CN110828926B - Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery - Google Patents
Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery Download PDFInfo
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- CN110828926B CN110828926B CN201910916926.8A CN201910916926A CN110828926B CN 110828926 B CN110828926 B CN 110828926B CN 201910916926 A CN201910916926 A CN 201910916926A CN 110828926 B CN110828926 B CN 110828926B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/215—Purification; Recovery or purification of graphite formed in iron making, e.g. kish graphite
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- C—CHEMISTRY; METALLURGY
- 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
- C22B1/005—Preliminary treatment of scrap
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- 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
- C22B7/007—Wet processes by acid leaching
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention discloses a method for cooperatively recovering metal and graphite from a positive electrode material and a negative electrode material of a waste lithium ion battery, and belongs to the technical field of lithium ion battery material recovery. The method comprises the steps of firstly mixing a positive electrode active material of a waste lithium ion battery and a graphite negative electrode active material, adding a proper amount of concentrated sulfuric acid, curing at a temperature below a boiling point to obtain a cured clinker, pulping and leaching the obtained cured clinker by using water or dilute acid, and then carrying out solid-liquid separation on leached ore pulp to obtain high-quality graphite and leachate. The obtained leachate is used for further recovering nickel, cobalt, lithium and the like in the leachate. The method of the invention does not need to separate the anode active material and the cathode active material in advance, simplifies the recovery process of the waste battery active material, and has high reaction temperature and high speed due to the adoption of solid-phase curing reaction, realizes the recovery of the cathode graphite and obtains high-quality graphite while recovering the useful elements of the anode material, and has low cost and high comprehensive utilization rate.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery, relates to a method for synergistically and comprehensively recovering anode and cathode materials of waste lithium ion batteries, and particularly relates to a method for synergistically and comprehensively recovering useful components such as lithium, cobalt, nickel, graphite and the like from the anode and cathode materials of the waste lithium ion batteries.
Background
The lithium battery positive electrode active material mainly comprises lithium cobaltate, lithium manganate, lithium iron phosphate, and ternary materials such as lithium nickel cobalt manganese, lithium nickel cobalt aluminate and the like; the lithium battery negative electrode material comprises a graphite negative electrode material, an alloy negative electrode material, a lithium titanate negative electrode material, a carbon nano negative electrode material, a silicon-carbon composite material and the like, wherein the graphite negative electrode material is widely used and comprises natural graphite, artificial graphite, graphitized mesocarbon microspheres, graphitized carbon fibers, graphene and the like. The rapid growth of 3C electrons and new energy automobiles leads to the rapid growth of lithium battery yield, the synchronous growth of demands for cobalt, lithium, graphite and the like, the rapid growth of retired lithium batteries, the comprehensive utilization of retired waste lithium batteries, the pollution of heavy metals and the like to the environment can be eliminated, the cobalt, lithium, graphite and the like can be recycled, and the consumption of strategic mineral resources is reduced.
For comprehensive recovery of waste lithium ion batteries, researchers at home and abroad carry out a great deal of research, and as the components and properties of the anode material and the cathode material of the lithium ion battery are completely different, the anode powder contains nickel, cobalt, manganese, lithium and the like, and needs to be reduced in advance, and then can be leached and extracted by acid, ammonia and the like; however, the negative active material, especially graphite negative material, is generally treated separately after the battery is dissociated and broken because of its chemical stability, acid resistance, alkali resistance and organic solvent resistance. Because the negative graphite powder is stable in chemical property, resistant to acid, alkali and organic solvent, when the positive powder is treated by a conventional wet method, part of the entrained graphite powder and part of unreacted positive electrode residues form black slag together.
