CN110835682A - Method for cooperatively treating positive and negative active materials of waste lithium ion battery - Google Patents
Method for cooperatively treating positive and negative active materials of waste lithium ion battery Download PDFInfo
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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
- C22B7/007—Wet processes by acid leaching
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B25/00—Obtaining tin
- C22B25/04—Obtaining tin by wet processes
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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
- C22B25/00—Obtaining tin
- C22B25/06—Obtaining tin from scrap, especially tin 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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
- C22B30/00—Obtaining antimony, arsenic or bismuth
- C22B30/02—Obtaining antimony
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
- C22B34/1236—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching
- C22B34/124—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors
- C22B34/125—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining titanium or titanium compounds from ores or scrap by wet processes, e.g. by leaching using acidic solutions or liquors containing a sulfur ion as active agent
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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
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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Abstract
The invention discloses a method for cooperatively processing anode materials and cathode materials of waste lithium ion batteries, and belongs to the technical field of lithium ion battery material recovery. The method comprises the steps of adding a proper amount of concentrated sulfuric acid into a mixture of a positive active material and a negative active material obtained by crushing and separating a waste lithium ion battery, reacting and curing to obtain a cured clinker, leaching the obtained cured clinker with water or dilute acid, settling and separating leached ore pulp to obtain a leachate containing useful metal elements such as cobalt, lithium, nickel, titanium and the like, and centrifugally grading the leached slag to obtain high-quality graphite and residues, so that the synergistic strengthening treatment of the positive active material and the negative active material in the waste lithium ion battery is realized, multiple components such as nickel, cobalt, manganese, lithium, graphite powder and the like can be comprehensively recovered, the recovery process of the active material of the waste battery is facilitated, the recovery rate of the useful elements is high, and the purity of the recovered graphite product is high. The method mainly consumes sulfuric acid, and has low cost.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery material recovery, relates to a method for cooperatively treating a positive electrode material and a negative electrode material of a waste lithium ion battery, and particularly relates to a method for comprehensively recovering useful components such as lithium, cobalt, nickel, manganese, titanium, graphite and the like.
Background
The lithium battery generally comprises five parts, namely a positive electrode material, a negative electrode material, a diaphragm, an electrolyte, a battery shell and the like, wherein the positive electrode is composed of a positive electrode active material, a conductive agent, a binder and an aluminum foil, and the negative electrode is composed of a negative electrode active material, a conductive agent, a binder and a copper foil. 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 cathode material comprises a graphite cathode material, an alloy cathode material, a lithium titanate cathode material, a carbon nano cathode material, a silicon-carbon composite material and the like, wherein the graphite cathode material comprises natural graphite, artificial graphite, graphitized mesocarbon microspheres, graphitized carbon fibers, graphene and the like, and the alloy cathode material comprises a tin-based alloy, a silicon-based alloy, an aluminum-based alloy, an antimony-based alloy, a magnesium-based alloy 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.
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 also influences the subsequent impurity removal process to a great extent, and the rate influences the rate of the whole process flow. The cost is high because a large amount of hydrogen peroxide is consumed. 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. Because the negative graphite powder is stable in chemical property, acid-resistant, alkali-resistant and organic solvent-resistant, the graphite powder and part of unreacted positive electrode residues form black residues together when the positive electrode powder is treated by a wet method.
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 obtain a sieved product, adding hydrogen peroxide into the soaked solution to oxidize, filter, wash and dry to obtain a preliminarily 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 the current collector or shell material such as copper foil, aluminum foil, stainless steel and the like which are remained due to incomplete dissociation and separation of the battery, the negative electrode is treated independently, and comprehensive recovery of the lithium and the like is not facilitated.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for cooperatively treating positive and negative active materials of waste lithium ion batteries, which comprises the steps of crushing and dissociating the waste lithium ion batteries to obtain a mixture of the positive active materials and graphite negative active materials, adding a proper amount of concentrated sulfuric acid to prepare a mixture, reacting and curing the mixture to obtain solid clinker, pulping and leaching the obtained solid clinker by using water or dilute sulfuric acid, separating leached ore pulp to obtain leachate, high-quality graphite and the like, and further recovering useful metal elements such as lithium, cobalt and the like from the leachate, so that the combination treatment of the positive and negative active materials in the waste lithium ion batteries is realized, and the comprehensive recovery of nickel, cobalt, lithium and the like in the positive materials and graphite, tin, antimony, titanium and the like in the negative materials is realized. The purpose of the invention is realized by the following technical scheme. The comprehensive recovery of nickel, cobalt, lithium and the like in the anode material and graphite in the cathode material is realized. The purpose of the invention is realized by the following technical scheme.
