CN108767354B - Method for recovering valuable metals from waste lithium ion battery anode materials - Google Patents

Method for recovering valuable metals from waste lithium ion battery anode materials Download PDF

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CN108767354B
CN108767354B CN201810531845.1A CN201810531845A CN108767354B CN 108767354 B CN108767354 B CN 108767354B CN 201810531845 A CN201810531845 A CN 201810531845A CN 108767354 B CN108767354 B CN 108767354B
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ammonium
roasting
lithium ion
valuable metals
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CN108767354A (en
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何仕超
刘志宏
夏隆巩
刘智勇
李启厚
朱银
黄辉
高禄鹏
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Central South University
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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
    • 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
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • 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
    • C22B7/001—Dry processes
    • 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
    • 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
    • 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

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Abstract

The invention provides a simple, high-efficiency ringThe method for recovering valuable metals from the anode materials of the waste lithium ion batteries in a protected area comprises the following steps: discharging the salt solution; disassembling and separating out the positive plate; crushing the positive plate to separate the positive material and the aluminum foil; the positive electrode material is mixed with a roasting agent ammonium sulfate and/or ammonium bisulfate for low-temperature roasting; soaking the roasted material in water, and separating to obtain carbon and leachate; adding precipitant into the leachate, and using the leachate containing NH3Regulating the pH value of the flue gas, precipitating other metals except Li, and carrying out solid-liquid separation; using a catalyst containing NH3Adjusting pH of the filtrate with flue gas, adding ammonium carbonate or ammonium bicarbonate or bubbling CO2And (5) gas is generated, and lithium is precipitated to obtain a lithium carbonate product. The preparation method has the advantages of simple preparation process, mild process conditions, short time required by the process, no need of consuming a large amount of acid and alkali, low cost, effective realization of recovery of valuable metals and carbon in the anode material, environmental protection, and no generation of a large amount of solid waste and wastewater.

Description

Method for recovering valuable metals from waste lithium ion battery anode materials
Technical Field
The invention relates to the field of electronic solid waste treatment and recycling, and relates to a method for recovering valuable metals from a waste lithium ion battery anode material.
Background
At present, since LiNixCoyMn1-x-yO2The battery positive active material contains a large amount of important rare metal resources such as Li, Co, Ni, Mn and the like, so the waste LiNixCoyMn1-x-yO2The recovery of the positive active material has attracted a wide range of attention worldwide. First generation LiCoO for lithium ion batteries2As anode material, simultaneously recovering LiCoO2As positive electrode materialA great deal of research has been conducted on spent lithium ion batteries. However, most of the lithium ion battery anode materials widely used at present are made of LiCoO2、LiMn2O4、LiNiO2、LiNixMnyCo1-x-yO2And LiFePO4Mainly comprises the following steps. The price of the cathode material is the most expensive part of each component of the lithium ion battery, and with the continuous development of new technologies of the lithium ion cathode material, the lithium ion battery with low production cost and high energy density is produced.
With the continuous development of the anode material, it is very important for lithium ion battery recyclers to know the mainstream of lithium ion battery recycling in the next 3-4 years. Currently, the major focus on recycling of lithium ion batteries is on LiCoO2Recovery of cathode material, however, LiCoO is now stage2Has not been the only lithium ion positive electrode material for commercial applications. LiCoO2The lithium ion anode material only accounts for 37.2 percent of the current lithium ion anode material market, and LiNi0.33Mn0.33Co0.33O229.0% LiMn2O421.4% LiNiO2Accounting for 7.2 percent. Therefore, it is necessary to recycle lithium ion battery materials to pay attention to battery components, and at present, no mature technology is available for recycling various waste lithium ion batteries.
The publication number CN106785177A discloses a method for recycling and preparing a nickel-cobalt-manganese-aluminum quaternary material cathode material from a waste nickel-cobalt-manganese ternary lithium ion battery, which is based on a method of technologies such as disassembling, magnetic separation and crushing, organic solvent soaking, screening, sulfuric acid leaching, impurity removal, primary vulcanization and sedimentation, secondary carbonic acid sedimentation, calcination and the like. The method has the main disadvantages that a small amount of iron exists in the front-stage magnetic separation; removing the binder by using an organic solvent to generate a large amount of organic waste liquid; sulfide is adopted to remove copper through sulfuration and sedimentation, partial nickel, cobalt and manganese can be taken away, and a large amount of alkali is consumed by adjusting the pH value with alkali liquor; lithium carbonate burden of secondary sedimentation is on the surface of primary sedimentation, the loss of roasting lithium is serious, and a material with stable performance cannot be obtained; meanwhile, the wastewater generated in the whole process cannot be reused.
