the first metal material can be improved, the synchronous recovery of the current collector material can be realized, and the recycling recovery effect of the battery anode material is improved.
In a further preferred embodiment, after obtaining the first filter residue and the first filtrate, the method comprises in particular the following steps:
screening the first filter residues to obtain slag and powder;
Mixing and stirring the slag, water and starch, and carrying out solid-liquid separation to obtain a current collector concentrate and starch water;
mixing and roasting the starch water, the powder and the positive electrode powder with sulfate, adding water after roasting, mixing and filtering to obtain second filter residues and second filtrate;
and carbonizing the second filtrate and the first filtrate to obtain carbonate precipitation of the first metal material.
In the scheme, the first filter residue is firstly screened to obtain slag and powder, so that part of the anode active material coated or mixed in the first filter residue enters the powder, and the current collector material enters the slag. Therefore, the separation of the positive electrode active material and the current collector material is further realized, and the purification and recovery of the positive electrode active material and the current collector material are facilitated, so that the recovery rate of the positive electrode material of the battery is improved.
In a further preferred scheme, the pretreatment specifically comprises the following steps of carrying out multistage crushing and screening on the battery anode material, collecting fine materials after crushing and screening of each stage to obtain anode powder, and collecting coarse materials after crushing and screening of the last stage to obtain the current collector coarse materials;
preferably, the particle size of the current collector coarse material is not more than 3mm, and the particle size of the positive electrode powder is less than 200 meshes;
preferably, the particle size of the current collector coarse material is not more than 0.85mm, and the particle size of the positive electrode powder is less than 300 meshes;
preferably, the current collector content in the positive electrode powder is 2% or less.
Because the binder exists between the current collector and the positive electrode powder, the structure of the binder cannot be completely destroyed by simple mechanical crushing, so that a large amount of positive electrode powder remains on the current collector coarse material, the current collector generally has better ductility, is easy to knead into an irregular shape in the crushing process, and can wrap and mix with the positive electrode powder, so that the current collector and the positive electrode powder are not easy to separate. In this scheme, after the battery positive electrode material is multistage broken, sieves, the collector coarse material is located on the sieve because of reasons such as granule is great, broken degree is not enough, and the positive electrode powder is located under the sieve because the particle diameter is less, utilizes particle diameter difference and multistage broken, sieves the cooperation, has realized separating positive electrode powder step by step from the collector coarse material, has improved the separation effect of collector coarse material and positive electrode powder.
In a further preferred embodiment, the current collector raw material is mixed with water and sodium sulfate and ball-milled before the first filter residue and the first filtrate are obtained;
preferably, the ball milling specifically comprises the following steps of mixing the current collector coarse material with sodium sulfate according to a mass ratio of 1:3-1:8, mixing with water according to a solid-liquid mass ratio of 1:5-1:15, ball milling, and filtering to obtain first filter residues and first filtrate.
In this scheme, make the thick material of mass flow body and water and sodium sulfate intensive mixing contact through ball-milling mode, be favorable to promoting first metal material and leach from the thick material of mass flow body, can promote the thick material of mass flow body and carry lithium effect preferentially to improve the rate of recovery of first metal material.
In a further preferred scheme, the first filter residue is subjected to wet screening to obtain slag and powder;
preferably, the wet screening specifically comprises the following steps of mixing the first filter residue with water according to a mass ratio of 1:10-1:20, screening by adopting 200-300 meshes, wherein the oversize material is slag, and the undersize material is powder.
The wet screening method is adopted in the scheme, so that the separation cost of the anode active material and the current collector material is low, the separation process is quick and convenient, and fine powder in the current collector material can be effectively separated.
In a further preferred scheme, the mixing and stirring and washing mode of the slag, water and starch specifically comprises the steps of preparing the slag, water and starch into slurry according to a mass ratio of 1:5-1:15, adding starch into the slurry according to a mass ratio of 1:3-1:8 for stirring and washing, and carrying out solid-liquid separation to obtain the current collector concentrate and starch water.
In this scheme, utilize the adsorptivity of starch to stir out the positive pole active material in the slag charge, can not lead to the fact the destruction to the mass flow body material in the slag charge, guaranteed the chemical nature of slag charge, and reduced its impurity content, simultaneously, through extracting the positive pole active material in the slag charge, can improve the total rate of recovery of positive pole active material.
In a further preferred embodiment, the method comprises the following treatment steps before the second filter residue and the second filtrate are obtained:
Mixing the starch water with the powder, the positive electrode powder and the sulfate, roasting to obtain a roasting material, adding water into the roasting material, mixing, and performing ball milling to obtain a ball milling mixed solution;
and (3) adjusting the pH value of the ball milling mixed solution to a first pH value, and filtering to obtain second filter residues and second filtrate.
In the scheme, starch water, powder, positive electrode powder and sulfate are mixed and roasted, starch has good carbon reducibility after roasting, and is favorable for subsequent leaching of the first metal material, and after adding water into the roasted material and mixing, the pH is adjusted to enable the first metal material to be dissolved into the second filtrate, so that the starch water and the first metal material contained in the powder are further extracted, and meanwhile, the first metal material contained in the positive electrode powder is extracted, so that the recovery rate of the positive electrode material of the battery is improved.
