CN112251776A - Method for recovering metal from waste lithium battery positive electrode material - Google Patents
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- 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
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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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
- 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
- C25C1/02—Electrolytic production, recovery or refining of metals by electrolysis of solutions of light metals
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to a method for recovering metal from a waste lithium battery anode material, and belongs to the technical field of waste lithium battery recovery. The method of the invention comprises the following steps: (1) preparing raw materials: coating a waste anode material on an electrode to prepare a cathode, inserting the cathode into electrolyte, and adopting a carbon rod as an anode; (2) electrolysis-electrodeposition: electrifying first, and dissolving the anode material; then the current direction is changed, and attachments are gradually generated on the other electrode, and the cycle is repeated until the anode material is completely dissolved; (3) collecting: after electrolysis-electrodeposition is finished, collecting attachments and electrolyte on the carbon rod; (4) preparation of a product: calcining the obtained attachment at high temperature to obtain metal; and adding alkali and sodium carbonate into the electrolyte to obtain lithium carbonate. The method realizes the dissolution and separation of lithium and heavy metal in one step by the electrolysis-electrodeposition of the anode material, and finally recovers the lithium and the heavy metal.
Description
Technical Field
The invention relates to the technical field of waste lithium ion battery recovery, in particular to a method for recovering metal from a positive electrode material of a waste lithium battery.
Background
The lithium ion battery has the characteristics of high energy density, long cycle life and no memory effect, and is widely applied to digital products such as mobile phones, computers, flat panels and the like. In recent years, with the increase of environmental protection pressure and the upgrading of technology, lithium ion batteries are gradually used on new energy automobiles, and particularly, the yield of ternary power batteries is rapidly increased. However, with the arrival of scrap trend brought by the use of lithium batteries, the scrap quantity of the power type lithium ion batteries reaches 32.2GWH in 2020, a large amount of valuable metals are contained in the scrap quantity, particularly the metal value of a positive electrode material is higher, and the scrap quantity is a problem which needs to be solved urgently for the development and utilization of the positive electrode material.
The existing method for recycling the scrapped lithium battery anode material mainly comprises the steps of dissolving the anode material by using acid and a reducing agent, and then separating metal ions one by using a precipitation or extraction method. In recent years, methods for selectively extracting lithium have been developed, mainly by carrying out oxidation roasting or reduction roasting, and then extracting lithium by water, and recovering metal oxides as precipitates. Both of these processes, while very selective in recovering lithium, have other problems: the consumption of sulfated roasting acid is large, the equipment corrosion is strong, the purity of the obtained product is not high, and the tail gas generated by the decomposition of sulfuric acid needs to be treated; the reduction roasting needs a large amount of reducing gas, the reduction is insufficient, the recovery rate of the reduction product is low, the process is long, and the like. Therefore, it is necessary to provide a method for recovering valuable metals from waste lithium batteries efficiently and simply.
Through search, the Chinese patent application numbers are: 201010199758.4, filing date: the invention and creation name is as follows on 6/12/2010: a method for recovering metallic lithium from waste lithium ion secondary batteries. The method in the application is to completely discharge the recovered waste lithium ion secondary battery, so that all reversible lithium ions on each negative plate of the waste battery are transferred to the positive electrode, and lithium salt is formed on the positive plate; completely taking out the positive plate of the battery after discharge treatment in a mechanical disassembly physical mode, and drying; metallic lithium or lithium-coated material is used as a negative plate to match with each positive plate processed in the previous step, and after the negative plate is placed in a special formation tank with electrolyte and electrically connected, the positive plate and the negative plate are respectively connected to a positive bus bar and a negative bus bar of a direct current power supply to carry out external formation treatment, so that reversible lithium ions are transferred from each positive plate to each negative plate to be deposited; and taking out the positive and negative electrode sheets after the external formation treatment, so that the metal lithium precipitated on the negative electrode sheet can be directly recycled. This application can retrieve the metal lithium in the old and useless lithium cell, and the metal lithium of retrieving is comparatively pure. However, the process of transferring lithium ions from each positive plate to each negative plate for deposition through the external formation treatment is difficult to control, the selection of voltage has a great influence on the deposition effect of the metal lithium, and the deposition effect is relatively poor in actual operation, so that the metal lithium is difficult to effectively recover.