The comprehensive recovery process of the anode active material of the waste lithium ion battery comprises a wet method and a fire method, wherein the recovery process based on hydrometallurgy is relatively mature, the application in the industry is relatively wide, and the most widely application is to react the anode material with inorganic acid and leach out valuable metals by taking hydrogen peroxide or sulfur dioxide as a reducing agent. CN103035977A discloses a method for recovering valuable metals from waste lithium ion batteries, which mainly adopts brine discharge, manual disassembly, alkaline leaching separation (or low-temperature roasting), reduction acid leaching (sulfuric acid and hydrogen peroxide), chemical precipitation and extraction of valuable metals in anode materials. In the process flow, the core lies in the leaching process of the anode material, the leaching process directly determines the recovery rate of valuable metals, the effect of the process flow can also influence the subsequent impurity removal process to a great extent, and the cost is high due to the consumption of a large amount of hydrogen peroxide. CN107083483A and CN106921000A disclose a ball mill mechanical activation leaching method, which shortens the leaching time, improves the metal leaching rate, and reduces the leaching liquid amount. The method also needs to consume a large amount of acid and reducing agent, the leaching ball milling has high requirements on equipment, and the energy consumption and the cost are increased.
The pyrogenic process treatment of the anode material is to treat the sorted waste anode material by reduction roasting or reduction smelting, and then recover nickel, cobalt, lithium and the like by a wet process. CN101170204A discloses a vacuum carbon heat recovery process for waste lithium ion batteries, which comprises mixing and granulating lithium cobaltate powder stripped from the anode of a waste lithium ion battery with starch as a binder and coal powder or carbon powder as a reducing agent, then carrying out heat treatment in a vacuum furnace at the furnace temperature of 1000 ℃ and 1200 ℃ and the vacuum degree of 10-1000Pa, wherein the residue after the heat treatment in the vacuum furnace is crude metal cobalt, and condensing steam in the vacuum furnace to obtain crude metal lithium. CN108123185A discloses a method for recovering valuable metals in waste lithium manganate batteries, which comprises the steps of mixing a lithium manganate positive electrode material subjected to disassembly and grinding treatment with a proper amount of carbon powder uniformly, carrying out reduction roasting at the temperature of 800-1300 ℃, and leaching lithium with dilute acid.
CN102569940B discloses a method for recycling waste lithium ion battery negative electrode materials, which comprises crushing the lithium ion battery negative electrode materials, performing air flow separation to obtain heavy metal-containing particles and light carbon powder-containing particles, collecting the light particles by a pulse dust collector, and feeding the light particles into an electrostatic separator to separate the metal powder in the light particles to obtain carbon powder. CN105552468A discloses a method for recovering graphite cathode materials of waste lithium ion batteries, which comprises the steps of sequentially carrying out alkali liquor soaking, acid liquor soaking and deionized water rinsing pretreatment on a cathode plate separated from a lithium ion battery, then carrying out pre-roasting, crushing and screening in an air atmosphere with the temperature of 300-500 ℃ to obtain a cathode active substance, then carrying out wet ball milling mixing on the obtained cathode active substance and oxalate, carrying out high-temperature treatment at the temperature of 450-800 ℃ in an inert atmosphere, and then carrying out cooling, crushing and screening to obtain the battery-grade graphite cathode material. CN103618120B discloses a method for separating and recovering graphite and copper sheets from a waste lithium ion battery negative electrode material, which comprises soaking the waste negative electrode material in dilute acid, sieving to remove copper sheets, adding hydrogen peroxide into the soaking solution to oxidize, filter, wash and dry to obtain a primarily purified graphite product, and then performing a two-step high-temperature treatment to obtain high-carbon graphite.
CN104593606B discloses a method for recycling anode and cathode scraps of waste lithium cobalt oxide lithium ion batteries, which comprises the steps of crushing and screening the anode and cathode scraps respectively, roasting the undersize at the temperature of 800-.