In a further preferred embodiment, after mixing the starch water with the powder, the positive electrode powder, and sulfate, the method further comprises:
and (3) pelletizing the mixture to obtain anode pellets, and roasting the anode pellets.
In the scheme, the mixture of the starch water, the powder, the positive electrode powder and the sulfate is palletized and then baked, so that the baking effect can be improved, the starch water generated after washing the starch can be used as an additive for palletizing and granulating the powder, the anode pellets can be formed by pelleting, the cost can be reduced, the starch has good carbon reducibility after palletizing and baking, a reducing agent is provided for the subsequent steps, and the cost can be further reduced.
In a further preferred scheme, the pelletizing specifically comprises the following steps of mixing the positive electrode powder and the powder according to a mass ratio of 3:1-5:1 to obtain a first mixture, adding sulfate according to a mass ratio of 1:3-1:7 to obtain a second mixture, adding starch water according to a mass ratio of 2:1-8:1 to uniformly mix and slurry, and pelletizing the materials to obtain positive electrode pellets;
Preferably, the roasting temperature is 400-500 ℃, the roasting time is 4-6 hours, and the mass ratio of the roasting material to water is 1:5-1:15;
preferably, the first pH value is 6.5 to 7.5.
Under the condition of the selected pelletization and roasting in the scheme, the recovery rate of the battery anode material is further improved.
In a further preferred embodiment, the carbonization treatment specifically includes introducing a reducing gas into the first filtrate and the second filtrate to obtain carbonate precipitation of the first metal material. The first metal materials in the first filtrate and the second filtrate can be precipitated by the method so as to be convenient for recycling.
In a further preferred scheme, the method further comprises the step of carrying out wet impurity removal on the second filter residues to obtain a second metal material.
Since the positive electrode active material generally includes various metal materials, a part of the positive electrode active material may enter the second filter residue during the process of treating the starch water and the positive electrode powder. Thus, the second metal material contained in the second filter residue can be extracted by reprocessing the second filter residue, thereby sufficiently recovering the metal material in the battery positive electrode material.
In a further preferred embodiment, the battery is a lithium ion battery, the first metal material is a lithium material, the second metal material is other metal materials except lithium in the battery positive electrode material, and preferably, the second metal material is at least one of nickel, cobalt and manganese.
According to the scheme, the lithium in the lithium ion battery can be preferentially extracted and recovered, the total recovery rate of the lithium can be improved through a two-stage recovery mode, and metals such as aluminum current collector, nickel, cobalt and manganese in the lithium ion battery can be recovered, so that the purpose of fully recovering the anode material of the lithium battery is achieved.
In summary, the recovery method of the battery anode material provided by the invention has at least the following beneficial effects:
1. According to the invention, the first metal material such as lithium is extracted by first-stage recovery, the first metal material left in the current collector coarse material is extracted again by a roasting reduction method in second-stage recovery, the problem of metal material loss caused by impurity carrying can be effectively avoided by a method of recovering the first metal material in multiple stages and steps, the impurity content is reduced, the first metal material in the positive electrode powder is extracted while the second-stage recovery is carried out, the recovery rate of the metal material in the positive electrode powder is improved, and the total recovery rate of the metal material is improved by respectively recovering the current collector coarse material and the positive electrode material in the positive electrode powder.
2. The water and sodium sulfate are added into the current collector coarse material to effectively extract the first metal material, and the auxiliary materials of the method have small influence on the quality of the product, so that the method is beneficial to effectively recycling the full-component metal material of the positive electrode powder in the subsequent step.
3. The powder is recovered by utilizing the adsorptivity of the starch, the powder is agglomerated by the pelletization, the extraction effect of the first metal material can be effectively improved by the pelletization, the added reagent is ensured to be fully contacted with the pelletization material, meanwhile, the skeleton carbon structure of the calcined starch has good carbon reducibility, a reducing agent is provided for the subsequent steps, and the cost can be further reduced.
4. And mixing and calcining the positive electrode powder and part of metal materials in the starch water through a lithium extraction process combining sulfate and organic carbon starch roasting, wherein the structure is changed and the positive electrode powder and part of metal materials are converted into leachable metal materials, so that the recovery rate of the first metal materials is improved.
5. And the second filter residue is treated in a wet method, so that the second metal material in the second filter residue can be recovered, and the full-component recovery of the battery anode material is realized.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
Fig. 1 is a flowchart of a method for recycling a battery positive electrode material according to an embodiment of the present invention.
Detailed Description
It should be understood that the specific embodiments presented herein are for purposes of explanation to those skilled in the art and are intended to be illustrative only and not limiting.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It will be apparent, however, to one skilled in the art that the specific details need not be employed to practice the present invention. In other instances, well-known steps or operations have not been described in detail in order to avoid obscuring the invention.
