CN110247129B - Method for recycling positive active substances of waste lithium ion batteries - Google Patents

Method for recycling positive active substances of waste lithium ion batteries Download PDF

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CN110247129B
CN110247129B CN201910514638.XA CN201910514638A CN110247129B CN 110247129 B CN110247129 B CN 110247129B CN 201910514638 A CN201910514638 A CN 201910514638A CN 110247129 B CN110247129 B CN 110247129B
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lithium ion
lithium
solid
ion battery
anode
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CN110247129A (en
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刘葵
张鹏
范小萍
史莹
王红强
黄有国
蔡业政
吴强
李庆余
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Guangxi Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/08—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • C01G51/40—Cobaltates
    • C01G51/42—Cobaltates containing alkali metals, e.g. LiCoO2
    • C01G51/44—Cobaltates containing alkali metals, e.g. LiCoO2 containing manganese
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    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • C22B7/006—Wet processes
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
    • C25C1/10—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of chromium or manganese
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • 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 discloses a method for recycling positive active substances of waste lithium ion batteries, which comprises the following steps: 1) leaching the positive plate of the waste lithium ion battery or the substance stripped from the positive plate by using a hydrochloric acid solution to obtain a leaching solution, and collecting the gas generated in the leaching process; 2) electrolyzing by taking the leachate as electrolyte, and respectively collecting gases generated on the anode sheet and the cathode sheet; 3) carrying out solid-liquid separation on the material obtained by electrolysis, and respectively collecting liquid and solid; 4) using the collected gas for producing hydrochloric acid solution; 5) the obtained hydrochloric acid solution is sold as a product or is prepared and then returns to the step 1) for use; 6) preparing the electrolyzed liquid into lithium carbonate and/or lithium hydroxide; 7) and calcining the electrolyzed solid and the product obtained in the step 6) to obtain the anode active substance. The method has simple process, and the closed-loop production of the lithium ion battery is realized by utilizing the waste lithium ion battery to prepare the positive active material of the lithium ion battery again.