Although there are many existing methods for comprehensively recovering active materials of waste lithium ion batteries, most of the methods separate the positive active materials and the negative active materials, which results in a complex recovery processing system of the waste batteries, and the existing physical dissociation technology is difficult to completely separate the positive active materials and the negative active materials, which are mixed with each other, resulting in a large amount of black slag produced in the processing of the positive active materials to form secondary pollution. In the treatment of the cathode active material, the process is complex, and the obtained graphite powder has low purity, poor quality and low value. Because the negative electrode material also contains lithium and a small amount of current collectors or shell materials such as copper foil, aluminum foil, stainless steel and the like are remained due to incomplete dissociation and separation processes of the battery, the single treatment of the negative electrode is not beneficial to the comprehensive recovery of the lithium and the like in the negative electrode material.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for mixing the positive active material and the graphite negative active material of the waste lithium ion battery, namely, the mixture of the positive active material and the graphite negative active material obtained by crushing and dissociating the waste lithium ion battery is mixed with a proper amount of concentrated sulfuric acid to prepare a mixture, then the mixture is reacted and cured to obtain a cured clinker, the obtained cured clinker is slurried and leached by water or dilute acid, then leached ore pulp is separated to obtain leachate and high-quality graphite, and the leachate can further recover useful elements such as lithium, cobalt, nickel and the like, so that the combination treatment of the positive active material and the negative active material in the waste lithium ion battery is realized, and the comprehensive recovery of the nickel, the cobalt, the lithium and the like in the positive material and the graphite in the negative material is realized. The purpose of the invention is realized by the following technical scheme.
The method for cooperatively recovering the useful metal and graphite from the anode and cathode active materials of the waste lithium ion battery is characterized by comprising the following steps of:
(1) uniformly mixing a mixture containing a positive active material and a negative active material of a waste lithium ion battery with a proper amount of concentrated sulfuric acid to prepare a mixture, and then carrying out curing reaction to obtain solid clinker, wherein the curing reaction temperature is 100-400 ℃, and the curing reaction time is 0.5-8 hours; the positive active material is one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate; the negative active material is a graphite negative material.
(2) Leaching the solid clinker with water to obtain leached ore pulp;
(3) carrying out solid-liquid separation on the leached ore pulp to obtain leachate and high-quality graphite;
(4) and further treating the leachate, and recovering useful metal elements in the leachate, wherein the useful metal elements at least comprise two or more of lithium, cobalt and nickel.
In order to ensure the operation safety in the comprehensive recovery process and improve the quality of carbon products and the curing reaction effect, the method for synergistically and comprehensively recovering the anode material and the cathode material of the waste lithium ion battery can also comprise a leaching solution circulation and countercurrent leaching link, and comprises the following specific steps of:
(1) mixing a mixture containing the anode active material and the cathode active material of the waste lithium ion battery with the second-stage leachate in a leaching tank for first-stage leaching, and filtering to obtain a pregnant solution and first-stage leaching residues;
(2) uniformly mixing the first-stage leaching residue with a proper amount of concentrated sulfuric acid to prepare a mixture, and performing curing reaction to obtain solid clinker;
(3) performing secondary leaching on the clinker obtained in the step (2) by using water or dilute sulfuric acid with the mass concentration of sulfuric acid being less than or equal to 20%, and then performing solid-liquid separation on leached ore pulp to obtain secondary leaching liquid and high-quality graphite;
(4) and (3) using the pregnant solution obtained in the step (1) for further treatment, and recovering useful metal elements in the pregnant solution.
Furthermore, when the solid clinker is pulped and leached by using dilute sulfuric acid, a proper amount of hydrogen peroxide or sulfur dioxide can be added for reduction, so that the part of the residual anode material which is not reduced and decomposed in the solid clinker is further reduced, and the adding amount of the hydrogen peroxide is 1-10% of the mass of the anode material of the waste lithium ion battery according to the mass of the hydrogen peroxide.
Further, when the leachate is recycled and leached in a counter-current mode, tail gas obtained by reacting and curing in the step (2) is introduced into a first-stage leaching tank to be leached in a first stage, and therefore the purpose of purifying the cured tail gas while strengthening the first-stage leaching process is achieved.
Furthermore, in the mixture composed of the anode active material and the cathode active material of the waste lithium ion battery, the mass percentages of the anode active material and the graphite cathode active material are respectively more than or equal to 20%.
