CN108069447A - The method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell positive Active Waste - Google Patents
The method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell positive Active Waste Download PDFInfo
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- CN108069447A CN108069447A CN201711326762.0A CN201711326762A CN108069447A CN 108069447 A CN108069447 A CN 108069447A CN 201711326762 A CN201711326762 A CN 201711326762A CN 108069447 A CN108069447 A CN 108069447A
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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
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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
- 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 present invention provides a kind of methods that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell positive Active Waste, comprise the following steps：Lithium ion cell positive Active Waste is handled using oxidation acid leaching method first, obtains acid leaching solution；Then by the way of the extraction of two steps and pH value separation manganese, cobalt and the nickel of solution are adjusted, realize the synthetical recovery of valuable metal, while the foreign particle of the elements such as deep removal Fe, Ni, Ca, Mg, Cu, Al, should during effectively prevent the loss of lithium；Deep impurity-removing processing is carried out to raffinate using storng-acid cation exchange resin again, is purified rich lithium solution；After bipolar membrane electrodialysis method treatment and purification richness lithium solution, lithium hydroxide solution and acid solution are obtained；Concentration is finally evaporated to lithium hydroxide solution, obtains LITHIUM BATTERY lithium hydroxide product.Using this method, the LITHIUM BATTERY lithium hydroxide product for being directly used in tertiary cathode material preparation can be obtained, realizes the immortalized processing of lithium.
Description
Technical field
The invention belongs to lithium ion battery technical field of waste recovery more particularly to a kind of utilization lithium ion cell positive to live
Property waste material prepare LITHIUM BATTERY lithium hydroxide method.
Background technology
The new-energy automobile industry boosting lithium industry of mass market flourishes, in recent years the market demand of lithium
It is exponentially increased, the concluded price of lithium remains high.Under the continuous stimulation in market, lithium resource exploitation industry is like a raging fire, nothing
By being containing lithium ore or rich lithium salts lake bittern water, with the continuous consumption of Resources, lithium resource is recycled to industry
The meaning of sustainable development is more and more important.
In today that new energy product makes rapid progress, dynamic lithium battery market development is very rapid.Global lithium electricity in 2012
Pond yield is 58.6 hundred million, has benefited from the fast development of New Energy Industry, it is contemplated that be up to the year two thousand twenty whole world lithium battery output value
32000000000 dollars.With the demand of lithium ion battery and constantly soaring, the quantity of the waste and old lithium ion battery after military service of yield
Rapidly increase therewith, conservative estimation has the power battery for accounting for total amount 15%~20% to scrap every year, it is contemplated that the year two thousand twenty whole world
Waste and old lithium ion battery quantity will reach 25,000,000,000, be roughly equal to 500,000 tons.
The positive electrode active materials of current driving force lithium battery mainly have LiFePO4, cobalt acid lithium, LiMn2O4, nickle cobalt lithium manganate
It disassembles Deng, these lithium ion battery premenstruum (premenstrua)s and usually contains Co 5%~20%, Ni 5% in obtained waste material after pretreatment
~10%, Li 5%~7%, Mn 1%~5%.If these waste and old lithium ion batteries cannot get safe disposal, one side battery
The noxious materials such as various heavy, organic and inorganic compound that inside is contained outflow, and various chemistry easily occur in the environment
Reaction can cause environment and public safety huge harm, and some of substances are even more to have carcinogenicity, endanger the mankind and are good for
Health；On the other hand the wasting of resources of inside battery valuable metal, particularly strategy metal Co and Li can be caused, it is current as China
Metals resources in short supply, recycle economic value it is high.
Existing lithium battery recovery process is mainly for single useless old lithium positive electrode, such as Chinese patent
CN104903475B discloses a kind of use hydrometallurgy partition method and lithium is recycled from LiFePO4 waste material and prepares lithium hydroxide
Method；Chinese patent application CN105304971A discloses a kind of using the waste and old cobalt acid lithium battery of mechanochemical reaction processing, choosing
Selecting property recycling lithium metal and beam system for cobalt-based magnetic functional material method；Chinese patent CN102163760B discloses one kind
The chemical method of cobalt is carried using high-temperature calcination-water logging separating Li-extraction, to realize Call Provision and lithium from cobalt acid lithium old and useless battery.