Description

Method for recycling positive active substances of waste lithium ion batteries
Technical Field
The invention relates to recovery treatment of waste lithium ion batteries, in particular to a method for recycling positive active substances of waste lithium ion batteries.
Background
The lithium ion battery has the characteristics of high energy density, high working voltage, long service life, no memory effect and the like, has performance superior to that of other various secondary batteries, and is widely applied to the fields of electronic equipment such as mobile phones and notebooks, electric automobiles, hybrid electric automobiles and the like.
With the development of lithium ion battery technology, the lithium ion battery anode material is developed from lithium cobaltate, lithium manganate, lithium iron phosphate, binary anode material to the third generation anode material, ternary NCM/NCA anode material era. Particularly, the cathode materials of NCM111 and NCM523, which have been mass-produced, have the advantages of long cycle life, high stability, strong conductivity and the like, and have been widely used as power core components of portable energy storage products and new energy electric vehicles. Lithium ion batteries are consumables, the service life of which is generally 3 to 5 years. With the development of national economy, the consumption of secondary batteries is gradually increased, and the number of generated waste lithium ion batteries is also greatly increased. The recovery amount of the power lithium ion battery in 2019 is expected to reach 11GWH, which accounts for about 1/3 of the total recovery amount of the whole lithium ion battery. With the advancement of new energy automobiles in China, the recovery amount of the power type lithium ion battery is expected to reach 32.2GWh, nearly 50 million tons in 2020. The waste lithium ion battery contains a large amount of valuable metals such as cobalt, nickel, manganese, lithium, aluminum, copper and the like, and the valuable metals belong to secondary resources and have remarkable economic benefit on recycling. If the waste lithium ion battery is improperly disposed, not only can resources be wasted, but also the environment can be seriously polluted, and finally the waste lithium ion battery is gathered in a human body through a long-time biological chain enrichment effect, so that the health of the human body is seriously damaged.
In the prior art, metals such as lithium, nickel, cobalt, manganese, iron and the like in the positive active material of the lithium ion battery are usually leached by adopting an acid solution, transferred into the solution in the form of ions, and then the metal ions in the solution are separated by adopting a precipitation method or a solvent extraction method. The precipitation method needs to add an alkaline precipitator for multiple times to precipitate iron, nickel, cobalt, manganese and other ions respectively, and has the defects of high consumption of the precipitator and high entrainment loss of lithium in the precipitation process; the solvent extraction method can separate metal ions one by one, but the process flow is longer. In addition, in the existing process for recycling the waste lithium ion batteries, residual acid in the leachate cannot be fully utilized, and the existence of the residual acid also influences the subsequent procedures of precipitating and separating metals such as nickel, cobalt and manganese or separating metals such as nickel, cobalt and manganese by adopting a solvent extraction method.
Therefore, a method for realizing closed-loop production of the lithium ion battery by using the waste lithium ion battery to prepare the positive active material of the lithium ion battery with simple process is needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a method for recycling the anode active substance of a waste lithium ion battery, which has simple process, prepares the anode active substance of the lithium ion battery again by using the waste lithium ion battery and realizes the closed-loop production of the lithium ion battery, aiming at the defects in the existing acid leaching process.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for recycling positive active substances of waste lithium ion batteries comprises the following steps:
1) leaching the positive plate of the waste lithium ion battery or the substance stripped from the positive plate by using a hydrochloric acid solution to obtain a leaching solution, and collecting gas generated in the leaching process;
2) taking the leachate as electrolyte, inserting an anode and a cathode into the leachate, electrifying the anode and the cathode for electrolysis, and respectively collecting gases generated on the anode piece and the cathode piece in the electrolysis process;
3) after the electrolysis is finished, performing solid-liquid separation on the material obtained by the electrolysis, and respectively collecting liquid and solid, wherein the liquid is a lithium-containing solution, and the solid is a mixture or deposit of other valuable metals;
4) sending the gas collected in the step 1), the gas generated on the anode sheet collected in the step 2) and the gas generated on the cathode sheet collected in the step 2) into a synthesis kettle to generate hydrogen chloride gas, then sending the generated hydrogen chloride gas into an absorption tower, and absorbing the hydrogen chloride gas with water to prepare hydrochloric acid solution;
5) the hydrochloric acid solution obtained in the step 4) is sold as a hydrochloric acid product, or is prepared into a corresponding concentration and then returns to the step 1) for use;
6) preparing the liquid collected in the step 3) into lithium carbonate and/or lithium hydroxide according to the prior art;
7) and (3) calcining the solid collected in the step 3) and the lithium carbonate and/or lithium hydroxide obtained in the step 6) in an oxygen-containing atmosphere to obtain the positive electrode active material.
In the method, the waste lithium ion battery can be a lithium ion battery with an active substance of nickel cobalt lithium manganate, and can also be a lithium ion battery with an active substance of lithium cobalt oxide or lithium manganate. When the positive active material of the waste lithium ion battery is nickel cobalt lithium manganate, performing solid-liquid separation to obtain a solid which is a mixture of nickel, cobalt and manganese; when the positive active material of the waste lithium ion battery is lithium cobaltate or lithium manganate, the solid obtained by solid-liquid separation is a cobalt deposit or a manganese deposit correspondingly.
In step 1) of the method of the present invention, the concentration of the hydrochloric acid solution is the same as that of the prior art, and is preferably 0.5 to 5 mol/L. The positive plate of the waste lithium ion battery or the substance stripped from the positive plate is obtained by the conventional method, and the waste lithium ion battery is generally discharged firstly, then disassembled, and then the positive plate is collected, or the substance on the positive plate is further collected. When the positive electrode plate is leached, in order to facilitate leaching, the positive electrode plate is preferably crushed and then leached. The leaching can be carried out under the condition of heating or not, particularly under the condition of 25-95 ℃, and the leaching time is determined according to the requirement, is preferably more than or equal to 30min, and is more preferably 1-7 h.
In step 2) of the method of the present invention, the selection of the anode and the cathode is the same as that of the prior art, and usually a platinum sheet or a graphite sheet is used as the anode, and an aluminum sheet or a copper sheet or a graphite sheet is used as the cathode. In this step, the power source for connecting the anode and the cathode is a DC power source, and the voltage is the same as that of the prior art, and the electrolysis is preferably performed under the condition of 1-40V, and more preferably under the condition of 5-32V. The electrolysis time is usually more than or equal to 10min, preferably 30-90min, and the separation of lithium and other valuable metals (such as nickel, cobalt or manganese and the like) in the active material can be realized in the time range.
In the step 4) of the method, the collected gas is sent into a synthesis kettle to synthesize hydrogen chloride gas according to the conventional process, and then the generated hydrogen chloride gas is sent into an absorption tower to be absorbed by water according to the conventional process to prepare the hydrochloric acid solution.
In step 7) of the process of the present invention, the calcination is typically carried out at 300-.
Compared with the prior art, the invention is characterized in that:
1. the method has wide application range, and the waste lithium ion batteries containing different active substances can be used for separating lithium and other metals.
2. According to the method, the lithium in the acid leaching solution of the positive active material is quickly and completely separated from other metals by a one-step electrolysis method, and the lithium is retained in the solution and can be subsequently used for preparing lithium carbonate or lithium hydroxide; the nickel, cobalt and manganese enter the slag in the form of mixture or deposit, and can be subsequently used for preparing lithium cobaltate or lithium manganate or nickel, cobalt and manganese oxide serving as a precursor of a nickel, cobalt and manganese lithium anode material. The whole method has the advantages of few separation steps, short production period, low cost and less lithium loss.
3. The gas generated in the acid leaching process and the gas generated in the electrolysis process are both used for preparing the hydrochloric acid solution and can be reused in the acid leaching process of the anode material of the waste battery, so that the residual acid in the leaching process is recycled, and the secondary pollution in the existing acid leaching process and the existing electrolysis process is avoided.
4. Because lithium is separated from other metals in the electrolysis process, and other metals are recovered in the form of mixture or deposit to become a precursor of the battery anode material, the precursor can be mixed with lithium carbonate to prepare the lithium ion battery anode active substance again, valuable metals in waste batteries are effectively recovered, and the closed-loop application of the lithium ion battery is realized.
Detailed Description
The present invention will be better understood from the following detailed description of specific examples, which should not be construed as limiting the scope of the present invention.
Example 1
1) Discharging waste nickel cobalt lithium manganate batteries according to the conventional technology, then disassembling, collecting the positive plates, crushing, dissolving the obtained crushed materials with 3mol/L hydrochloric acid solution at 80 ℃ for 1h, transferring metals such as lithium, nickel, cobalt, manganese and the like into liquid, filtering, collecting the liquid, namely leachate, and collecting gas generated in the leaching process;
2) taking a platinum sheet as an anode, an aluminum sheet as a cathode, taking the leachate obtained in the step 1) as an electrolyte, electrifying the anode and the cathode, and electrolyzing for 80min under the condition that the voltage is 20V; simultaneously, respectively collecting gas generated on the anode plate and gas generated on the cathode plate in the electrolysis process;
3) after the electrolysis is finished, filtering the material obtained by the electrolysis, and respectively collecting liquid and solid, wherein the liquid is a lithium-containing solution, and the solid is a mixture of nickel, cobalt and manganese;
4) sending the gas collected in the step 1), the gas generated on the anode sheet collected in the step 2) and the gas generated on the cathode sheet collected in the step 2) into a synthesis kettle to synthesize hydrogen chloride gas according to the conventional process, then sending the generated hydrogen chloride gas into an absorption tower, and absorbing the hydrogen chloride gas with water according to the conventional process to prepare a hydrochloric acid solution (6 mol/L);
5) selling a part of the hydrochloric acid solution obtained in the step 4) as a hydrochloric acid product, and mixing the rest part according to the ratio of 1: 1, uniformly mixing the mixture with water according to the volume ratio of 1, and returning to the step 1) for repeated use;
6) sending the lithium-containing solution obtained in the step 3) into a lithium carbonate production procedure to prepare lithium carbonate according to the conventional process;
7) introducing the mixture of nickel, cobalt and manganese obtained in the step 3) and the lithium carbonate prepared in the step 6) into a sintering furnace, introducing air, heating to 1200 ℃, and carrying out heat preservation and calcination for 2h to obtain the nickel cobalt lithium manganate positive electrode active material.
Example 2
1) Discharging waste lithium cobaltate batteries according to the conventional technology, then disassembling, collecting positive plates therein, crushing, dissolving the obtained crushed materials with 4mol/L hydrochloric acid solution at 70 ℃ for 1.5h, transferring metals such as lithium, cobalt and the like into liquid, filtering, collecting the liquid, namely leachate, and collecting gas generated in the leaching process;
2) taking a graphite sheet as an anode, an aluminum sheet as a cathode, taking the leachate obtained in the step 1) as electrolyte, electrifying the anode and the cathode, and electrolyzing for 40min under the condition that the voltage is 15V; simultaneously, respectively collecting gas generated on the anode plate and gas generated on the cathode plate in the electrolysis process;
3) after the electrolysis is finished, filtering the material obtained by the electrolysis, and respectively collecting liquid and solid, wherein the liquid is a lithium-containing solution, and the solid is a cobalt deposit;
4) sending the gas collected in the step 1), the gas generated on the anode sheet collected in the step 2) and the gas generated on the cathode sheet collected in the step 2) into a synthesis kettle to synthesize hydrogen chloride gas according to the conventional process, then sending the generated hydrogen chloride gas into an absorption tower, and absorbing the hydrogen chloride gas with water according to the conventional process to prepare a hydrochloric acid solution (6 mol/L);
5) selling a part of the hydrochloric acid solution obtained in the step 4) as a hydrochloric acid product, and mixing the rest part according to the ratio of 2: 1, uniformly mixing the mixture with water according to the volume ratio of 1, and returning to the step 1) for repeated use;
6) sending the lithium-containing solution obtained in the step 3) into a lithium carbonate production procedure to prepare lithium carbonate according to the conventional process;
7) introducing the cobalt deposit obtained in the step 3) and the lithium carbonate prepared in the step 6) into a sintering furnace, introducing air, heating to 900 ℃, and carrying out heat preservation and calcination for 4 hours to obtain the lithium cobaltate positive electrode active substance.
Example 3
1) Discharging waste lithium manganate batteries according to the conventional technology, disassembling, collecting positive plates therein, crushing, dissolving the obtained crushed materials with 1.5mol/L hydrochloric acid solution at 50 ℃ for 2.5h, transferring metals such as lithium, manganese and the like into liquid, filtering, collecting the liquid, namely leachate, and collecting gas generated in the leaching process;
2) taking a graphite sheet as an anode, an aluminum sheet as a cathode, taking the leachate obtained in the step 1) as electrolyte, electrifying the anode and the cathode, and electrolyzing for 15min under the condition that the voltage is 30V; simultaneously, respectively collecting gas generated on the anode plate and gas generated on the cathode plate in the electrolysis process;
3) after the electrolysis is finished, filtering the material obtained by the electrolysis, and respectively collecting liquid and solid, wherein the liquid is a lithium-containing solution, and the solid is a manganese deposit;
4) sending the gas collected in the step 1), the gas generated on the anode sheet collected in the step 2) and the gas generated on the cathode sheet collected in the step 2) into a synthesis kettle to synthesize hydrogen chloride gas according to the conventional process, then sending the generated hydrogen chloride gas into an absorption tower, and absorbing the hydrogen chloride gas with water according to the conventional process to prepare a hydrochloric acid solution (2 mol/L);
5) selling a part of the hydrochloric acid solution obtained in the step 4) as a hydrochloric acid product, and mixing the rest part according to the weight ratio of 7: 1, uniformly mixing the mixture with water according to the volume ratio of 1, and returning to the step 1) for repeated use;
6) sending the lithium-containing solution obtained in the step 3) into a lithium carbonate production process to prepare lithium hydroxide according to the conventional process;
7) introducing the manganese deposit obtained in the step 3) and the lithium hydroxide prepared in the step 6) into a sintering furnace, introducing air, heating to 1400 ℃, and carrying out heat preservation and calcination for 2.5 hours to obtain the nickel cobalt lithium manganate positive electrode active material.