In addition, a method for recovering cobalt and lithium from a waste lithium ion battery positive plate is available at present, and the method is based on the processes of mixing and roasting the waste lithium ion battery positive plate and ammonium sulfate, screening, acid leaching, impurity removal, Co precipitation and Li precipitation. The main disadvantage of the process is that the amount of ammonium sulfate required for roasting is large; and the recovery difficulty is high, so the subsequent use of acid leaching is needed, and the alkali consumption of the system is increased. The whole process does not treat the roasting flue gas and solid waste and waste water obtained by subsequent treatment, so that great environmental risks exist.
In summary, conventional waste LiCoO2In the lithium ion battery recovery process, a large amount of acid and alkali are consumed, and a large amount of solid waste and wastewater are generated, which inevitably brings about serious environmental problems.
Disclosure of Invention
The method for recovering valuable metals from the waste lithium ion battery anode material is simple in preparation process, mild in process condition, short in process time, free of large-amount acid and alkali consumption and low in cost, can effectively recover metals and carbon in the anode material lithium cobaltate, lithium manganate, lithium nickelate and ternary materials, is green and environment-friendly, and does not generate a large amount of solid waste and waste water.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for recovering valuable metals from a waste lithium ion battery anode material comprises the following steps:
(1) disassembling at least one of the discharged waste nickel-cobalt-manganese ternary, lithium cobaltate, lithium manganate and lithium nickel-acid lithium ion batteries, separating out a positive plate, and then separating a positive material in the positive plate from an aluminum foil;
(2) mixing the separated positive electrode material with a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium sulfate and/or ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material satisfies { n ((NH))4)2SO4)+n((NH4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.5;
(3) stirring and leaching the obtained roasting material, and then carrying out solid-liquid separation to obtain carbon and a leaching solution;
(4) adjusting the pH value of the obtained leachate, adding a precipitator into the leachate, stirring the solution to precipitate other metal elements except Li, and then carrying out solid-liquid separation;
(5) adjusting the pH value of the filtrate obtained in the step (4) through solid-liquid separation, and adding ammonium carbonate or ammonium bicarbonate or bubbling CO into the filtrate2And precipitating lithium, and after the reaction is finished, carrying out solid-liquid separation to obtain lithium carbonate.
In the above technical solution, specifically, the precipitation of other metal elements except Li may be as follows:
when the waste battery disassembled in the step (1) is a lithium cobalt oxide lithium ion battery, other metal elements except Li are Co;
when the waste battery disassembled in the step (1) is a lithium manganate lithium ion battery, the other metal elements except Li are Mn;
when the waste battery disassembled in the step (1) is a lithium nickel oxide lithium ion battery, other metal elements except Li are Ni;
when the waste battery disassembled in the step (1) is a nickel-cobalt-manganese ternary lithium ion battery, and optionally, a lithium nickelate and/or lithium manganate and/or a lithium cobaltate battery is also disassembled, other metal elements except Li are Ni, Co and Mn;
when the waste batteries disassembled in the step (1) are lithium cobaltate and lithium manganate batteries, other metal elements except Li are Co and Mn;
when the waste batteries disassembled in the step (1) are lithium cobaltate and lithium nickelate batteries, other metal elements except Li are Co and Ni;
when the waste batteries disassembled in the step (1) are lithium manganate and nickel acid lithium batteries, other metal elements except Li are Ni and Mn.
In the above technical solutions, ammonium carbonate or ammonium bicarbonate is preferably added in the form of a solution.
In the above method, preferably, the method further comprises the step (6): and (4) adjusting the pH value of the filtrate obtained after the solid-liquid separation in the step (5) to 5-8, and then evaporating and crystallizing to obtain ammonium sulfate.
In the above method, preferably, when the roasting agent is ammonium bisulfate, the step (6) further comprises a roasting step of calcining the obtained ammonium sulfate to obtain ammonium bisulfate and returning the ammonium bisulfate to the step (2).