For the waste lithium cell of early stage based on cobalt acid lithium, LiFePO4, LiMn2O4 etc., research object is single, but with just
The technological progress of pole material and commercialized development, the binary or ternary material of various different compositions start to occur, and metal ion is in
Existing diversity so that the later separation purification process of battery recycling becomes complicated and difficult.Particularly in production practices, recycle
To waste lithium cell in dopant species and content difference it is very big, positive electrode species be difficult to completely it is single；It is a large amount of different
How the waste and old positive electrode of species unifies batch processing and recycles valuable metal, is battery recycling industry difficulty urgently to be resolved hurrily
Topic.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, provide one
The method that kind prepares LITHIUM BATTERY lithium hydroxide using lithium ion cell positive Active Waste, the adaptability to raw material of this method is strong, lithium
Organic efficiency is high, and environmental friendly pollution is small, and cost of investment is low, it is easy to accomplish industrialization promotion.
In order to solve the above technical problems, technical solution proposed by the present invention is：
A kind of method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell positive Active Waste, is comprised the following steps：
(1) lithium ion cell positive Active Waste is handled using oxidation acid leaching method, obtains the acidic leaching of metal ion
Liquid, the metal ion include lithium ion；
(2) organic extractant extract and separate manganese and cobalt, load organic phases warp are added in into the acid leaching solution after step (1)
It is stripped to obtain the pregnant solution of manganese and cobalt through diluted acid again after pure water, it is follow-up that recycling manganese and cobalt, raffinate can be used for enter step
Suddenly (3) are handled, and the removing of entrainment portions Fe, Cu, Al, Ca and Mg element is gone back during step (2)；
(3) lithium hydroxide is added in into the raffinate after step (2) and adjusts pH value, then add in organic extractant extraction point
From nickel, and further realize while extraction of nickel the deep removal of low concentration manganese cobalt, load organic phases after pure water again
It is stripped to obtain rich nickel liquid through diluted acid, follow-up to can be used for recycling nickel, raffinate enters step (4) and handles, during step (3)
The also removing of entrainment portions Fe, Cu, Al, Ca and Mg elements；
(4) deep impurity-removing processing, abjection carry out the raffinate after step (3) using storng-acid cation exchange resin
The elements such as Na, K are purified rich lithium solution；
(5) using the purification richness lithium solution after bipolar membrane electrodialysis method processing step (4), lithium hydroxide solution and acid are obtained
Property solution；
(6) lithium hydroxide solution after step (5) is evaporated concentration, obtains LITHIUM BATTERY lithium hydroxide product.
Above-mentioned method, it is preferred that Na, content≤5mg/L of K element in the rich lithium solution of purification, Fe, Mn, Co,
Content≤2mg/L of Ni, Ca, Mg, Cu, Al element.Applicant passes through a large number of experiments the study found that containing in rich lithium scavenging solution
The content of foreign ion need to control within the scope of the invention, could so be directly obtained in subsequent bipolar membrane electrodialysis
The qualified lithium hydroxide solution of LITHIUM BATTERY lithium hydroxide product can be prepared；If beyond the scope of this invention, richness lithium solution warp
Impurity content is high in the lithium hydroxide solution obtained after bipolar membrane electrodialysis processing, could be steamed after also needing further deep impurity-removing
Hair prepares LITHIUM BATTERY lithium hydroxide product.
Above-mentioned method, it is preferred that the concentration of the lithium hydroxide solution obtained in the step (5) is 1~5mol/L, sour
Property solution concentration be 1~5mol/L.
Above-mentioned method, it is preferred that it is 5~7 that pH value is adjusted in the step (3).
Above-mentioned method, it is preferred that bipolar membrane electrodialysis system is tied for three Room used by the bipolar membrane electrodialysis method
The bipolar membrane electrodialysis system of structure.The method of the present invention, using the bipolar membrane electrodialysis system of three cell structures, convenient for obtaining simultaneously
Target product lithium hydroxide and recycling acid solution.