Referring to fig. 1, the recovery method of the battery positive electrode material provided by the embodiment of the invention comprises the following steps of carrying out pretreatment on the battery positive electrode material to obtain positive electrode powder and current collector coarse material, mixing the current collector coarse material with water for reaction, filtering to obtain first filter residue and first filtrate, mixing and stirring and washing the first filter residue with water and starch, carrying out solid-liquid separation to obtain current collector fine material and starch water, mixing and roasting the starch water with the positive electrode powder and sulfate, adding water for mixing and filtering to obtain second filter residue and second filtrate, and carrying out carbonization treatment on the second filtrate and the first filtrate to obtain carbonate precipitate of the first metal material.
The battery is a lithium ion battery with a positive electrode part made of a positive electrode material containing lithium and a negative electrode part made of a graphite component, and can be a ternary lithium battery, a lithium cobaltate battery, a lithium manganate battery and the like. The battery anode material is an anode plate, the current collector is an aluminum material, the first metal material is a lithium material, and the second metal material is other metal materials except lithium in the battery anode material, such as nickel, cobalt, manganese and the like. In the embodiment of the invention, the positive plate is subjected to two-stage lithium extraction, sodium sulfate can be added in the first stage lithium extraction, the aluminum in the crude aluminum material reacts with water to release heat to improve the extraction rate of lithium, al has reducibility, a part of lithium with stronger activity can be separated and extracted under the action of the additive sodium sulfate, the recovery rate of the lithium in the stage is more than 50 percent, and in the second stage lithium extraction, the pellet material, sulfate and organic carbon are controlled to reduce and bake to extract lithium, and the recovery rate of the total lithium in the two stages can reach more than 98 percent. By the sectional lithium extraction mode, separation and extraction of aluminum and other metal materials such as nickel, cobalt, manganese and the like are synchronously realized, and energy consumption can be reduced.
In some alternative embodiments, the method of recycling battery positive electrode material includes the steps of:
S1, disassembling the waste lithium ion battery to obtain the positive plate.
S2, pretreating a battery anode material, namely an anode plate, to obtain anode powder and a current collector coarse material, namely coarse aluminum material.
Optionally, the step S2 specifically comprises the steps of carrying out primary crushing on the positive plate, keeping the particle size of the crushed material within 3mm, screening by using a 200-mesh screen, wherein the undersize material is first-stage positive electrode powder, the oversize material is second-stage crushed, keeping the particle size of the crushed material within 2mm, screening by using a 200-mesh screen, wherein the undersize material is second-stage positive electrode powder, the oversize material is third-stage crushed, keeping the crushed material within 1mm, screening by using a 300-mesh screen, the undersize material is third-stage positive electrode powder, the oversize material is fourth-stage positive electrode powder, the crushed material is kept within 0.85mm, screening by using a 300-mesh screen, the undersize material is fourth-stage positive electrode powder, the oversize material is coarse aluminum, mixing the first-stage positive electrode powder, the second-stage positive electrode powder, the third-stage positive electrode powder and the fourth-stage positive electrode powder, and finally obtaining the positive electrode powder, and controlling the content of the positive electrode powder to be below 2%.
It is understood that in other alternative embodiments, the number of crushing and sorting operations of the positive electrode sheet may not be limited to four, and for example, five crushing operations, six crushing operations, seven crushing operations, etc. may be performed.
S3, mixing and reacting the current collector coarse material, namely coarse aluminum material, with water and sodium sulfate, and filtering to obtain first filter residue and first filtrate.
Optionally, the step S3 specifically comprises the following steps of mixing coarse aluminum materials and sodium sulfate in a mass ratio of 1:3-1:8, mixing and ball milling the mixture and water in a solid-liquid mass ratio of 1:5-1:15, and filtering and separating to obtain first filter residues, namely ball milling residues, and first filtrate, namely first-stage lithium extraction liquid.
Optionally, an auxiliary medium is added during the ball milling process, wherein the auxiliary medium may be zirconia beads, steel balls, etc. For example, zirconia beads with diameters of 5mm,10mm and 15mm respectively with different sizes can be added in the ball milling process, so that the ball milling lithium extraction effect can be improved. It will be appreciated that in alternative embodiments, the zirconia beads are not limited to the above examples, e.g., the zirconia beads may also be 20mm,25mm,30mm, etc. in diameter.
S4, screening the first filter residue, namely ball mill residue, to obtain slag and powder.
Optionally, the step S4 specifically comprises the steps of mixing the first filter residue and water according to a mass ratio of 1:10-1:20, and carrying out wet screening by adopting 200-300 meshes, wherein the oversize material is slag, namely aluminum slag, and the undersize material is powder, namely nickel-cobalt-manganese powder.
S5, mixing and stirring the slag, namely aluminum slag, water and starch, and carrying out solid-liquid separation to obtain a current collector concentrate, namely high-purity aluminum slag and starch water.
Optionally, the step S5 specifically comprises the steps of preparing slag and water into slurry according to a mass ratio of 1:5-1:15, adding starch according to a mass ratio of 1:3-1:8 into the slurry for stirring and washing, and carrying out solid-liquid separation to obtain a current collector concentrate, namely high-purity aluminum slag and starch water. The total content of nickel, cobalt, manganese and lithium in the aluminum slag can be controlled within 1-2% by stirring and washing the aluminum slag with starch, the purity of the recovered aluminum is greatly improved, acid is not used in the process of recovering the aluminum, and the reduction of the recovery value of the aluminum and pollution caused by acid washing can be avoided.