The method for the cooperative treatment of the positive and negative active materials of the waste lithium ion battery is characterized by comprising the following steps of:
(1) adding concentrated sulfuric acid into a mixture consisting of a positive active material and a negative active material of a waste lithium ion battery according to a proportion to prepare a mixture, and then carrying out reaction and solidification to obtain clinker;
(2) pulping and leaching the clinker obtained in the step (1) by using water or dilute sulfuric acid, and then separating leached ore pulp to obtain leachate and leaching residues;
(3) and (3) using the leachate obtained in the step (2) for further treatment, and recovering useful metal elements in the leachate, wherein the useful metal elements at least comprise two or more of lithium, cobalt, nickel, tin, antimony and titanium.
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 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;
(2) mixing the first-stage leaching residue and concentrated sulfuric acid in proportion to prepare a mixture, and then reacting and curing to obtain clinker;
(3) performing secondary leaching on the clinker obtained in the step (2) by using water or dilute acid, and then separating leached ore pulp to obtain a secondary leaching solution and secondary leaching residues;
(4) and (3) using the pregnant solution obtained in the step (1) for further treatment, and recovering useful metal elements in the pregnant solution.
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.
The positive active material is a positive powder material obtained by splitting and crushing waste lithium ion batteries, and at least contains one or more of nickel cobalt lithium manganate, lithium cobaltate, lithium nickelate and lithium nickel cobalt aluminate; the negative electrode active material is a negative electrode powder material obtained by splitting and crushing waste lithium ion batteries, and at least contains one or more of a lithium titanate negative electrode material, an alloy negative electrode material, a silicon-carbon composite negative electrode material and a graphite negative electrode material.
Preferably, in the mixture composed 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 10%.
Preferably, the mixed material is prepared by proportioning the raw materials and concentrated sulfuric acid according to a certain proportion, the mass percentage concentration of the concentrated sulfuric acid is more than or equal to 80%, and the adding amount of the concentrated sulfuric acid is 1-2 times of the total mole number of all metal elements in the mixed material. In some embodiments, the battery anode material and the solid reducing agent are allowed to contain certain moisture, and the allowable moisture content is limited to the sulfuric acid mass percentage concentration in the mixed material after the mixing is not lower than 70%.
Preferably, the conditions for reaction and solidification of the mixture are as follows: the reaction temperature is 100-350 ℃, the reaction time is 0.5-8 h, the preferable reaction temperature is 150-300 ℃, and the reaction time is 1-4 h.
Preferably, the leaching conditions of slurry leaching of the solid clinker by using water or dilute sulfuric acid are as follows: the leaching temperature is 20-100 ℃, the leaching time is 10-120 min, and the dilute acid is dilute sulfuric acid with the mass concentration less than or equal to 10%.
Furthermore, when the solid clinker is pulped and leached by dilute sulfuric acid, a proper amount of hydrogen peroxide or sulfur dioxide can be added for reduction, so that the residual part of the unreduced and decomposed anode material in the solid clinker is further reduced, 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, and the sulfuric acid mass concentration of the dilute sulfuric acid is less than or equal to 20%.
Further, the alloy negative electrode material is one or a mixture of tin-based alloy, silicon-based alloy, aluminum-based alloy, antimony-based alloy and magnesium-based alloy.
Further, the negative electrode active material is a graphite-based negative electrode material.
Further, when the cathode active material is a graphite cathode material, after the clinker is leached by dilute sulfuric acid, the leached slurry is subjected to settling separation and washing to obtain a leaching solution and high-quality graphite.
Compared with the prior art, the method has the advantages that the anode material and the cathode material of the waste lithium ion battery are mixed, the reaction activity of the anode active material and the cathode material is improved by utilizing the oxidation catalysis effect of concentrated sulfuric acid, the self-oxidation reduction of the anode active material and the cathode active material of the lithium ion battery is realized, and the effect of synergistic strengthening treatment between the anode active material and the cathode active material is achieved. Except sulfuric acid, other agents are not needed to be consumed, and the comprehensive recovery cost of nickel, cobalt, manganese, lithium and the like is reduced; meanwhile, the metal or compound carried in the negative active material can be removed and recovered through mutual promotion of concentrated sulfuric acid and the positive active material.
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 has rapid and complete reaction, high recovery rate of useful elements because the curing reaction is carried out in a higher temperature environment, and can fully utilize the reaction heat during curing, reduce the energy consumption and have good comprehensive utilization effect.