Above-mentioned method, it is preferred that the organic extractant be organic phosphates extractant, selected from P204, P507,
At least one of Cyanex272, Cyanex301, Cyanex471X, Cyanex921, Cyanex923.
Above-mentioned method, it is preferred that acid solution return to step (1) is used as leaching agent, the step in the step (5)
(2) wash water is incorporated in the acid leaching solution after step (1) in, and the wash water in the step (3) is incorporated to the raffinate after step (2)
In.
Above-mentioned method, it is preferred that content >=5g/L of lithium ion in the acid leaching solution of the step (1).
Above-mentioned method, it is preferred that the lithium ion cell positive Active Waste refers to waste and old lithium ion battery through safety
The positive-active waste material and/or lithium ion battery obtained after aluminium foil, conductive agent and binding agent is disassembled and separated to electric discharge, physics
Positive electrode waste product, the leftover pieces generated in production process.Positive-active waste material selected by the present invention for removal conductive agent and
The Active Waste of binding agent to avoid organic matter is introduced in leachate, causes to damage to the film of electrodialysis system.
Above-mentioned method, it is preferred that the lithium ion cell positive Active Waste is cobalt acid lithium (LiCoO2), LiMn2O4
(LiMn2O4), nickel manganese binary composite positive pole (LiNixMn1-xO2, 0 ＜ x ＜, 1,0 ＜ y ＜ 1), nickel cobalt binary anode composite material
Expect (LiNixCo1-xO2, 0 ＜ x ＜, 1,0 ＜ y ＜ 1), cobalt manganese binary composite positive pole (LiCoxMn1-xO2, 0 ＜ x ＜, 1,0 ＜ y
＜ 1), nickel-cobalt-manganese ternary composite positive pole (LiNixCoyMn1-x-yO2At least one of, 0 ＜ x ＜, 1,0 ＜ y ＜ 1).
Compared with prior art, the advantage of the invention is that：
(1) method using the present invention, the rate of recovery of lithium is more than 97% in lithium ion cell positive Active Waste, while real
The immortalized processing of existing lithium, obtains the LITHIUM BATTERY lithium hydroxide product that can be directly used for tertiary cathode material preparation.
(2) method of the invention, by the way of the extraction of two steps and the pH value of adjusting solution separates manganese, cobalt and nickel, real
The synthetical recovery of existing valuable metal, while the foreign particle of the elements such as deep removal Fe, Ni, Ca, Mg, Cu, Al, and in the process
In effectively prevent the loss of lithium.
(3) method of the invention is handled through the extraction of two steps and a step resin adsorption, and the foreign metal ion in addition to Li is
Below horizontal through having reached 2~5ppm, after bipolar membrane electrodialysis is handled, obtained product purity is high.
(4) method of the invention, it is applied widely, technological process is simple, processing cost is low, three-waste free discharge.The present invention
Method avoid the problems such as chemical agent consumption present in traditional chemical partition method is high, lithium resource entrainments at different levels are scattered, save
The treatment facility of hydrogen and chlorine in conventional ion membrane electrolysis has been removed, various different types of lithium ion cell positives can be handled
Waste material is suitble to carry out extensive recycling recycling to waste lithium ion cell anode material.
Description of the drawings
It in order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the method for preparing LITHIUM BATTERY lithium hydroxide in the embodiment of the present invention 1 using lithium ion cell anode waste
Process flow chart.