S6, mixing starch water with powder, namely nickel cobalt manganese powder, anode powder and sulfate, and then pelletizing the mixture to obtain anode pellets.
Optionally, the step S6 specifically comprises the steps of mixing the positive electrode powder and the powder according to a mass ratio of 3:1-5:1 to obtain a first mixture, adding sulfate according to a mass ratio of 1:3-1:7 to obtain a second mixture, adding starch water according to a mass ratio of 2:1-8:1 to obtain a second mixture, uniformly mixing, pulping, and controlling the rotation speed at 300-500 r/min to pellet the materials by using a pelletizer with an inclination angle of 15-45 degrees, wherein the pelletization grain size is kept within 6mm, so as to obtain the positive electrode pellets.
Optionally, the sulfate is at least one of sodium sulfate, ammonium sulfate, potassium sulfate and calcium sulfate.
And S7, roasting the anode pellets to obtain roasting materials, adding water into the roasting materials for mixing, and performing ball milling to obtain ball milling mixed liquid.
Optionally, the roasting temperature is 400-500 ℃, the roasting time is 4-6 hours, the mass ratio of the roasting material to the water is 1:5-1:15, for example, the roasting temperature can be 400 ℃,410 ℃,420 ℃,430 ℃,440 ℃,450 ℃,460 ℃,470 ℃,480 ℃,490 ℃,500 ℃ or any value between 400-500 ℃, the roasting time can be 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours, 5 hours, 5.2 hours, 5.6 hours, 5.8 hours, 6 hours or any value between 4-6 hours, and the mass ratio of the roasting material to the water can be 1:5,1:6,1:7,1:8,1:9,1:10,1:11,1:12,1:13,1:14,1:15 or any value between 1:5-1:15.
Optionally, an auxiliary medium is added during the ball milling process, wherein the auxiliary medium may be zirconia beads, steel balls, etc. For example, zirconia beads with diameters of 5mm,10mm and 15mm respectively with different sizes can be added in the ball milling process, so that the ball milling lithium extraction effect can be improved. It will be appreciated that in alternative embodiments, the zirconia beads are not limited to the above examples, e.g., the zirconia beads may also be 20mm,25mm,30mm, etc. in diameter.
And S8, adjusting the pH value of the ball milling mixed solution to a first pH value, and filtering to obtain second filter residues and second filtrate.
Optionally, the first pH is 6.5 to 7.5. For example, the first pH may be 6.5,6.6,6.7,6.8,6.9,7.0,7.1,7.2,7.3,7.4,7.5 or any value between 6.5 and 7.5.
Optionally, the step S8 specifically comprises the steps of adding sulfuric acid into the ball milling mixed solution to adjust the pH to 6.5-7.5, and then filtering and separating to obtain second filter residues, namely ball milling residues, and second filtrate, namely lithium-rich solution.
And S9, carbonizing the second filtrate, namely the lithium-rich liquid, and the first filtrate, namely the lithium-extracted liquid, to obtain carbonate precipitation of the first metal material.
Alternatively, the second filtrate and the first filtrate may be carbonized to obtain the first metal material, respectively, or the second filtrate and the first filtrate may be mixed and carbonized to obtain the first metal material.
Optionally, the step S9 specifically comprises the steps of introducing a reducing gas such as carbon dioxide into the mixed solution of the first filtrate and the second filtrate to obtain a carbonate precipitate of the first metal material such as lithium carbonate precipitate, washing, dehydrating, removing impurities, separating and drying the lithium carbonate precipitate to obtain lithium carbonate, wherein the recovery rate of lithium reaches more than 98% in the whole process.
S10, performing wet impurity removal on the second filter residues, namely ball mill residues, to obtain a second metal material.
Optionally, the second metal material is at least one of nickel, cobalt, and manganese. For example, the second metal material may be a nickel material, a cobalt material, a manganese material, a mixture of nickel and cobalt, a mixture of nickel and manganese, a mixture of cobalt and manganese, or a mixture of nickel and cobalt and manganese.
Optionally, the step S10 specifically comprises the following steps of carrying out wet impurity removal and purification on the second filter residue to obtain nickel cobalt manganese salt.
The present invention will be further described in detail with reference to the following specific embodiments for the purpose of making the objects, technical solutions and advantageous effects of the present invention more apparent, but the described specific embodiments are only for explaining the present invention and are not intended to limit the present invention.