Further, the graphite negative electrode material is one or a mixture of natural graphite, artificial graphite, modified graphite and graphene.
And performing solid-liquid separation on the leached ore pulp to obtain leachate and high-quality graphite, performing sedimentation separation on the leached ore pulp to obtain suspension and concentrated ore pulp, performing solid-liquid separation on the suspension to obtain the leachate and the high-quality graphite, and performing solid-liquid separation on the concentrated ore pulp to obtain the leachate and the high-quality graphite.
Further, the suspension is subjected to solid-liquid separation, namely, a proper amount of alkali is added into the suspension until the pH value of the solution is 1.5-4, and then the solution is filtered or centrifugally separated to obtain leachate and high-quality graphite.
Further, the solid-liquid separation of the concentrated ore pulp is to filter or centrifugally separate the concentrated ore pulp to obtain leaching liquid and leaching residues, rinse the leaching residues to obtain suspension and residues, and filter the suspension to obtain high-quality graphite. The sedimentation separation is one or the combination of gravity sedimentation and centrifugal separation.
In addition, the leached ore pulp is subjected to solid-liquid separation to obtain leachate and high-quality graphite, or the leached ore pulp is filtered to obtain leachate and leached residues, the leached residues are pulped and washed, and then the leached residues are subjected to centrifugal separation to obtain high-quality graphite and residues. The residue is mainly unreacted positive electrode active material and can be returned to the curing ingredient.
Preferably, a proper amount of concentrated sulfuric acid is added into the positive and negative electrode active material mixture and uniformly mixed to prepare a mixture, the adding amount of the concentrated sulfuric acid is more than 1 time of the total mole number of all metal elements in the mixture, and the mass percentage concentration of sulfuric acid in the prepared mixture is not lower than 70%.
Preferably, the conditions of the mixture curing reaction are as follows: the reaction temperature is 150-300 ℃, and the reaction time is 1-4 hours.
Further, the high-quality graphite obtained by the solid-liquid separation of the leached ore pulp is graphite oxide, and the content of the graphite oxide is more than or equal to 96%.
The method for synergistically and comprehensively recovering the anode material and the cathode material of the waste lithium ion battery mixes the anode active material and the cathode active material, improves the interaction activity between the anode active material and the cathode material by utilizing the catalytic action of concentrated sulfuric acid, further strengthens and decomposes the anode active material, simultaneously modifies and purifies graphite, realizes comprehensive recovery of lithium in the cathode material, and achieves the effect of synergistic and strengthened treatment of the anode active material and the cathode active material. Except for the consumption of sulfuric acid, other agents are not required to be consumed, and the comprehensive recovery cost of nickel, cobalt, lithium and the like is reduced; meanwhile, metal or compound carried in the graphite cathode active material can be removed through mutual promotion of concentrated sulfuric acid and the anode active material, and then high-quality graphite is obtained through subsequent thickening or centrifugal separation, so that the recovery and high-value utilization of the cathode graphite material are realized, and lithium and other useful metal elements carried in the cathode powder can be further recovered.
The method of the invention does not need to separate the anode active material and the cathode active material in advance, simplifies the recovery process of the waste battery active material, reduces the cost, and because the curing reaction is carried out in a higher temperature environment, the reaction is rapid and complete, the recovery rate of useful elements is high, the purity of the recovered graphite product is high, and simultaneously, the reaction heat can be fully utilized during curing, the energy consumption is reduced, and the comprehensive utilization effect is good.
Drawings
FIG. 1 is a schematic diagram of the principle process of the method of the present invention.
Detailed Description
The invention is further described below with reference to fig. 1.