Specific embodiment
For the ease of understanding the present invention, done more entirely below in conjunction with Figure of description and preferred embodiment to inventing herein
Face meticulously describes, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell anode waste of the present invention, technological process
Figure is as shown in Figure 1, comprise the following steps：
(1) nickel-cobalt-manganese ternary composite positive pole, leaching agent H are handled using oxidation acid leaching method2SO4Solution and Na2S2O8
The mixed solution of solution obtains sulphuric leachates of the 10L containing metal ions such as lithium ions；
(2) add in the P507 extraction manganese and cobalt through saponification process in the sulphuric leachate after step (1), separation water phase and
Load organic phases；Load organic phases add pure water, and nickeliferous lithium wash water is incorporated to before extraction in the sulphuric leachate of liquid i.e. step (1),
Then the H that concentration is 1mol/L is added in into load organic phases2SO4It is stripped, obtains the sulfuric acid solution of enrichment manganese and cobalt,
Raffinate enters step (3) processing；
(3) it is 5.5~6.5 that LiOH solution is added in into the raffinate after step (2) and adjusts pH value, is then added in through saponification
The P507 extraction of nickel of processing, separates water phase and load organic phases, load organic phases add pure water, and wash water containing lithium, which is incorporated to, once to be extracted
The H that concentration is 1mol/L is added in extraction raffinate, in load organic phases2SO4Be stripped, obtain rich nickel solution, secondary raffinate into
Enter step (4) processing；
(4) deep impurity-removing is carried out to the secondary raffinate after step (3) using 001 × 7 storng-acid cation exchange resin
Processing removes Na, K, is purified lithium sulfate solution；
(5) using the three obtained purification lithium sulfate solutions of cell structure bipolar membrane electrodialysis system processing step (4), in alkali
The lithium hydroxide solution that concentration is 2.7mol/L is obtained in room, the sulfuric acid solution that concentration is 1.4mol/L, sulfuric acid are obtained in sour room
Solution return to step is used as leachate in (1)；
(6) lithium hydroxide solution after step (5) is evaporated concentration, obtains 375.0g battery-stage monohydrate lithium hydroxides
Powder, the rate of recovery of Li is 97.8%.
The main chemical compositions of involved each solution and content are as shown in table 1 in the present embodiment.
The involved main chemical compositions of each solution and content (unit in 1 embodiment 1 of table：mg/L)
| Element | Li | Mn | Co | Ni | Al | Fe | Cu | Ca | Mg | Na | K |
| Pickle liquor | 6250 | 4820 | 27100 | 32500 | 152 | 0.76 | 190 | 250 | 200 | 12400 | 1.55 |
| Raffinate | 6210 | 2.90 | 16.23 | 30988 | 5.68 | 0.55 | 14.5 | 108.4 | 96.54 | 10536 | 1.62 |
| Secondary raffinate | 6190 | 0.45 | 3.56 | 4.68 | 0.43 | 0.42 | 0.53 | 65.43 | 5.95 | 22883 | 1.53 |
| The rich lithium solution of purification | 9225 | 0.89 | 1.46 | 1.25 | 0.03 | 0.38 | 0.39 | 1.78 | 1.43 | 4.11 | 1.29 |
Embodiment 2：
A kind of method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell anode waste of the present invention, including following step
Suddenly：
(1) using oxidation acid leaching method handle lithium ion cell positive Active Waste, the waste material for cobalt acid lithium, LiMn2O4 and
The mixture of nickle cobalt lithium manganate, leaching agent are HCl solution and H2O2The mixed solution of solution, obtain 10L containing the metals such as lithium ion from
The acid leaching solution of son；
(2) Cyanex272 extraction manganese and cobalt through saponification process are added in the hydrochloric acid leachate obtained by step (1), point
From water phase and load organic phases；Load organic phases add pure water, wash water be incorporated to step (1) acid leaching solution extract before liquid
In, then to load organic phases dilute hydrochloric acid solution is added to be stripped, obtain the enrichment solution of manganese and cobalt, one time raffinate enters
Step (3) processing；
(3) it is 5.2~5.8 that the raffinate after step (2), which adds in LiOH solution and adjusts pH value, is then used at through saponification
The P507 extraction of nickel of reason, separates water phase and load organic phases, load organic phases add pure water, and wash water containing lithium is incorporated to step (3)
Liquid before extracting in a raffinate afterwards, load organic phases add dilute hydrochloric acid or sulfuric acid solution to be stripped, and obtain rich nickel solution, and two
Secondary raffinate enters step (4) processing；
(4) deep impurity-removing is carried out to the secondary raffinate after step (3) using 001 × 7 storng-acid cation exchange resin,
Na, K are removed, is purified lithium chloride solution；
(5) using the three obtained purification lithium chloride solutions of cell structure bipolar membrane electrodialysis system processing step (4), in alkali
The lithium hydroxide solution that concentration is 1.8mol/L is obtained in room, the hydrochloric acid solution that concentration is 1.8mol/L, hydrochloric acid are obtained in sour room
Solution return to step is used as leachate in (1)；
(6) lithium hydroxide solution after step (5) is evaporated concentration, obtains 229.6g LITHIUM BATTERY list water hydrogen-oxygens
Change lithium powder, the rate of recovery of Li is 97.2%.