Example 1
The method for recycling the battery cathode material in the embodiment comprises the following steps:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
Mixing coarse aluminum material and sodium sulfate according to a mass ratio of 1:5, mixing the mixture and water according to a solid-liquid mass ratio of 1:10, adding three zirconia beads with diameters of 5mm, 10mm and 15mm according to a number ratio of 3:4:3, performing ball milling, and separating ball milling liquid through suction filtration to obtain ball milling slag and lithium extraction liquid;
mixing ball-milling slag after ball milling with water according to a mass ratio of 1:15, and carrying out wet screening by using a 300-mesh screen to obtain aluminum slag and nickel cobalt manganese powder;
Proportioning aluminum slag and water into slurry according to the mass ratio of 1:10, adding starch according to the mass ratio of 1:5, stirring and washing, and carrying out solid-liquid separation to obtain high-purity aluminum slag and starch water;
Mixing the anode powder and the nickel-cobalt-manganese powder according to a mass ratio of 4:1 to obtain a first mixture, adding sodium sulfate according to a mass ratio of 1:5 of the first mixture to sodium sulfate to obtain a second mixture, adding starch water according to a mass ratio of 5:1 of the second mixture to starch water to uniformly mix, pulping, regulating an inclination angle of a pelletizer to 30 degrees, regulating a rotating speed to 400r/min, pelletizing the materials by the pelletizer, and controlling the particle size to be within 6mm to obtain anode pellets;
Roasting the anode pellets, controlling the roasting temperature at 450 ℃ for 6 hours, mixing the roasting material with water according to the mass ratio of 1:10, and then adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm, respectively according to the mass ratio of 3:4:3, and performing secondary ball milling;
adding sulfuric acid into the secondary ball milling mixed solution to adjust the pH value to 6.8, and filtering and separating to obtain secondary ball milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, performing carbonization treatment and purification to obtain lithium carbonate precipitate, and washing, dehydrating, removing impurities, separating and drying the lithium carbonate precipitate to obtain a lithium carbonate product;
And leaching the secondary ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Example 2
The method for recycling the battery cathode material in the embodiment comprises the following steps:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
mixing the coarse aluminum material and sodium sulfate according to the mass ratio of 1:3, mixing the mixture and water according to the solid-liquid mass ratio of 1:5, adding three zirconia beads with the diameters of 5mm, 10mm and 15mm according to the number ratio of 3:4:3 for ball milling, and separating ball milling liquid through suction filtration to obtain ball milling slag and lithium extraction liquid;
mixing ball-milling slag after ball milling with water according to a mass ratio of 1:10, and carrying out wet screening by using a 200-mesh screen to obtain aluminum slag and nickel cobalt manganese powder;
Proportioning aluminum slag and water into slurry according to the mass ratio of 1:5, adding starch according to the mass ratio of 1:3, stirring and washing, and carrying out solid-liquid separation to obtain high-purity aluminum slag and starch water;
mixing the anode powder and the nickel-cobalt-manganese powder according to a mass ratio of 3:1 to obtain a first mixture, adding ammonium sulfate according to a mass ratio of 1:3 of the first mixture to the ammonium sulfate to obtain a second mixture, adding starch water according to a mass ratio of 3:1 of the second mixture to the starch water to uniformly mix, pulping, regulating an inclination angle of a pelletizer to 15 degrees, regulating a rotating speed to 300r/min, pelletizing the materials by the pelletizer, and controlling the particle size to be within 6mm to obtain anode pellets;
Roasting the anode pellets, controlling the roasting temperature at 400 ℃ for 4 hours, mixing the roasting material with water according to the mass ratio of 1:5, and then adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm, respectively according to the mass ratio of 3:4:3 for secondary ball milling;
Adding sulfuric acid into the secondary ball milling mixed solution to adjust the pH to 7.2, and filtering and separating to obtain secondary ball milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, performing carbonization treatment and purification to obtain lithium carbonate precipitate, and washing, dehydrating, removing impurities, separating and drying the lithium carbonate precipitate to obtain a lithium carbonate product;
And leaching the secondary ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Example 3
The method for recycling the battery cathode material in the embodiment comprises the following steps:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
Mixing the coarse aluminum material and sodium sulfate according to the mass ratio of 1:8, mixing the mixture and water according to the solid-liquid mass ratio of 1:15, adding three zirconia beads with the diameters of 5mm, 10mm and 15mm according to the number ratio of 3:4:3 for ball milling, and separating ball milling liquid through suction filtration to obtain ball milling slag and lithium extraction liquid;
Mixing ball-milling slag after ball milling with water according to a mass ratio of 1:20, and carrying out wet screening by using a 300-mesh screen to obtain aluminum slag and nickel cobalt manganese powder;
Proportioning aluminum slag and water into slurry according to the mass ratio of 1:15, adding starch according to the mass ratio of 1:8, stirring and washing, and carrying out solid-liquid separation to obtain high-purity aluminum slag and starch water;
Mixing the anode powder and the nickel-cobalt-manganese powder according to a mass ratio of 5:1 to obtain a first mixture, adding sodium sulfate according to a mass ratio of 1:7 of the first mixture to sodium sulfate to obtain a second mixture, adding starch water according to a mass ratio of 8:1 of the second mixture to starch water to uniformly mix, pulping, regulating an inclination angle of a pelletizer to 45 degrees, regulating a rotating speed to 500r/min, pelletizing the materials by the pelletizer, and controlling the particle size to be within 6mm to obtain anode pellets;
Roasting the anode pellets, controlling the roasting temperature at 500 ℃ for 4 hours, mixing the roasting material with water according to the mass ratio of 1:15, and then adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm, respectively according to the mass ratio of 3:4:3 for secondary ball milling;