Claims (4)

1. A method for recycling positive active substances of waste lithium ion batteries comprises the following steps:
1) leaching the positive plate of the waste lithium ion battery or the substance stripped from the positive plate by using a hydrochloric acid solution to obtain a leaching solution, and collecting gas generated in the leaching process;
2) taking the leachate as electrolyte, inserting an anode and a cathode into the leachate, electrifying the anode and the cathode for electrolysis, and respectively collecting gases generated on the anode piece and the cathode piece in the electrolysis process; the electrolysis is carried out under the condition that the voltage is 1-40V;
3) after the electrolysis is finished, performing solid-liquid separation on the material obtained by the electrolysis, and respectively collecting liquid and solid, wherein the liquid is a lithium-containing solution, and the solid is a mixture or deposit of other valuable metals;
4) sending the gas collected in the step 1), the gas generated on the anode sheet collected in the step 2) and the gas generated on the cathode sheet collected in the step 2) into a synthesis kettle to generate hydrogen chloride gas, then sending the generated hydrogen chloride gas into an absorption tower, and absorbing the hydrogen chloride gas with water to prepare hydrochloric acid solution;
5) the hydrochloric acid solution obtained in the step 4) is sold as a hydrochloric acid product, or is prepared into a corresponding concentration and then returns to the step 1) for use;
6) preparing the liquid collected in the step 3) into lithium carbonate and/or lithium hydroxide according to the prior art;
7) calcining the solid collected in the step 3) and the lithium carbonate and/or lithium hydroxide obtained in the step 6) in an aerobic atmosphere to obtain a positive electrode active material;
when the positive active material of the waste lithium ion battery is nickel cobalt lithium manganate, performing solid-liquid separation to obtain a solid which is a mixture of nickel, cobalt and manganese; when the positive active material of the waste lithium ion battery is lithium cobaltate or lithium manganate, the solid obtained by solid-liquid separation is a cobalt deposit or a manganese deposit correspondingly.
2. The method of claim 1, wherein: the electrolysis time is more than or equal to 10 min.
3. The method of claim 1, wherein: the electrolysis time is 30-90 min.
4. The method according to any one of claims 1-3, wherein: platinum sheet or graphite sheet is used as anode, and aluminum sheet or copper sheet or graphite sheet is used as cathode.
CN201910514638.XA 2019-06-14 2019-06-14 Method for recycling positive active substances of waste lithium ion batteries Active CN110247129B (en)

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