Disclosure of Invention
1. Technical problem to be solved by the invention
The invention provides a method for recovering metal from a waste lithium battery anode material, aiming at the defects of complex process flow, low purity of the obtained product, low recovery rate, large consumption of chemical reagents and high cost in the prior art when the waste lithium battery anode material is recovered. The invention realizes the dissolution and separation of lithium and other metals by one step through the electrolysis-electrodeposition of the anode material, and finally recovers the lithium and other metals.
2. Technical scheme
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the invention discloses a method for recovering metal from a waste lithium battery anode material, which comprises the following steps:
(1) preparing raw materials: coating a waste anode material on an electrode to prepare a cathode, inserting the cathode into electrolyte, and adopting a carbon rod as an anode;
(2) electrolysis-electrodeposition: electrifying first, and dissolving the anode material; then the current direction is changed, and attachments are gradually generated on the anode and are circulated until the anode material is completely dissolved;
(3) collecting: after electrolysis-electrodeposition is finished, collecting attachments and electrolyte on the carbon rod;
(4) preparation of a product: calcining the attachment obtained in the step (3) at high temperature to obtain metal; and adding alkali and sodium carbonate into the electrolyte to obtain lithium carbonate.
Furthermore, in the step (2), the voltage range is 0-5V when the power is on.
Furthermore, in the step (2), the electrolysis voltage range is preferably 0.2-0.8V, and the electrolysis time is controlled to be 0.01 s; the range of the electrodeposition voltage is preferably 0.8-2V, and the electrodeposition time is controlled to be 0.02 s; the electrolysis-electrodeposition process is circulated until the positive electrode material is completely dissolved.
Furthermore, in the step (1), the positive electrode material is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate or lithium nickel cobalt aluminate, and the positive electrode material is coated on the electrode by using a binder and a conductive agent.
Furthermore, in the step (1), the positive electrode material is uniformly mixed with the binder and the conductive agent before being coated, and the coating thickness is less than 5 mm.
Furthermore, PVDF is adopted as the binder, and acetylene black is adopted as the conductive agent.
Further, the electrolyte in the step (1) is a mixed solution of sulfuric acid and lithium sulfate.
Furthermore, in the step (4), the calcining temperature is 800-1000 ℃, and the calcining time is 2-5 h.
3. Advantageous effects
Compared with the prior art, the technical scheme provided by the invention has the following remarkable effects:
(1) the invention relates to a method for recovering metal from a waste lithium battery anode material, which realizes the dissolution of the anode material and the separation of the metal in one step by optimally designing the steps and the operation of metal recovery, particularly adopting electrifying and changing the current direction to carry out electrolysis-electrodeposition treatment on the anode material, wherein lithium ions are dissolved in electrolyte, other metals are attached to a carbon rod, and finally the separation and recovery of the lithium and other heavy metals are realized.
(2) According to the method for recovering the metal from the anode material of the waste lithium battery, the control parameters and the treatment process of electrolysis-electrodeposition are optimized, and particularly, on one hand, the full reaction in the electrolysis-electrodeposition process is ensured by setting the electrified voltage; on the other hand, the electrolysis-electrodeposition process is controlled to be alternately carried out and circularly reciprocated until the anode material is completely dissolved, so that the redox reaction on the electrode is favorably and fully carried out, and pure lithium carbonate and heavy metal oxide can be finally obtained.
(3) According to the method for recovering the metal from the anode material of the waste lithium battery, the electrolytic voltage and time and the electrodeposition voltage and time in the electrolytic-electrodeposition process are controlled, so that the phenomenon that decomposed heavy metal ions are subjected to reduction reaction and return to the cathode in the conventional electrolysis process can be effectively avoided or remarkably relieved, heavy metal ions dissolved in the electrolyte can be fully deposited on the electrode, and the separation effect of lithium and heavy metal in the recovery process can be guaranteed. Meanwhile, in the electrolysis-electrode process, the electrolysis is finished, the current direction is changed, the cathode and the anode are exchanged, heavy metal ions can be further subjected to reduction reaction and deposited on the electrode, and the separation effect of lithium and heavy metal is further improved.
(4) According to the method for recovering the metal from the anode material of the waste lithium battery, the attachment after electrodeposition is calcined at high temperature, the collected electrolyte is subjected to precipitation treatment, and meanwhile, the calcining temperature section and the calcining time length are controlled, so that the calcining temperature settings of different temperature sections can be controlled according to actual requirements, and therefore, each metal in the anode material of the waste lithium battery can be effectively separated and recovered, and the recovery rate and the purity are high.