adding sulfuric acid into the secondary ball milling mixed solution to adjust the pH value to 6.5, and filtering and separating to obtain secondary ball milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, performing carbonization treatment and purification to obtain lithium carbonate precipitate, and washing, dehydrating, removing impurities, separating and drying the lithium carbonate precipitate to obtain a lithium carbonate product;
And leaching the secondary ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Example 4
The method for recycling the battery cathode material in the embodiment comprises the following steps:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
Mixing coarse aluminum material and sodium sulfate according to a mass ratio of 1:5, mixing the mixture and water according to a solid-liquid mass ratio of 1:10, adding three zirconia beads with diameters of 5mm, 10mm and 15mm according to a number ratio of 3:4:3, performing ball milling, and separating ball milling liquid through suction filtration to obtain ball milling slag and lithium extraction liquid;
Mixing ball-milling slag after ball milling with water according to a mass ratio of 1:20, and carrying out wet screening by using a 300-mesh screen to obtain aluminum slag and nickel cobalt manganese powder;
Proportioning aluminum slag and water into slurry according to the mass ratio of 1:10, adding starch according to the mass ratio of 1:5, stirring and washing, and carrying out solid-liquid separation to obtain high-purity aluminum slag and starch water;
Mixing the anode powder and the nickel-cobalt-manganese powder according to a mass ratio of 4:1 to obtain a first mixture, adding sodium sulfate according to a mass ratio of 1:5 of the first mixture to sodium sulfate to obtain a second mixture, adding starch water according to a mass ratio of 5:1 of the second mixture to starch water to uniformly mix, and pulping;
Roasting the slurry, controlling the roasting temperature at 450 ℃ for 6 hours, mixing the roasting material with water according to the mass ratio of 1:10, and adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm respectively, according to the mass ratio of 3:4:3 for secondary ball milling;
Adding sulfuric acid into the secondary ball milling mixed solution to adjust the pH value to 7.5, and filtering and separating to obtain secondary ball milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, performing carbonization treatment and purification to obtain lithium carbonate precipitate, and washing, dehydrating, removing impurities, separating and drying the lithium carbonate precipitate to obtain a lithium carbonate product;
And leaching the secondary ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Comparative example 1
This comparative example provides a method for recovering a battery positive electrode material, which, unlike example 1, does not use two-stage lithium extraction and does not use wet ball milling for preferential lithium extraction, and specifically comprises the steps of:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
mixing the crude aluminum material and water according to the mass ratio of 1:10 to form slurry, adding starch according to the mass ratio of 1:5 of starch to aluminum slag, stirring and washing, and carrying out solid-liquid separation to obtain aluminum slag and starch water;
Mixing the anode powder and sodium sulfate according to the mass ratio of 1:5 to obtain a mixture, adding starch water according to the mass ratio of 5:1 to uniformly mix, regulating the slurry, regulating the inclination angle of a pelletizer to 45 degrees, regulating the rotating speed to 500r/min, pelletizing the materials by the pelletizer, and controlling the particle size to be within 6mm to obtain anode pellets;
Roasting the anode pellets, controlling the roasting temperature at 450 ℃ for 6 hours, mixing the roasting material with water according to the mass ratio of 1:10, and then adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm, respectively according to the mass ratio of 3:4:3 for ball milling;
adding sulfuric acid into the ball-milling mixed solution to adjust the pH to 6.8, and then filtering and separating to obtain ball-milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, carbonizing, purifying to obtain lithium carbonate precipitate, washing, dehydrating, removing impurities, separating, and oven drying to obtain lithium carbonate product.
And leaching ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Comparative example 2
This comparative example provides a method for recovering a battery positive electrode material, which is different from example 1 in that the comparative example does not use two-stage lithium extraction, does not use starch to stir aluminum slag and is used for pelletizing, but adopts acid-washed coarse aluminum material, and specifically comprises the following steps:
disassembling the waste ternary lithium ion battery to obtain a positive plate and a negative plate in the battery;
The positive plate is subjected to multistage crushing and sorting to obtain positive powder and crude aluminum, the particle size of the crude aluminum is controlled to be more than 300 meshes, and the aluminum content of the positive powder is controlled to be less than 2%;
proportioning the crude aluminum material and water into slurry according to the mass ratio of 1:10, and then adding sulfuric acid to adjust the pH value to 0.5-1 to obtain aluminum slag and slag washing water;
Mixing the anode powder and sodium sulfate according to the mass ratio of 1:5 to obtain a mixture, uniformly mixing the mixture and slag washing water according to the mass ratio of 5:1, regulating the inclination angle of a pelletizer to 45 degrees, regulating the rotating speed to 500r/min, pelletizing the materials by the pelletizer, and controlling the particle size within 6mm to obtain anode pellets;
Roasting the anode pellets, controlling the roasting temperature at 450 ℃ for 6 hours, mixing the roasting material with water according to the mass ratio of 1:10, and then adding three zirconia beads with different sizes, wherein the diameters of the zirconia beads are 5mm, 10mm and 15mm, respectively according to the mass ratio of 3:4:3 for ball milling;
adding sulfuric acid into the ball-milling mixed solution to adjust the pH to 6.8, and then filtering and separating to obtain ball-milling slag and lithium-rich solution;
Mixing the lithium-rich liquid with the lithium-extracting liquid, introducing reducing gas such as carbon dioxide, carbonizing, purifying to obtain lithium carbonate precipitate, washing, dehydrating, removing impurities, separating, and oven drying to obtain lithium carbonate product.