Detailed Description
The invention relates to a method for cooperatively treating positive and negative electrode materials of waste lithium ion batteries and comprehensively recovering useful elements in the positive and negative electrode materials, which comprises the steps of mixing and blending the positive electrode active materials and the negative electrode active materials obtained by crushing and separating the waste lithium ion batteries, adding a proper amount of concentrated sulfuric acid, mixing, reacting and curing to obtain cured clinker, pulping and leaching the obtained cured clinker by using water or dilute acid, settling and separating leached ore pulp, filtering the settled suspension to obtain carbon and leachate, and filtering the settled concentrated ore pulp underflow to obtain leached slag and leachate. The obtained leachate is used for further recovering nickel, cobalt, manganese, 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 one or a mixture of a plurality of carbon-based negative electrode materials, lithium titanate negative electrode materials, silicon-based negative electrode materials and silicon-carbon composite negative electrode materials.
Adding concentrated sulfuric acid into a mixture consisting of a positive active material and a negative active material of a waste lithium ion battery according to a proportion to prepare a mixture, and then carrying out reaction and solidification to obtain clinker; pulping the clinker with water or dilute sulfuric acid to leach lithium, cobalt, nickel, titanium, antimony and the like in the clinker, and separating leached ore pulp to obtain leachate and leached residues; the leachate is used for further processing and recovering the useful metal elements such as lithium, cobalt, nickel, tin, antimony, titanium and the like.
When the negative active material contains graphite negative material, the leached ore pulp can be settled, separated and washed to obtain leachate and high-quality graphite.
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 for first-stage leaching, and filtering to obtain a first-stage leaching solution and a first-stage leaching residue; then, the first-stage leaching residues and concentrated sulfuric acid are proportioned according to a proportion to prepare a mixture, the mixture is cured through reaction to obtain a cured clinker, the obtained cured clinker is subjected to second-stage leaching by using water or dilute acid, then leaching ore pulp is separated to obtain second-stage leaching liquid and second-stage leaching residues, and the second-stage leaching liquid returns to the first-stage leaching circulation; the first-stage leachate, namely the pregnant solution, is further treated to recover useful metal elements.
In some embodiments, when leaching is performed in a recycle and counter current manner, the reaction-aged tail gas is introduced into a primary leaching tank for primary leaching.
In some embodiments, when the solid clinker is slurried and leached by dilute sulfuric acid, a proper amount of hydrogen peroxide or sulfur dioxide can be added for reduction, wherein the adding amount of the hydrogen peroxide is 1-10% of the mass of the anode material of the waste lithium ion battery by mass, and the sulfuric acid mass concentration of the dilute sulfuric acid is less than or equal to 20%.
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 with a lithium titanate negative electrode material and a graphite negative electrode material according to a mass ratio of 4:1:1, then mixing the mixture with concentrated sulfuric acid with a mass percentage concentration of 98% to prepare a mixture, wherein the addition amount of the concentrated sulfuric acid is 1.5 times of the total mole number of metal elements in the mixture, 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 80 ℃ under the condition of a liquid-solid ratio of 5:1mL/g, then carrying out filtration separation on leached ore pulp to obtain leachate containing cobalt, nickel, lithium and manganese, further purifying and separating the leachate, and recovering the nickel, the cobalt and the lithium.
Example 2
Mixing and batching nickel-cobalt-manganese ternary positive electrode material powder and graphite negative electrode material powder which are separated from waste lithium batteries according to the mass ratio of 5:1, then mixing the nickel-cobalt-manganese ternary positive electrode material powder and the graphite negative electrode material powder with the mass percentage concentration of 98% to prepare a mixture, adding concentrated sulfuric acid with the addition amount being 1.5 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 80 ℃ and under the condition of the liquid-solid ratio of 5:1mL/g, then carrying out sedimentation separation on leached ore pulp, filtering suspension to obtain high-quality graphite with the purity of more than 96% 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. And combining the leaching solution-1 and the leaching solution-2 for further purification and separation and then recovering nickel, cobalt and lithium.
Example 3
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 5:1, adding the obtained mixture and a second-stage leaching solution into a first-stage leaching tank for first-stage leaching, filtering first-stage leaching ore pulp to obtain first-stage leaching residue with water content of less than 20% 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 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 80 ℃ 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 suspension obtained by sedimentation to obtain graphite with the purity of more than 95% and a second-stage leaching solution-1, filtering the sedimentation underflow to obtain leaching residues 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.