Detailed Description
When metals in traditional waste anode materials are recovered, metal ions are generally leached by acid, and then the metals are recovered by extraction, chemical precipitation and other modes. The invention provides a method for recovering metal from a waste lithium battery anode material, which comprises the following steps:
(1) raw material preparation
Uniformly stirring the waste anode material, the binder and the conductive agent, coating the mixture on an electrode, controlling the coating thickness to be less than 5mm to prepare a cathode, and inserting the cathode into electrolyte. Wherein the waste positive electrode material comprises one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganese oxide or lithium nickel cobalt aluminate. PVDF is adopted as the binder. Acetylene black is used as the conductive agent. The electrolyte is a mixed solution of sulfuric acid and lithium sulfate.
(2) Electrolysis-electrodeposition
And when the power is on, controlling the range of the power-on voltage to be 0-5V. Specifically, considering that the positive electrode material is mainly subjected to a reduction reaction to be dissolved into ions during electrolysis, in the actual production, the phenomenon that the decomposed heavy metal ions are subjected to a reduction reaction and then return to the cathode is often generated during conventional electrolysis, and repeated electrolysis is easily caused. According to the invention, researches show that the electrolytic voltage range is reasonably selected to avoid or slow down the phenomenon, so that the electrolytic voltage is not too high, the electrolytic voltage is preferably controlled to be 0.2-0.8V, and the electrolytic time is controlled to be 0.01 s. At this time, the positive electrode material starts to be dissolved, and the following reaction occurs during electrolysis:
cathode: 2LiMO2+2H++2e-＝2Li++2M2++2H2O；
Anode: h2O-2e--＝O2↑+2H+；
Wherein M is metal such as nickel, cobalt and the like.
After the electrolysis is finished, the current direction is changed, and the cathode and the anode are exchanged, so that the heavy metal ions are subjected to reduction reaction and deposited on the other electrode. In order to ensure that heavy metal dissolved in electrolyte is electrodeposited on an electrode and further ensure that the electrodeposition is as sufficient as possible, the electrodeposition voltage is controlled to be 0.8-2V and the electrodeposition duration is controlled to be 0.02s through research, so that the electrodeposition can be effectively ensured to be sufficient. At this time, the other electrode gradually generates attachments, and the following reaction occurs in the process of electrodeposition;
cathode: m2++2e-＝M；
Anode: 2H+-2e-＝H2↑；
Wherein M is metal such as nickel, cobalt and the like.
The electrolysis-electrodeposition process is circularly repeated until the positive electrode material is completely dissolved.
It should be noted that the conventional electrolysis-electrodeposition does not change the direction of current, and usually an oxidation reaction occurs at the anode, the metal is dissolved in the electrolyte, a reduction reaction occurs at the cathode, and metal ions in the electrolyte are deposited on the cathode. However, according to the technical scheme of the invention, on one hand, by changing the current direction during electrolysis-electrodeposition, the metal ions dissolved in the electrolyte can be effectively prevented or reduced from depositing on the electrode made of the anode material, and the dissolution of the anode material and the separation of lithium and heavy metal are further realized. On the other hand, the electrolysis-electrodeposition process is carried out repeatedly in the system by controlling the electrolysis-electrodeposition time until the anode material is completely dissolved, so that the redox reaction on the electrode can be fully carried out, and pure lithium carbonate and heavy metal oxide can be obtained finally.
(3) Collecting
After the electrolysis-electrodeposition is finished, the attached matters on the carbon rod are scraped off by a scraper, and the electrolyte is collected.
(4) Product preparation
Calcining the collected attachments in a high-temperature furnace at 800-1000 ℃ for 2-5 h until carbon is completely gasified and volatilized to obtain a metal oxide product, wherein the chemical reaction is as follows: xM + O2＝MxO2(ii) a Wherein M is a metal such as nickel, cobalt, etc., and x is 0.5-2. Adding alkali into the electrolyte, controlling the pH to be 6-8, adding sodium carbonate, and carrying out chemical reaction: 2Li++CO3 2-＝Li2CO3Filtering and drying to obtain the lithium carbonate product.
For a further understanding of the present invention, reference will now be made to the following examples.