The method for recovering useful metal and graphite by using the positive and negative active materials of the waste lithium ion battery synergistically comprises the steps of mixing the positive active material and the negative active material obtained by crushing and separating the waste lithium ion battery, adding a proper amount of concentrated sulfuric acid, mixing, reacting and curing to obtain cured clinker, wherein the reaction curing temperature is controlled to be below the boiling point of sulfuric acid. And pulping and leaching the obtained cured clinker by using water or dilute acid, and then carrying out solid-liquid separation on leached ore pulp to obtain high-quality graphite and leachate. The obtained leachate is used for further recovering nickel, cobalt, lithium and the like. The positive electrode active material contains one or a mixture of more of lithium cobaltate, lithium nickelate, lithium manganate, lithium iron phosphate and ternary positive electrode materials; the negative electrode material is a graphite negative electrode material and is one or a mixture of more of natural graphite, artificial graphite, modified graphite and graphene.
In some embodiments, leach liquor circulation and counter current leaching links may be included, namely: mixing a mixture consisting of a positive active material and a negative active material of the waste lithium ion battery with a second-stage leaching solution in a leaching tank for first-stage leaching, and filtering to obtain a pregnant solution and first-stage leaching residues; then uniformly mixing the first-stage leaching residue with a proper amount of concentrated sulfuric acid to prepare a mixture, and carrying out curing reaction to obtain solid clinker; and performing secondary leaching on the clinker obtained in the step (1) by using water or dilute acid, and performing solid-liquid separation on leached ore pulp to obtain secondary leachate and high-quality graphite. The pregnant solution is used for further treatment, and useful metal elements in the pregnant solution are recovered.
In some implementations, the leached ore pulp is first settled and separated to obtain a suspension liquid, which is subjected to solid-liquid separation, a suspension liquid and a concentrated ore pulp, the suspension liquid is subjected to solid-liquid separation to obtain a leaching solution and high-quality graphite, and the concentrated ore pulp is filtered or centrifugally separated and rinsed to obtain the high-quality graphite, the leaching solution and a small amount of unreacted anode material residues.
In some implementations, a proper amount of alkali is added into the suspension obtained by settling separation of the leached ore pulp until the pH of the solution is 1.5-4, and then the leaching solution and high-quality graphite are obtained by filtration or centrifugal separation.
In some implementations, when leaching is performed using both recycle and counter current leaching of the leachate, the reaction-matured off-gas is introduced into a primary leaching tank for primary leaching.
In some implementations, the leaching pulp solid-liquid separation is to filter the leaching pulp to obtain leaching liquid and leaching residues, the leaching residues are pulped, washed and centrifugally separated to obtain high-quality graphite and residues, the residues are mainly unreacted positive electrode active materials, and the residues can be returned to the curing ingredients.
The process of the present invention is further illustrated by the following non-limiting examples to facilitate the understanding of the contents of the invention and its advantages, but not to limit the scope of the invention, which is defined by the claims.
Example 1
Mixing nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries and graphite negative electrode material powder according to the mass ratio of 1:1, mixing the mixture with concentrated sulfuric acid with the mass percentage concentration of 98% to prepare a mixture, adding the concentrated sulfuric acid in an amount which is 2 times of the total mole number of metal elements in the positive electrode material, curing and reacting the mixture at 250 ℃ for 2 hours to obtain cured clinker, soaking the obtained cured clinker in water at 95 ℃ for 1 hour under the condition of the liquid-solid ratio of 5:1mL/g, performing sedimentation separation on the leached ore pulp, filtering the suspension to obtain high-quality graphite with the purity of more than 96% and leachate-1, filtering the settled concentrated ore pulp to obtain leached slag and leachate-2, rinsing the leached slag with deionized water, performing sedimentation separation to obtain the suspension, and filtering the suspension to obtain high-quality graphite. And combining the leaching solution-1 and the leaching solution-2 for further purification and separation and then recovering nickel, cobalt and lithium.