Example 4
Mixing and batching nickel-cobalt-manganese ternary positive electrode material powder separated from waste lithium batteries and graphite negative electrode material according to a mass ratio of 6:4, then mixing the batching and concentrated sulfuric acid with a 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, leaching the obtained cured clinker with dilute sulfuric acid with a mass concentration of 10% for 1 hour under the conditions of 95 ℃ and a liquid-solid ratio of 5:1mL/g, adding a proper amount of hydrogen peroxide during leaching, wherein the adding amount of the hydrogen peroxide is 2% of the mass of the positive electrode powder according to the amount of hydrogen peroxide, and filtering after leaching to obtain leachate and leaching slag containing cobalt, nickel, manganese and lithium ions, wherein the leachate and the leaching slag are used for further purifying and separating and then recovering the nickel, the cobalt, the manganese and the lithium. And rinsing and centrifugally separating the leached residues to obtain graphite oxide.
Claims (12)
1. The method for the cooperative treatment of the positive and negative active materials of the waste lithium ion battery is characterized by comprising the following steps of:
(1) adding concentrated sulfuric acid into a mixture consisting of a positive active material and a negative active material of a waste lithium ion battery according to a proportion to prepare a mixture, and then carrying out reaction and solidification to obtain clinker;
(2) pulping and leaching the clinker obtained in the step (1) by using water or dilute sulfuric acid, and then separating leached ore pulp to obtain leachate and leaching residues;
(3) and (3) using the leachate obtained in the step (2) for further treatment, and recovering useful metal elements in the leachate, wherein the useful metal elements at least comprise two or more of lithium, cobalt, nickel, tin, antimony and titanium.
2. The method according to claim 1, comprising a leachate circulation and counter-current leaching stage, comprising the following steps:
(1) 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;
(2) mixing the first-stage leaching residue and concentrated sulfuric acid in proportion to prepare a mixture, and then reacting and curing to obtain clinker;
(3) performing secondary leaching on the clinker obtained in the step (2) by using water or dilute sulfuric acid, and then separating leached ore pulp to obtain a secondary leaching solution and secondary leaching residues;
(4) and (3) 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), the tail gas generated in the reaction aging of the step (2) is introduced into a primary leaching tank for primary leaching.
4. The method according to claim 1 and 2, wherein the positive active material in the step (1) is a positive powder material obtained by splitting and crushing a waste lithium ion battery, and at least contains one or more of lithium nickel cobalt manganese oxide, lithium cobalt oxide, lithium nickel oxide and lithium nickel cobalt aluminate; the negative electrode active material is a negative electrode powder material obtained by splitting and crushing waste lithium ion batteries, and at least contains one or more of a lithium titanate negative electrode material, an alloy negative electrode material, a silicon-carbon composite negative electrode material and a graphite negative electrode material.
5. The method according to claim 1 and 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 10%.
6. The method according to claims 1 and 2, characterized in that the concentrated sulfuric acid is sulfuric acid with a mass percentage concentration of more than or equal to 80%, the concentrated sulfuric acid and the concentrated sulfuric acid are mixed in proportion to prepare a mixture, the addition amount of the concentrated sulfuric acid is 1-2 times 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%.
7. The method according to claim 1 or 2, wherein the reaction curing conditions are as follows: the reaction temperature is 100-350 ℃, the reaction time is 0.5-8 h, the preferable reaction temperature is 150-300 ℃, and the reaction time is 1-4 h.
8. The method as claimed in claim 1 and 2, wherein the leaching conditions for slurry leaching of the clinker with water or dilute sulphuric acid are as follows: the leaching temperature is 20-100 ℃, the leaching time is 10-120 min, and the dilute acid is dilute sulfuric acid with the mass concentration less than or equal to 10%.
9. The method as claimed in claims 1 and 2, wherein when the solid clinker is slurried and leached by dilute sulfuric acid, a proper amount of hydrogen peroxide or sulfur dioxide is added for reduction, the adding amount of hydrogen peroxide is 1-10% of the mass of the anode material of the waste lithium ion battery according to the mass of hydrogen peroxide, and the sulfuric acid mass concentration of the dilute sulfuric acid is less than or equal to 20%.
10. The method of claim 4, wherein the alloy-based negative electrode material is one or more of tin-based alloy, silicon-based alloy, aluminum-based alloy, antimony-based alloy and magnesium-based alloy.
11. The method of claim 4, wherein the negative active material is a graphite-based negative electrode material.
12. The method of claim 11, wherein after the clinker is leached with dilute sulfuric acid, the leaching slurry is settled, separated and washed to obtain leachate and high-quality graphite.
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