In the above method, preferably, when the baking agent is ammonium sulfate, n ((NH)4)2SO4) N (Ni + Co + Mn +2Li) is 1-1.5; when the roasting agent is ammonium bisulfate, n ((NH)4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.4; when the roasting agent is a mixture of ammonium sulfate and ammonium bisulfate, { n ((NH)4)2SO4)+n((NH4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.5.
In the above method, preferably, in the step (4), the precipitant is ammonium oxalate, ammonium hydrogen oxalate, oxalic acid, ammonium carbonate, ammonium hydrogen carbonate, CO2At least one of (1). In the technical scheme, ammonium oxalate, ammonium hydrogen oxalate, oxalic acid, ammonium carbonate and ammonium bicarbonate are preferably added in a solution mode.
In the above method, preferably, the precipitant is ammonium oxalate, the precipitation temperature is 25 ℃ to 90 ℃, and the precipitation time is 0.5h to 3 h.
In the above method, preferably, in the step (2), the roasting temperature of the low-temperature roasting is 350 ℃ to 600 ℃;
and/or the roasting time of the low-temperature roasting is 20 min-120 min.
In the above method, preferably, in the step (3), the stirring water immersion conditions are: the liquid-solid ratio of the water leaching is 5: 1 ml/g-2: 1ml/g, the leaching temperature is 25-70 ℃, and the leaching time is 10-60 min.
In the above method, preferably, in the step (4), NH-containing gas generated by the low-temperature calcination in the step (2) is used3Adjusting the pH value of the flue gas;
and/or in the step (5), the NH containing material generated in the step (2) by low-temperature roasting is used3Regulating the pH value of the flue gas.
In the above method, preferably, in the step (5), the pH value of the precipitated lithium is 10.5 to 12.5, the temperature is 30 to 90 ℃, and the time is 0.5 to 3 hours.
According to the invention, the anode material on the anode piece is effectively separated from the aluminum foil, then is fully mixed with ammonium bisulfate and then is roasted, leaching of metal elements and recovery of carbon are realized through water leaching, and then recovery of valuable metal elements is realized through precipitation.
Compared with the prior art, the invention has the advantages that:
(1) according to the invention, ammonium sulfate or ammonium bisulfate is used for roasting, metal elements such as Co, Ni, Mn and Li in the anode material are converted into water-soluble sulfate, the roasted material is directly soaked by water, the use of acid and alkali is completely avoided, the recovery cost is reduced, the process is simple and easy to operate, the energy consumption is low, a large amount of secondary solid waste and waste water is avoided, the environment is friendly, the safety is good, and the industrial application prospect is very high.
(2) The method not only effectively recovers valuable metals in the anode material of the waste battery, but also realizes the recovery of carbon in the anode material.
(3) The inventor discovers through research that if the aluminum foil of the positive plate is not separated from the positive active material, the amount of ammonium sulfate or ammonium bisulfate required by roasting is increased, the aluminum foil and the active material cannot be effectively separated after roasting, the recovery rate of the active material is reduced, and meanwhile, the aluminum foil reacts with the positive active material in the roasting process, so that the recovery difficulty is increased.
(4) NH contained by roasting in the invention3The flue gas can be used for adjusting the pH value, the metal sulfate formed by roasting is subjected to water leaching and multiple precipitation, the metal is recovered, the sulfate radical is still remained in the solution to finally form ammonium sulfate, the reutilization is realized through recrystallization, the environment-friendly atom economic characteristic is realized, the closed loop is completely closed, no waste gas exists, and the process is simple and convenient to operate,And (4) discharging waste water and solid waste.
(5) In the invention, ammonium oxalate is preferably used as a precipitator, on one hand, the oxalate precipitation effect is best, on the other hand, because the pH values of the precipitates corresponding to Ni, Co and Mn are different when the oxalate precipitation is adopted, the three can be effectively separated, and in addition, ammonium ions are used as cations, so that the subsequent recovery of ammonium sulfate is convenient.
Drawings
Fig. 1 is a process flow diagram of a method for recovering valuable metals from ternary materials of positive electrode materials of waste lithium ion batteries in embodiment 3 of the invention.
Fig. 2 is a schematic process flow diagram of a method for recovering valuable metals from lithium manganate, which is a waste lithium ion battery positive electrode material, in embodiment 5 of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific examples.