Example 1
(1) Preparing raw materials: coating 100g of waste lithium cobaltate positive electrode material on an electrode to prepare a cathode, wherein the cathode and the anode both adopt a graphite electrode and a mixed solution of sulfuric acid and lithium sulfate as an electrolyte, the anode and the anode are inserted into the electrolyte and are externally connected with a power supply;
(2) electrolysis-electrodeposition: controlling the power supply voltage to be 0.5V, switching on the power supply for 0.01s, gradually dissolving lithium cobaltate on the cathode, then changing the current direction, exchanging the cathode and the anode, controlling the power supply voltage to be 1V, electrifying for 0.02s, gradually generating attachments on the other electrode, and repeating the steps until the anode material is completely dissolved.
(3) Collecting: after electrolysis-electrodeposition is finished, respectively collecting attachments and electrolyte on the carbon rod, and hanging the attachments down by a scraper;
(4) preparation of a product: and (3) calcining the attachment in a high-temperature furnace at 800 ℃ for 2h, and cooling to obtain calcined slag, namely the cobalt oxide. And adding sodium hydroxide into the electrolyte, adjusting the pH to 7, adding sodium carbonate, filtering, washing and drying to obtain the lithium carbonate.
The purity and the metal recovery rate of the obtained cobalt oxide and lithium carbonate are both measured to be more than 99%.
Example 2
(1) Preparing raw materials: coating 100g of waste lithium manganate positive electrode material on an electrode to prepare a cathode, wherein graphite electrodes and a mixed solution of sulfuric acid and lithium sulfate are adopted as an electrolyte for the cathode and the anode, the anode and the anode are inserted into the electrolyte and are externally connected with a power supply;
(2) electrolysis-electrodeposition: controlling the power supply voltage to be 0.8V, switching on the power supply for 0.01s, gradually dissolving the lithium manganate on the cathode, then changing the current direction, exchanging the cathode and the anode, controlling the power supply voltage to be 1.5V, electrifying for 0.02s, gradually generating attachments on the other electrode, and repeating the steps until the anode material is completely dissolved.
(3) Collecting: after electrolysis-electrodeposition is finished, respectively collecting attachments and electrolyte on the carbon rod, and hanging the attachments down by a scraper;
(4) preparation of a product: and (3) calcining the attachment in a high-temperature furnace at 900 ℃ for 5h, and cooling to obtain calcined slag, namely the manganese oxide. And adding sodium hydroxide into the electrolyte, adjusting the pH to 8, adding sodium carbonate, filtering, washing and drying to obtain the lithium carbonate.
The purity and the metal recovery rate of the obtained manganese oxide and lithium carbonate are both over 99 percent.
Example 3
(1) Preparing raw materials: coating 100g of waste nickel cobalt lithium manganate positive electrode material on an electrode to prepare a cathode, wherein graphite electrodes and a mixed solution of sulfuric acid and lithium sulfate are adopted as electrolyte for a cathode and an anode, the anode and the anode are inserted into the electrolyte and are externally connected with a power supply;
(2) electrolysis-electrodeposition: controlling the power supply voltage to be 0.3V, switching on the power supply for 0.01s, gradually dissolving the nickel cobalt lithium manganate on the cathode, then changing the current direction, exchanging the cathode and the anode, controlling the power supply voltage to be 1.8V, enabling the electrifying time to be 0.02s, gradually generating attachments on the other electrode, and repeating the steps until the anode material is completely dissolved.
(3) Collecting: after electrolysis-electrodeposition is finished, respectively collecting attachments and electrolyte on the carbon rod, and hanging the attachments down by a scraper;
(4) preparation of a product: and (3) calcining the attachment in a high-temperature furnace at 1000 ℃ for 3h, and cooling to obtain the calcined slag, namely the nickel-cobalt-manganese metal oxide. And adding sodium hydroxide into the electrolyte, adjusting the pH to 7, adding sodium carbonate, filtering, washing and drying to obtain the sodium carbonate.
The purity and the metal recovery rate of the nickel-cobalt-manganese metal oxide and the lithium carbonate are both over 99 percent.