The main chemical compositions of involved each solution and content are as shown in table 2 in the present embodiment.
The involved main chemical compositions of each solution and content (unit in 2 embodiment 2 of table：mg/L)
The ingredient of monohydrate lithium hydroxide product to being obtained in embodiment 1 and embodiment 2 is detected, testing result such as table
Shown in 3.
Main component (the unit of monohydrate lithium hydroxide product in 3 embodiment 1 of table and embodiment 2：%)
| Product national standard | Embodiment 1 | Embodiment 2 | |
| LiOH·H2O | 98.0 | 98.2 | 98.3 |
| HCl insoluble matters | 0.005 | 0.0048 | 0.0048 |
| Fe | 0.0008 | 0.0005 | 0.0005 |
| Mn | 0.005 | 0.005 | 0.005 |
| Cu | 0.005 | 0.003 | 0.003 |
| Na | 0.003 | 0.003 | 0.003 |
| K | 0.003 | 0.002 | 0.001 |
| Ca | 0.005 | 0.003 | 0.004 |
| Mg | 0.005 | 0.003 | 0.004 |
| Si | 0.005 | 0.003 | 0.002 |
| CO3 2- | 0.7 | 0.04 | 0.05 |
| Cl- | 0.007 | 0.003 | 0.007 |
| SO4 2- | 0.01 | 0.008 | 0.005 |
As shown in Table 3, the LITHIUM BATTERY lithium hydroxide that preparation in accordance with the present invention is prepared, meets national standard,
It can be directly used for the preparation of lithium battery anode active material.
Claims (10)
- A kind of 1. method that LITHIUM BATTERY lithium hydroxide is prepared using lithium ion cell positive Active Waste, which is characterized in that including Following steps：(1) lithium ion cell positive Active Waste is handled using oxidation acid leaching method, obtains the acid leaching solution of metal ion, institute It states metal ion and includes lithium ion；(2) organic extractant extract and separate manganese and cobalt are added in into the acid leaching solution after step (1), load organic phases are through pure water It is stripped to obtain the pregnant solution of manganese and cobalt through diluted acid again after washing, raffinate enters step (3) processing；(3) lithium hydroxide is added in into the raffinate after step (2) and adjusts pH value, then add in organic extractant extract and separate Nickel, load organic phases are stripped to obtain rich nickel liquid again through diluted acid after pure water, and raffinate enters step (4) processing；(4) deep impurity-removing processing is carried out to the raffinate after step (3) using storng-acid cation exchange resin, is purified richness Lithium solution；(5) using the purification richness lithium solution after bipolar membrane electrodialysis method processing step (4), obtain lithium hydroxide solution and acidity is molten Liquid；(6) lithium hydroxide solution after step (5) is evaporated concentration, obtains LITHIUM BATTERY lithium hydroxide product.
- 2. according to the method described in claim 1, it is characterized in that, the content of Na in the rich lithium solution of the purification, K element≤ Content≤2mg/L of 5mg/L, Fe, Mn, Co, Ni, Ca, Mg, Cu, Al element.
- 3. according to the method described in claim 1, it is characterized in that, the lithium hydroxide solution obtained in the step (5) it is dense It spends for 1~5mol/L, acid solution concentration is 1~5mol/L.
- 4. according to the method described in claim 1, it is characterized in that, it is 5~7 that pH value is adjusted in the step (3).