Example 1
The invention relates to a method for recovering valuable metals from a waste lithium ion battery anode material lithium cobaltate, which comprises the following steps:
(1) discharging lithium cobalt oxide lithium ion waste batteries by using 100g/L salt solution; disassembling and removing the metal shell (or soft package shell), and separating out the positive plate, the negative plate, the diaphragm and the electrolyte; and crushing the obtained positive plate, and screening to separate the aluminum foil and the positive material.
(2) The separated positive electrode material was mixed with ammonium bisulfate in accordance with the formula of n ((NH)4)HSO4) Mixing the mixture with the molar ratio of 1.1/n (Co +2Li), and roasting in a tubular furnace at 500 ℃ for 1 h.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out liquid-solid separation on the slurry which is completely reacted to obtain carbon slag and a leaching solution containing Co and Li, and recovering the carbon slag. Wherein the leaching rate of Co is 98.6 percent, and the leaching rate of Li is 99.2 percent.
(4) And (4) adding an ammonium oxalate solution into the leachate obtained in the step (3), stirring and reacting for 2 hours at the temperature of 60 ℃, and after the reaction is finished, carrying out solid-liquid separation to obtain a cobalt oxalate product and a filtrate, wherein the recovery rate is 99.5%.
(5) NH collected in the roasting stage3And (4) introducing the filtrate obtained in the step (4), adjusting the pH value to 11.5, then adding an ammonium carbonate solution to precipitate lithium, reacting for 2 hours at the temperature of 70 ℃, and after the reaction is finished, carrying out solid-liquid separation to obtain a lithium carbonate product and a post-liquid, wherein the recovery rate is 95.7%.
(6) And (3) adjusting the pH value of the filtrate obtained by filtering in the step (5) to 5-8 by using ammonia-containing flue gas, then heating for crystallization, calcining the obtained crystallization product at 300 ℃ for 1h to obtain an ammonium bisulfate product, crushing for later use, and returning to the roasting and mixing process in the step (2).
In this embodiment, the positive electrode material on the positive electrode plate is effectively separated from the aluminum foil, and then is fully mixed with ammonium bisulfate to perform liquid-solid and gas-solid reactions at a proper baking temperature, so that valuable elements in the positive electrode material are converted into water-soluble sulfate, and the doped carbon powder does not react. Therefore, the leaching of valuable elements can be realized by using water.
Example 2
The invention relates to a method for recovering valuable metals from lithium manganate used as a positive material of a waste lithium ion battery, which comprises the following steps:
(1) discharging the lithium manganate lithium ion waste battery by using 100g/L of salt water; disassembling and removing the metal shell (or soft package shell), and separating out the positive plate, the negative plate, the diaphragm and the electrolyte; the obtained positive electrode sheet was pulverized and sieved to separate the aluminum foil and the positive electrode material.
(2) The obtained positive electrode material was mixed with ammonium bisulfate in accordance with the formula of n ((NH)4)HSO4) Mixing the mixture with the concentration of 1.2/n (Mn +2Li), and roasting in a tube furnace at 500 ℃ for 1 h.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out liquid-solid separation on the slurry which is completely reacted to obtain carbon slag and leaching solution containing Mn and Li, and recycling the carbon slag. Wherein the leaching rate of Mn is 99.4 percent, and the leaching rate of Li is 99.5 percent.
(4) Using a catalyst containing NH3Adjusting the pH value of the flue gas to 8-10 and containing NH3And (3) adding an ammonium oxalate solution into the obtained leaching solution, stirring and reacting for 2 hours at 40 ℃, and after the reaction is finished, carrying out solid-liquid separation to obtain a manganese oxalate product and a filtrate, wherein the recovery rate is 99.2%.
(5) NH collected in the roasting stage3And (4) introducing the filtrate obtained in the step (4), adjusting the pH value to 11.5, adding an ammonium carbonate solution to precipitate lithium, reacting for 2 hours at the temperature of 90 ℃, and after the reaction is finished, carrying out solid-liquid separation to obtain a lithium carbonate product with the recovery rate of 96.5%.
(6) And (3) adjusting the pH value of the filtrate obtained by filtering in the step (5) to 5-8 by using ammonia-containing flue gas, then heating for crystallization, calcining the obtained crystallization product at 300 ℃ for 1h to obtain an ammonium bisulfate product, and crushing for later use.