And leaching ball-milling slag under normal pressure, and then carrying out pressure leaching, wherein the pressure leaching pressure is controlled to be 1.2-1.6 MPa, and the temperature is controlled to be 176-180 ℃ to obtain nickel cobalt manganese salt and leaching slag.
Table 1 shows the recovery rates of lithium and the contents of main content and impurity (%)
Where lithium recovery = weight of lithium in lithium carbonate product/weight of lithium in positive electrode sheet material.
As can be seen from table 1, the lithium recovery rate in example 1 was 98.3%, the lithium recovery rate in example 2 was 96.8%, the lithium recovery rate in example 3 was 96.2%, the lithium recovery rate in example 4 was 95.6%, the lithium recovery rate in comparative example 1 was 92%, the lithium recovery rate in comparative example 2 was 85%, the lithium recovery rate in comparative example was significantly higher than that in comparative example, and the Li 2CO3 content in example was higher and the Na, fe and other impurities content were lower. According to the embodiment of the invention, the lithium recovery rate is effectively improved and the impurity content in the lithium carbonate product is reduced by two-stage lithium extraction, starch stirring and washing and pelleting.
Table 2 shows the above examples and comparative examples the main content and impurity content (%)
| Al | Ni | Co | Mn | Li | Li total ratio | |
| Coarse aluminum material | 72.38 | 8.70 | 6.95 | 3.03 | 6.89 | 20.57 |
Wherein Li total ratio = weight of lithium in the coarse aluminum material/weight of lithium in the positive electrode sheet raw material.
Table 3 shows the main content and impurity content (%)
From tables 2 and 3, it can be seen that the Al content of the aluminum slag obtained in example 1 was 99.6%, the Al content of the aluminum slag obtained in example 2 was 99.5%, the Al content of the aluminum slag obtained in example 3 was 99.4%, the Al content of the aluminum slag obtained in example 4 was 99.5%, the Al content of the aluminum slag obtained in comparative example 1 was 99.3%, the Al content of the aluminum slag obtained in comparative example 2 was 99.1%, and the Al content of the coarse aluminum material was 72.38%. In comparison, the Al content of the aluminum slag in the examples and the comparative examples is improved as compared with the Al content of the crude aluminum material, and the Al content of the aluminum slag in the examples is higher than that of the aluminum slag in the comparative examples, and the contents of impurities such as Ni, co, etc. of the aluminum slag in the examples are lower. According to the embodiment of the invention, through two-stage lithium extraction and starch stirring and washing, agglomerating and pelletizing, the separation effect of the metal active material and the aluminum foil is comprehensively improved, and the metal active material is obtained through extraction and the high-purity aluminum material is obtained through separation.
Table 4 shows the above examples and comparative examples Main content and impurity content (%)
As can be seen from Table 4, the Ni 2SO4 content of the cobalt nickel salt product obtained in example 1 was 99.6%, the Ni 2SO4 content of the cobalt nickel salt product obtained in example 2 was 99.5%, the Ni 2SO4 content of the cobalt nickel salt product obtained in example 3 was 99.6%, the Ni 2SO4 content of the cobalt nickel salt product obtained in example 4 was 99.6%, the Ni 2SO4 content of the cobalt nickel salt product obtained in comparative example 1 was 99.2%, the Ni 2SO4 content of the cobalt nickel salt product obtained in comparative example 2 was 98.9%, the Ni 2SO4 content of the cobalt nickel salt product obtained in comparative example was higher than the Ni 2SO4 content of the cobalt nickel salt product obtained in comparative example, the CoSO 3995 content of the cobalt nickel salt product obtained in example 1 was 99.5%, the CoSO 4 content of the cobalt nickel salt product obtained in example 2 was 99.6%, the CoSO 2 content of the cobalt salt product obtained in example 3 was 99.5%, the cobalt 35% of the cobalt 35, the CoSO 96 content of the cobalt salt product obtained in example 4 was 58.9%, the cobalt 35% of the cobalt salt product obtained in comparative example 1, and the cobalt SO 99.35 content of the cobalt 35% of the cobalt salt product obtained in comparative example 1 was obtained, the content of impurities such as Fe is lower. According to the embodiment of the invention, through two-stage lithium extraction and starch stirring and washing, agglomerating and pelletizing, the purity of the nickel-cobalt sulfate salt is improved, and the impurity content in the nickel-cobalt sulfate salt is effectively reduced.
The technical features described above may be arbitrarily combined. Although not all possible combinations of features are described, any combination of features should be considered to be covered by the description provided that such combinations are not inconsistent.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the above embodiments, it should be understood by those skilled in the art that the technical solution described in the above embodiments may be modified or some or all of the technical features may be equivalently replaced, and these modifications or substitutions do not make the essence of the corresponding technical solution deviate from the scope of the technical solution of the embodiments of the present invention.