Example 4
(1) Preparing raw materials: coating 100g of waste nickel cobalt lithium aluminate anode material on an electrode to prepare a cathode, wherein the cathode and the anode are graphite electrodes, a mixed solution of sulfuric acid and lithium sulfate is used as an electrolyte, the anode and the anode are inserted into the electrolyte, and a power supply is externally connected;
(2) electrolysis-electrodeposition: controlling the voltage of a power supply to be 0.6V, switching on the power supply for 0.01s, gradually dissolving the nickel-cobalt lithium aluminate on the cathode, then changing the current direction, exchanging the cathode and the anode, controlling the voltage power supply to be 2V, switching on for 0.02s, gradually generating attachments on the other electrode, and repeating the steps until the anode material is completely formed.
(3) Collecting: after electrolysis-electrodeposition is finished, respectively collecting attachments and electrolyte on the carbon rod, and hanging the attachments down by a scraper;
(4) preparation of a product: and (3) calcining the attachment in a high-temperature furnace at 900 ℃ for 2h, and cooling to obtain calcined slag, namely the nickel-cobalt-aluminum metal oxide. And adding sodium hydroxide into the electrolyte, adjusting the pH to 6, adding sodium carbonate, filtering, washing and drying to obtain the sodium carbonate.
The nickel cobalt aluminum metal oxidation and lithium carbonate purity and metal recovery rate are measured to be more than 99%.
The foregoing is directed to embodiments of the present invention, and it is understood that various modifications and improvements can be made by those skilled in the art without departing from the spirit of the invention.
Claims (8)
1. A method for recovering metal from a waste lithium battery anode material is characterized by comprising the following steps:
(1) preparing raw materials: coating a waste anode material on an electrode to prepare a cathode, inserting the cathode into electrolyte, and adopting a carbon rod as an anode;
(2) electrolysis-electrodeposition: electrifying first, and dissolving the anode material; then the current direction is changed, attachments are gradually generated on the anode, and the electrolysis-electrodeposition process is circulated until the anode material is completely dissolved;
(3) collecting: after electrolysis-electrodeposition is finished, collecting attachments and electrolyte on the carbon rod;
(4) preparation of a product: calcining the attachment obtained in the step (3) at high temperature to obtain metal; and adding alkali and sodium carbonate into the electrolyte to obtain lithium carbonate.
2. The method for recovering metal from the positive electrode material of waste lithium batteries as claimed in claim 1, wherein in the step (2), the voltage range is 0-5V when the electricity is applied.
3. The method for recovering metal from the positive electrode material of the waste lithium battery as claimed in claim 2, wherein in the step (2), the electrolysis voltage is preferably in the range of 0.2 to 0.8V, and the electrolysis time is controlled to be 0.01 s; the range of the electrodeposition voltage is preferably 0.8-2V, and the electrodeposition time is controlled to be 0.02 s.
4. The method for recovering metal from the positive electrode material of waste lithium batteries according to any one of claims 1 to 3, wherein the positive electrode material in the step (1) is one or more of lithium cobaltate, lithium manganate, lithium nickel cobalt manganate and lithium nickel cobalt aluminate, and the positive electrode material is coated on the electrode by using a binder and a conductive agent.
5. The method for recovering metal from the positive electrode material of the waste lithium battery as claimed in claim 4, wherein in the step (1), the positive electrode material is uniformly mixed with the binder and the conductive agent before being coated, and the coating thickness is less than 5 mm.
6. The method for recovering metal from the positive electrode material of the waste lithium battery as claimed in claim 5, wherein the binder is PVDF, and the conductive agent is acetylene black.
7. The method for recovering metal from the positive electrode material of waste lithium batteries as recited in claim 5, wherein the electrolyte in the step (1) is a mixed solution of sulfuric acid and lithium sulfate.
8. The method for recovering metal from the positive electrode material of the waste lithium battery as claimed in claim 5, wherein the calcination temperature in the step (4) is 800-1000 ℃ and the calcination time is 2-5 h.
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| CN113881850A (en) * | 2021-09-28 | 2022-01-04 | 华东理工大学 | Method for simultaneously recovering anode and cathode of lithium ion battery |
| CN114875450A (en) * | 2022-05-27 | 2022-08-09 | 湖南世纪垠天新材料有限责任公司 | Comprehensive recovery processing method of ternary power battery material |
| CN114875450B (en) * | 2022-05-27 | 2023-11-03 | 湖南世纪垠天新材料有限责任公司 | Comprehensive recovery processing method for ternary power battery material |
| CN117448577A (en) * | 2023-10-11 | 2024-01-26 | 江西江铼新材料科技有限公司 | Process for recycling lithium sulfate and ferric phosphate based on waste lithium iron phosphate battery |
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