Example 3
The invention discloses a method for recovering valuable metals from ternary materials of anode materials of waste lithium ion batteries, which has a process flow diagram shown in figure 1 and comprises the following steps:
(1) discharging the nickel-cobalt-manganese ternary lithium ion waste battery by using 100g/L salt solution, disassembling and removing a metal shell (or a soft package shell), and separating out a positive plate, a negative plate, a diaphragm and electrolyte. And crushing the obtained positive plate, and screening out the aluminum foil and the positive material.
(2) The obtained positive electrode material was mixed with ammonium bisulfate in accordance with the formula of n ((NH)4)HSO4) Mixing the mixture with/n (Ni + Co + Mn +2Li) ═ 1.3, and roasting in a tube furnace at the temperature of 550 ℃ for 2 h.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out solid-liquid separation on the slurry which is completely reacted to obtain carbon slag and leaching solution containing Ni, Co, Mn and Li, and recycling the carbon slag. Wherein the leaching rate of Ni is 99.4%, the leaching rate of Co is 99.2%, the leaching rate of Mn is 99.5%, and the leaching rate of Li is 98.9%.
(4) Using a catalyst containing NH3Regulating the pH value of the flue gas to be 5-10 and containing NH3And (3) adding an ammonium oxalate solution into the obtained leachate, stirring and reacting for 2 hours at the temperature of 60 ℃, and filtering after the reaction is finished to obtain cobalt oxalate, nickel oxalate and manganese oxalate products and filtrate, wherein the recovery rates are 99.5%, 98.6% and 98.5% respectively.
(5) NH collected in the roasting section in the step (2)3And (4) introducing into the filtrate obtained in the step (4), adjusting the pH value to 11.5, adding an ammonium carbonate solution to precipitate lithium, reacting for 2 hours at the temperature of 70 ℃, and filtering after the reaction is finished to obtain a lithium carbonate product with the recovery rate of 97.9%.
(6) Using a catalyst containing NH3And (3) adjusting the pH value of the filtrate obtained by filtering in the step (5) to 5-8 by using flue gas, then heating and crystallizing, calcining the obtained crystallized product at 300 ℃ for 1h to obtain an ammonium bisulfate product, and crushing the ammonium bisulfate product for later use, wherein the ammonium bisulfate product can be used as a roasting agent in the step (2).
In this embodiment, the ammonium oxalate solution may be replaced by oxalic acid; the ammonium carbonate solution can be ammonium bicarbonate solution or CO2And (4) replacing.
Example 4
The invention relates to a method for recovering valuable metals from a waste lithium ion battery anode material lithium cobaltate, which comprises the following steps:
(1) the lithium cobalt oxide lithium ion waste battery is subjected to discharge treatment by using 100g/L of salt solution, a metal shell (or a soft package shell) is disassembled and removed, and a positive plate, a negative plate, a diaphragm and electrolyte are separated. And crushing the obtained positive plate, and screening out the aluminum foil and the positive material.
(2) The obtained positive electrode material was mixed with ammonium bisulfate in accordance with the formula of n ((NH)4)2SO4) Mixing the mixture with the/n (Co +2Li) ═ 1.3, and roasting in a tube furnace, wherein the roasting temperature is 650 ℃ and the roasting time is 2 hours.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out liquid-solid separation on the slurry which is completely reacted to obtain carbon slag and a leaching solution containing Co and Li, and recovering the carbon slag. Wherein the leaching rate of Co is 98.6 percent, and the leaching rate of Li is 99.2 percent.
(4) Adding ammonium oxalate solution into the obtained leaching solution to precipitate lithium, stirring and reacting for 2 hours at the temperature of 60 ℃, and after the reaction is finished, carrying out liquid-solid separation to obtain a cobalt oxalate product and a filtrate, wherein the recovery rates are respectively 99.5%.
(5) NH collected in the roasting section in the step (2)3And (4) introducing the lithium carbonate into the filtrate obtained in the step (4), adjusting the pH to 11.5, adding an ammonium carbonate solution, reacting for 2 hours at the temperature of 70 ℃, and after the reaction is finished, carrying out liquid-solid separation to obtain a lithium carbonate product, wherein the recovery rate is 95.7%.
(6) And (3) adjusting the pH value of the liquid obtained after liquid-solid separation in the step (5) to 5-8 by using ammonia-containing flue gas, then heating and crystallizing to obtain an ammonium sulfate product, and crushing the ammonium sulfate product for later use, wherein the ammonium sulfate product can be used as a roasting agent in the step (2).