Example 2
Mixing nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries with graphite negative electrode material powder according to the mass ratio of 1:1, adding the obtained mixture and a second-stage leaching solution into a first-stage leaching tank for first-stage leaching, filtering first-stage leached ore pulp to obtain first-stage leached slag with water content less than 10% and a first-stage leaching solution, namely a pregnant solution, and using the obtained pregnant solution for further recovering nickel-cobalt-manganese-lithium and the like; uniformly mixing the first-stage leaching residue with concentrated sulfuric acid with the mass percentage concentration of 90%, adding the concentrated sulfuric acid in an amount which is 2 times of the total mole number of metal elements in the positive electrode material, curing and reacting the uniformly mixed material at 250 ℃ for 2 hours to obtain cured clinker, soaking the obtained cured clinker with water at 95 ℃ and a liquid-solid ratio of 5:1mL/g for 1 hour to obtain second-stage leaching, carrying out centrifugal sedimentation on second-stage leaching ore pulp, filtering a sedimentation obtained suspension to obtain graphite with the purity of more than 96% and a second-stage leaching solution-1, filtering the sedimentation obtained concentrated ore pulp to obtain a second-stage leaching residue and a second-stage leaching solution-2, combining the obtained second-stage leaching solution-1 and the second-stage leaching solution-2, and returning to the first-stage leaching. Rinsing the second-stage leaching residue with deionized water, settling and separating to obtain a suspension, and filtering the suspension to obtain graphite oxide.
Example 3
Mixing nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries with graphite negative electrode material powder according to the mass ratio of 1:1, adding the obtained mixture and a second-stage leaching solution into a first-stage leaching tank, introducing tail gas of curing reaction into the first-stage leaching tank for first-stage leaching, filtering first-stage leaching ore pulp to obtain first-stage leaching residue with water content less than 10% and first-stage leaching solution, namely pregnant solution, and using the obtained pregnant solution for further recovering nickel-cobalt-manganese-lithium and the like; uniformly mixing the first-stage leaching residue with concentrated sulfuric acid with the mass percentage concentration of 90%, adding the concentrated sulfuric acid in an amount which is 2 times of the total mole number of metal elements in the anode material, curing and reacting the uniformly-stirred materials at 250 ℃ for 2 hours to obtain cured clinker, leaching the obtained cured clinker with water for 1 hour at the temperature of 95 ℃ and the liquid-solid ratio of 5:1mL/g, namely second-stage leaching, carrying out centrifugal sedimentation on second-stage leaching ore pulp, filtering the settled suspension to obtain graphite with the purity of more than 96% and second-stage leaching liquid-1, filtering the settled concentrated ore pulp to obtain second-stage leaching residue and second-stage leaching liquid-2, combining the obtained second-stage leaching liquid-1 and second-stage leaching liquid-2, and returning to the first-stage leaching. Rinsing the second-stage leaching residue with deionized water, settling and separating to obtain a suspension, and filtering the suspension to obtain graphite oxide.
Example 4
Mixing and batching lithium cobaltate positive electrode material powder and graphite negative electrode material powder separated from waste lithium batteries according to the mass ratio of 8:2, then mixing the batching and concentrated sulfuric acid with the mass percentage concentration of 98% to prepare a mixture, adding the concentrated sulfuric acid in an amount which is 2 times of the total mole number of metal elements in the positive electrode material, then carrying out curing reaction on the mixture at 250 ℃ for 2 hours to obtain cured clinker, carrying out water immersion on the obtained cured clinker for 1 hour at the temperature of 95 ℃ and at the liquid-solid ratio of 5:1mL/g, then filtering to obtain leachate containing cobalt and lithium ions and leaching slag, recycling the cobalt and lithium after the leachate is used for further purification and separation, rinsing and settling separation on the leaching slag to obtain suspension, and filtering the suspension to obtain high-quality graphite.