Claims (19)
1. The method for recycling the battery anode material is characterized by comprising the following steps of:
The method comprises the steps of carrying out multistage crushing and screening on battery anode materials, collecting fine materials after crushing and screening of each stage to obtain anode powder, and collecting coarse materials after crushing and screening of the last stage to obtain current collector coarse materials;
Mixing the current collector coarse material with water for reaction, and filtering to obtain first filter residue and first filtrate;
mixing and stirring the first filter residue, water and starch, and carrying out solid-liquid separation to obtain a current collector concentrate and starch water;
mixing and roasting the starch water, the positive electrode powder and sulfate, adding water after roasting, mixing and filtering to obtain second filter residues and second filtrate;
And carbonizing the second filtrate and the first filtrate to obtain carbonate precipitate of a first metal material, wherein the first metal material is a lithium material.
2. The method for recycling a battery cathode material according to claim 1, characterized in that after obtaining the first filter residue and the first filtrate, the method specifically comprises the steps of:
screening the first filter residues to obtain slag and powder;
Mixing and stirring the slag, water and starch, and carrying out solid-liquid separation to obtain a current collector concentrate and starch water;
And mixing and roasting the starch water, the powder, the positive electrode powder and sulfate, adding water after roasting, mixing and filtering to obtain second filter residues and second filtrate.
3. The method for recycling a battery positive electrode material according to claim 1, wherein the particle size of the current collector coarse material is not more than 3mm, and the particle size of the positive electrode powder is less than 200 mesh.
4. The method for recycling a battery positive electrode material according to claim 3, wherein the particle size of the current collector coarse material is not more than 0.85mm, and the particle size of the positive electrode powder is less than 300 mesh.
5. The method for recycling a battery positive electrode material according to claim 3, wherein the content of the current collector in the positive electrode powder is 2% or less.
6. The method for recycling battery cathode materials according to claim 1, wherein the current collector coarse material is mixed with water and sodium sulfate and ball-milled before the first filter residue and the first filtrate are obtained.
7. The method for recycling battery cathode material according to claim 6, wherein the ball milling specifically comprises the steps of:
Mixing the current collector coarse material with sodium sulfate according to a mass ratio of 1:3-1:8, mixing with water according to a solid-liquid mass ratio of 1:5-1:15, ball milling, and filtering to obtain first filter residues and first filtrate.
8. The method for recycling battery cathode materials according to claim 2, wherein the first filter residue is subjected to wet screening to obtain slag and powder.
9. The method for recycling battery cathode material according to claim 8, wherein the wet screening specifically comprises the steps of:
mixing the first filter residue with water according to a mass ratio of 1:10-1:20, sieving with 200-300 meshes, wherein the oversize material is slag, and the undersize material is powder.
10. The method for recycling battery cathode materials according to claim 2, wherein the mixing and stirring method of the slag, water and starch specifically comprises the following steps:
And (3) preparing slurry from the slag and water according to a mass ratio of 1:5-1:15, adding starch according to a mass ratio of 1:3-1:8 of starch to the slag, stirring and washing, and carrying out solid-liquid separation to obtain a current collector concentrate and starch water.
11. The method for recycling a battery cathode material according to claim 2, characterized by comprising the following processing steps, before obtaining the second filter residue and the second filtrate:
Mixing the starch water with the powder, the positive electrode powder and the sulfate, roasting to obtain a roasting material, adding water into the roasting material, mixing, and performing ball milling to obtain a ball milling mixed solution;
and (3) adjusting the pH value of the ball milling mixed solution to a first pH value, and filtering to obtain second filter residues and second filtrate.
12. The method for recycling a battery positive electrode material according to claim 11, characterized in that, after mixing the starch water with the powder, the positive electrode powder, sulfate, the method further comprises:
and (3) pelletizing the mixture to obtain anode pellets, and roasting the anode pellets.
13. The method for recycling battery cathode material according to claim 12, characterized in that the pelletizing specifically comprises the steps of:
Mixing the anode powder and the powder according to the mass ratio of 3:1-5:1 to obtain a first mixture, adding sulfate according to the mass ratio of 1:3-1:7 to obtain a second mixture, adding starch water according to the mass ratio of 2:1-8:1 to uniformly mix, size mixing, and pelletizing the materials to obtain anode pellets.
14. The method for recycling battery cathode materials according to claim 13, wherein the roasting temperature is 400-500 ℃, the roasting time is 4-6 hours, and the mass ratio of the roasting material to water is 1:5-1:15.
15. The method for recycling battery positive electrode material according to claim 13, wherein the first pH value is 6.5 to 7.5.
16. The method for recycling a battery positive electrode material according to claim 1 or 2, characterized in that the specific steps of the carbonization treatment include:
And introducing carbon dioxide into the first filtrate and the second filtrate to obtain carbonate precipitation of the first metal material.
17. The method for recycling the battery positive electrode material according to claim 16, further comprising the step of wet-process impurity removal of the second filter residue to obtain a second metal material.
18. The method for recycling a positive electrode material of a battery according to claim 17, wherein the battery is a lithium ion battery, and the second metal material is other metal material than lithium in the positive electrode material of the battery.
19. The method for recycling a battery positive electrode material according to claim 18, wherein the second metal material is at least one of nickel, cobalt, and manganese.
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