Example 5
The invention relates to a method for recovering valuable metals from lithium manganate used as a positive material of a waste lithium ion battery, which comprises the following steps:
(1) the lithium manganate lithium ion waste battery is subjected to discharge treatment by using 100g/L of salt solution, a metal shell (or a soft package shell) is disassembled and removed, and a positive plate, a negative plate, a diaphragm and electrolyte are separated. And crushing the obtained positive plate, and screening out the aluminum foil and the positive material.
(2) The obtained positive electrode material was mixed with ammonium bisulfate in accordance with the formula of n ((NH)4)2SO4) Mixing the mixture with the concentration of 1.1/n (Mn +2Li), and roasting in a tubular furnace at the low-temperature of 550 ℃ for 2 h.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out solid-liquid separation on the slurry which is completely reacted to obtain carbon slag and leaching solution containing Mn and Li, and recycling the carbon slag. Wherein the leaching rate of Mn is 99.4 percent, and the leaching rate of Li is 99.5 percent.
(4) Using NH-containing gas collected at the roasting stage in step (2)3Adjusting the pH value of the flue gas to 8-10, adding an ammonium oxalate solution into the obtained leaching solution, stirring and reacting for 2 hours at 40 ℃, and filtering after the reaction is finished to obtain a manganese oxalate product and a filtrate, wherein the recovery rate is 99.2%.
(5) NH contained in the roasting section collected in the step (2)3And (4) introducing the flue gas into the filtrate obtained in the step (4), adjusting the pH to 11.5, adding an ammonium carbonate solution to precipitate lithium, reacting for 2 hours at 90 ℃, and filtering after the reaction is finished to obtain a lithium carbonate product, wherein the recovery rate is 96.5%.
(6) Using a catalyst containing NH3And (3) adjusting the pH value of the filtrate obtained by filtering in the step (5) to 5-8 by using flue gas, then heating and crystallizing to obtain an ammonium sulfate product, and crushing the ammonium sulfate product for later use, wherein the ammonium sulfate product can be used as a roasting agent in the step (2).
In this embodiment, the ammonium oxalate solution may be replaced by oxalic acid; the ammonium carbonate solution can be ammonium bicarbonate solution or CO2And (4) replacing.
Example 6
The invention relates to a method for recovering valuable metals from ternary materials of anode materials of waste lithium ion batteries, which comprises the following steps:
(1) discharging the nickel-cobalt-manganese ternary lithium ion waste battery by using 100g/L salt solution, disassembling and removing a metal shell (or a soft package shell), and separating out a positive plate, a negative plate, a diaphragm and electrolyte. And crushing the obtained positive plate, and screening out the aluminum foil and the positive material.
(2) The obtained positive electrode material was mixed with ammonium sulfate in the ratio of n ((NH)4)2SO4) Mixing the mixture with the concentration of 1.2/n (Ni + Co + Mn +2Li), and roasting in a tubular furnace at the roasting temperature of 600 ℃ for 2 h.
(3) Crushing the obtained roasted material, mixing with pure water (or tap water) at a liquid-solid ratio of 3: 1ml/g, and leaching under stirring in water bath at 60 deg.C for 30 min. And after leaching, carrying out liquid-solid separation on the slurry which is completely reacted to obtain carbon slag and leachate containing Ni, Co, Mn and Li, and recycling the carbon slag. Wherein, the leaching rate of Ni is 99.4%, the leaching rate of Co is 99.2%, the leaching rate of Mn is 99.5%, and the leaching rate of Li is 98.9%.
(4) Using a catalyst containing NH3Adjusting the pH value of the flue gas to 5-10, adding an ammonium oxalate solution into the obtained leaching solution, stirring and reacting for 2 hours at the temperature of 60 ℃, and after the reaction is finished, carrying out liquid-solid separation. The cobalt oxalate, nickel oxalate, manganese oxalate products and the leached filtrate are obtained by separation, and the recovery rates are respectively 99.3%, 98.9% and 98.7%.
(5) NH collected in the roasting section in the step (2)3And (4) introducing into the filtrate obtained in the step (4), adjusting the pH value to 11.5, adding an ammonium carbonate solution to precipitate lithium, reacting for 2 hours at the temperature of 90 ℃, and after the reaction is finished, carrying out liquid-solid separation to obtain a lithium carbonate product, wherein the recovery rate is 97.4%.