Example 5
Mixing and batching nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries and mixed powder consisting of graphite negative electrode materials according to the mass ratio of 2:8, then mixing the batching and concentrated sulfuric acid with the mass percentage concentration of 98% to prepare a mixed material, adding the concentrated sulfuric acid in an amount which is 3 times of the total mole number of metal elements in the positive electrode materials, then curing and reacting the mixed material at 250 ℃ for 2 hours to obtain cured clinker, and soaking the obtained cured clinker in water for 1 hour at the temperature of 95 ℃ and the liquid-solid ratio of 5:1 mL/g. And then carrying out sedimentation separation on the leached ore pulp, filtering the suspension to obtain high-quality graphite with the purity of more than 95% and leachate-1, filtering the concentrated ore pulp obtained by sedimentation to obtain leached slag and leachate-2, rinsing the leached slag by using deionized water, carrying out sedimentation separation to obtain suspension, and filtering the suspension to obtain high-quality graphite. And combining the leaching solution-1 and the leaching solution-2 for further purification and separation and then recovering nickel, cobalt and lithium.
Example 6
Mixing nickel-cobalt-aluminum ternary positive electrode material powder separated from waste lithium batteries and mixed powder consisting of various carbon-based negative electrode materials according to the mass ratio of 5:5, then mixing the mixed powder with concentrated sulfuric acid with the mass percentage concentration of 98% to prepare a mixed material, adding the concentrated sulfuric acid in an amount which is 2 times of the total mole number of metal elements in the positive electrode materials, then carrying out curing reaction on the mixed material at 250 ℃ for 2 hours to obtain cured clinker, carrying out water immersion on the obtained cured clinker for 1 hour at the temperature of 95 ℃ and under the condition of the liquid-solid ratio of 5:1mL/g, adding a proper amount of hydrogen peroxide and sulfuric acid during leaching, controlling the sulfuric acid concentration of final acid to be 45g/L, adding the hydrogen peroxide in an amount which is 2% of the mass of the positive electrode powder, carrying out sedimentation separation after leaching, adding a proper amount of alkali into a suspension until the pH of the solution is 1.5-4, then filtering to obtain high-quality graphite and leachate-1 with the purity of more than 96%, and filtering the concentrated ore pulp obtained by settling to obtain leaching slag and leaching solution-2, rinsing the leaching slag by using deionized water, settling and separating to obtain suspension, and filtering the suspension to obtain high-quality graphite. And combining the leaching solution-1 and the leaching solution-2 for further purification and separation and then recovering nickel, cobalt and lithium.
Example 7
Mixing and batching nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries and mixed powder consisting of graphite negative electrode materials according to the mass ratio of 2:8, then mixing the batching and concentrated sulfuric acid with the mass percentage concentration of 98% to prepare a mixed material, adding the concentrated sulfuric acid in an amount which is 3 times of the total mole number of metal elements in the positive electrode materials, then curing and reacting the mixed material at 300 ℃ for 2 hours to obtain cured clinker, and soaking the obtained cured clinker in water for 1 hour at the temperature of 95 ℃ and the liquid-solid ratio of 5:1 mL/g. And then filtering the leached ore pulp to obtain leachate and leached residues, wherein the leachate is used for further purifying and separating and then recovering nickel, cobalt and lithium. And pulping and washing the leached residues, then centrifugally separating to obtain graphite oxide and residues, wherein the residues are mainly unreacted positive electrode active materials, and returning to the curing ingredient.
Claims (13)
1. The method for cooperatively recovering metal and graphite from the anode material and the cathode material of the waste lithium ion battery is characterized by comprising the following specific steps of:
(1) uniformly mixing a mixture containing a positive active material and a negative active material of a waste lithium ion battery with a proper amount of concentrated sulfuric acid to prepare a mixture, and then carrying out curing reaction to obtain solid clinker, wherein the curing reaction temperature is 100-400 ℃, and the curing reaction time is 0.5-8 hours; the positive active material is one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate; the negative active material is a graphite negative material; no other medicament is consumed except the consumption of sulfuric acid;
(2) leaching the solid clinker with water to obtain leached ore pulp;
(3) carrying out solid-liquid separation on the leached ore pulp to obtain leachate and high-quality graphite;
(4) and further treating the leachate, and recovering useful metal elements in the leachate, wherein the useful metal elements at least comprise two or more of lithium, cobalt and nickel.