- 5. according to the method described in claim 1, it is characterized in that, Bipolar Membrane electric osmose used by the bipolar membrane electrodialysis method Analysis system is the bipolar membrane electrodialysis system of three cell structures.
- 6. according to the method described in claim 1, it is characterized in that, the organic extractant be organic phosphates extractant, be selected from At least one of P204, P507, Cyanex272, Cyanex301, Cyanex471X, Cyanex921, Cyanex923.
- 7. according to the method described in claim 1, it is characterized in that, acid solution return to step (1) is used as leaching in the step (5) Go out agent, wash water is incorporated in the acid leaching solution after step (1) in the step (2), and wash water is incorporated to step in the step (3) (2) in the raffinate after.
- 8. according to the method described in claim 1, it is characterized in that, lithium ion contains in the acid leaching solution of the step (1) Amount >=5g/L.
- 9. according to the method described in claim 1, it is characterized in that, the lithium ion cell positive Active Waste refers to waste and old lithium The positive-active waste material that ion battery obtains after aluminium foil, conductive agent and binding agent are disassembled and separated to safe-discharge, physics, And/or positive electrode waste product, the leftover pieces generated in lithium ion battery production process.
- 10. according to the method described in claim 9, it is characterized in that, the lithium ion cell positive Active Waste for cobalt acid lithium, LiMn2O4, nickel manganese binary composite positive pole, nickel cobalt binary composite positive pole, cobalt manganese binary composite positive pole, nickel cobalt manganese At least one of ternary composite cathode material.
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| CN108840354A (en) * | 2018-08-16 | 2018-11-20 | 湖北上和化学有限公司 | LITHIUM BATTERY lithium chloride deep impurity-removing method |
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| CN110013822A (en) * | 2018-01-07 | 2019-07-16 | 中南大学 | A kind of method of waste and old lithium ion battery recycling co-production lithium adsorbent |
| CN110013822B (en) * | 2018-01-07 | 2020-02-14 | 中南大学 | Method for recycling waste lithium ion batteries and co-producing lithium adsorbent |
| CN108840354A (en) * | 2018-08-16 | 2018-11-20 | 湖北上和化学有限公司 | LITHIUM BATTERY lithium chloride deep impurity-removing method |
| CN108840354B (en) * | 2018-08-16 | 2020-12-15 | 湖北上和化学有限公司 | Deep impurity removal method for battery-grade lithium chloride |
| CN109055746A (en) * | 2018-09-28 | 2018-12-21 | 中南大学 | A method of recycling valuable metal from nickelic lithium ion cell anode waste |
| CN109761415A (en) * | 2019-02-19 | 2019-05-17 | 北京中科康仑环境科技研究院有限公司 | A kind of recycling treatment process of cobalt deposition with ammonium bicarbonate waste water |
| CN112158894A (en) * | 2020-09-24 | 2021-01-01 | 广东邦普循环科技有限公司 | Method for recovering anode material of waste lithium battery |
| WO2022242186A1 (en) * | 2021-05-19 | 2022-11-24 | 广东邦普循环科技有限公司 | Method for preparing high-purity iron phosphate by using ferrophosphorus waste |
| CN113955753A (en) * | 2021-08-24 | 2022-01-21 | 安徽南都华铂新材料科技有限公司 | Method for recovering waste lithium iron phosphate battery powder |
| EP4245869A1 (en) * | 2022-03-17 | 2023-09-20 | Fortum OYJ | Method for processing black mass to battery chemicals |
| WO2023175157A1 (en) * | 2022-03-17 | 2023-09-21 | Fortum Oyj | Method for processing black mass to battery chemicals |
| CN114725556A (en) * | 2022-04-06 | 2022-07-08 | 山东大学 | Method for recovering lithium from waste lithium ion battery |
| CN114772565A (en) * | 2022-04-28 | 2022-07-22 | 西南科技大学 | Method for recovering lithium dihydrogen phosphate from leachate of phosphoric acid system of waste lithium iron phosphate battery |
| WO2024014540A1 (en) * | 2022-07-14 | 2024-01-18 | Jx Metals Corporation | Method for removing impurities, and method for recovering metals |
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