(6) And (3) adjusting the pH value of the liquid obtained by liquid-solid separation in the step (5) to 5-8 by using ammonia-containing flue gas, then heating and crystallizing to obtain an ammonium sulfate product, and crushing the ammonium sulfate product for later use, wherein the ammonium sulfate product can be used as a roasting agent in the step (2).
The foregoing is merely a preferred embodiment of the invention and is not intended to limit the invention in any manner. Although the present invention has been described with reference to the preferred embodiments, it is not intended to be limited thereto. Those skilled in the art can make many possible variations and modifications to the disclosed embodiments, or equivalent modifications, without departing from the spirit and scope of the invention, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent replacement, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention.

Claims (8)

1. A method for recovering valuable metals from a waste lithium ion battery anode material is characterized by comprising the following steps:
(1) disassembling at least one of the discharged waste nickel-cobalt-manganese ternary, lithium cobaltate, lithium manganate and lithium nickel-acid lithium ion batteries, separating out a positive plate, and then separating a positive material in the positive plate from an aluminum foil;
(2) separating the obtained positive electrodeMixing the material with a roasting agent, and roasting at low temperature to obtain a roasted material, wherein the roasting agent is ammonium sulfate and/or ammonium bisulfate, and the quantity of the roasting agent and the positive electrode material satisfies { n ((NH))4)2SO4)+n((NH4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.5; the roasting temperature of the low-temperature roasting is 350-500 ℃, and the roasting time of the low-temperature roasting is 20-60 min;
(3) stirring and leaching the obtained roasting material, and then carrying out solid-liquid separation to obtain carbon and a leaching solution;
(4) adjusting the pH value of the obtained leachate, adding a precipitator into the leachate, stirring the solution to precipitate other metal elements except Li, and then carrying out solid-liquid separation; in the step (4), NH-containing gas generated by the low-temperature roasting in the step (2) is used3Adjusting the pH value of the flue gas; the precipitant is ammonium oxalate, ammonium hydrogen oxalate, oxalic acid, ammonium carbonate, ammonium bicarbonate and CO2At least one of;
(5) adjusting the pH value of the filtrate obtained in the step (4) through solid-liquid separation, and adding ammonium carbonate or ammonium bicarbonate or bubbling CO into the filtrate2And precipitating lithium, and after the reaction is finished, carrying out solid-liquid separation to obtain lithium carbonate.
2. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries according to claim 1, characterized by further comprising the step (6): and (3) adjusting the pH value of the filtrate obtained after the solid-liquid separation in the step (5) to 5-8, and then evaporating and crystallizing to obtain ammonium sulfate.
3. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries according to claim 2, wherein when the roasting agent is ammonium bisulfate, the step (6) further comprises calcining the obtained ammonium sulfate to obtain ammonium bisulfate, and returning the ammonium bisulfate to the roasting process in the step (2).
4. The method for recovering valuable metals from the anode materials of waste lithium ion batteries according to claim 1, wherein when the roasting agent is sulfurAt ammonium salt, n ((NH)4)2SO4) N (Ni + Co + Mn +2Li) is 1-1.5; when the roasting agent is ammonium bisulfate, n ((NH)4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.4; when the roasting agent is a mixture of ammonium sulfate and ammonium bisulfate, { n ((NH)4)2SO4)+n((NH4)HSO4) N (Ni + Co + Mn +2Li) is 0.9-1.5.
5. The method for recovering valuable metals from the anode materials of the waste lithium ion batteries according to claim 1, wherein the precipitator is ammonium oxalate, the temperature of the precipitation is 25-90 ℃, and the time of the precipitation is 0.5-3 h.
6. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries according to any one of claims 1 to 5, wherein in the step (3), the stirring water immersion conditions are as follows: the liquid-solid ratio of the water leaching is 5: 1 ml/g-2: 1ml/g, the leaching temperature is 25-70 ℃, and the leaching time is 10-60 min.
7. The method for recovering valuable metals from waste lithium ion battery positive electrode materials according to any one of claims 1 to 5, wherein in the step (5), NH-containing substances generated by the low-temperature roasting in the step (2) are used3Regulating the pH value of the flue gas.
8. The method for recovering valuable metals from the positive electrode materials of the waste lithium ion batteries according to any one of claims 1 to 5, wherein in the step (5), the pH value of the precipitated lithium is 10.5-12.5, the temperature is 30-90 ℃, and the time is 0.5-3 h.
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