2. The method for recovering metal and graphite by the synergy of the anode material and the cathode material of the waste lithium ion battery is characterized by comprising a leaching solution circulation and countercurrent leaching link, and comprises the following specific steps:
(1) mixing a mixture containing the anode active material and the cathode active material of the waste lithium ion battery with the second-stage leachate in a leaching tank for first-stage leaching, and filtering to obtain a pregnant solution and first-stage leaching residues; the positive active material is one or more of lithium cobaltate, lithium nickelate, lithium nickel cobalt manganese oxide and lithium nickel cobalt aluminate; the negative active material is a graphite negative material;
(2) uniformly mixing the first-stage leaching residue with a proper amount of concentrated sulfuric acid to prepare a mixture, and then carrying out curing reaction to obtain solid clinker; the curing reaction temperature is 100-400 ℃, and the curing reaction time is 0.5-8 hours; no other agents are consumed except for the consumption of sulfuric acid;
(3) performing secondary leaching on the clinker obtained in the step (2) by using water, and then performing solid-liquid separation on leached ore pulp to obtain secondary leaching liquid and high-quality graphite; returning the second-stage leachate to the first-stage leaching in the step (1);
(4) and (2) using the pregnant solution obtained in the step (1) for further treatment, and recovering useful metal elements in the pregnant solution.
3. The method according to claim 2, characterized in that, in the primary leaching of the step (1), tail gas generated in the reaction of the step (2) is introduced into a primary leaching tank for primary leaching.
4. The method according to claim 1 or 2, wherein in the mixture of the anode active material and the cathode active material of the waste lithium ion battery, the mass percentage of each of the anode active material and the cathode active material is more than or equal to 20%.
5. The method of claim 1 or 2, wherein the graphite negative electrode material is a mixture of one or more of natural graphite, artificial graphite, modified graphite and graphene.
6. The method according to claim 1 or 2, wherein the leaching ore pulp is subjected to solid-liquid separation to obtain a leaching solution and high-quality graphite, the leaching ore pulp is subjected to sedimentation separation to obtain a suspension and concentrated ore pulp, the suspension is subjected to solid-liquid separation to obtain the leaching solution and the graphite, and the concentrated ore pulp is subjected to solid-liquid separation to obtain the leaching solution and the high-quality graphite.
7. The method according to claim 6, wherein the solid-liquid separation of the suspension is carried out by adding an appropriate amount of alkali into the suspension until the pH of the solution is 1.5-4, and then filtering or centrifuging to obtain the leachate and high-quality graphite.
8. The method according to claim 6, wherein the concentrated ore pulp is subjected to solid-liquid separation by filtering or centrifugal separation to obtain leaching liquid and leaching residues, rinsing and centrifugal separation are performed to obtain suspension, and the suspension is filtered to obtain high-quality graphite.
9. The method of claim 6, wherein the settling separation is one or a combination of gravity settling and centrifugation.
10. The method according to claim 1 or 2, wherein the leaching ore pulp is subjected to solid-liquid separation to obtain a leaching solution and high-quality graphite, the leaching ore pulp is filtered to obtain the leaching solution and leaching residues, the leaching residues are pulped and washed, and then the leaching solution and the leaching residues are subjected to centrifugal separation to obtain the high-quality graphite.
11. The method according to claim 1 or 2, wherein the proper amount of concentrated sulfuric acid is that the adding amount of the concentrated sulfuric acid is more than 1 time of the total mole number of all metal elements in the mixture, and the mass percentage concentration of the sulfuric acid in the prepared mixture is not lower than 70%.
12. The process according to claim 1 or 2, characterized in that the ripening reaction conditions are: the reaction temperature is 150-350 ℃, and the reaction time is 1-4 hours.
13. The method as claimed in claim 1 or 2, wherein the high-quality graphite obtained by the solid-liquid separation of the leaching ore pulp is graphite oxide, and the content of the graphite oxide is more than or equal to 96%.
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