CN106935923A - The method that valuable metal is reclaimed from waste nickel hydrogen battery - Google Patents
The method that valuable metal is reclaimed from waste nickel hydrogen battery Download PDFInfo
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- CN106935923A CN106935923A CN201710207458.8A CN201710207458A CN106935923A CN 106935923 A CN106935923 A CN 106935923A CN 201710207458 A CN201710207458 A CN 201710207458A CN 106935923 A CN106935923 A CN 106935923A
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- hydrogen battery
- nickel hydrogen
- waste nickel
- battery
- waste
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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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- 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
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- 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
- C22B7/007—Wet processes by acid leaching
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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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of method that valuable metal is reclaimed from waste nickel hydrogen battery, step is:(1), the physical arrangement and chemical composition to waste nickel hydrogen battery are analyzed, and specify the content and its existence form of battery composition and every kind of metallic element in battery various pieces;(2), by waste nickel hydrogen battery through disassembling, it is broken after sieve, realize that collector is separated with active material, using vacuum distillation technique, the vapour pressure low-melting-point metal high in waste nickel hydrogen battery is reclaimed;(3) after, waste nickel hydrogen battery is processed through vacuum distillation, its residue uses magnetic separation process;The method that the present invention passes through Pressure hydrometallurgy, the technique of valuable metal recovery treatment in the technique study waste nickel hydrogen battery such as Aided Machine Physical, magnetic method, it is suitable to the characteristics for the treatment of is complicated to select smelting nonferrous metal resource with difficulty using Pressure hydrometallurgy technology, realizes the comprehensive utilization of resource.
Description
Technical field
The present invention relates to metal recovery technical field, specifically one kind reclaims valuable from waste nickel hydrogen battery
The method of metal.
Background technology
The recovery of waste nickel hydrogen battery has great resource reclaim meaning, it may have important environmental protection meaning, money
Sourceization reclaims the theory for embodying recycling economy and sustainable development.From in terms of material angle, these negative materials are temporarily to lose
Use value is gone, its essential characteristic does not change.Waste nickel hydrogen battery contains the rare metals such as nickel, cobalt, rare earth, is rich
Rich " secondary resource ".With being on the rise for environmental pollution and oil crisis, high-energy-density type battery is increasingly favored, with
The continuous research and development of electric automobile, Ni-MH battery is as one of great industry of this century energy field so that energy density per unit volume is high, electricity
Pond low cost, power characteristic advantage high have found new market in electric automobile field.Therefore large-scale waste and old ni-mh is electric
The recovery of pond material is all significant to environmental protection and material recovery.And research and develop waste nickel hydrogen battery material
Regenerative use technology, effective for metals resources be worth using with Important Economic.
Waste nickel-hydrogen battery per ton is recyclable to obtain the rare earth metal that 37.5kg purity is 80%, is in close proximity to bastnaesite
Composition[1].It is largely the processing method for inheriting or having used for reference cadmium nickel battery to waste nickel hydrogen battery treatment technology,
The negative material of Ni-MH battery such as contains Ni, Co, RE, Mn, Fe than the negative pole complicated component of cadmium nickel battery.Current waste nickel
Hydrogen battery regeneration treatment technology is generally speaking divided into two kinds of pyrogenic process and wet method, and pyrogenic process reclaims typically use can produce higher temperature
Electric furnace smelted, under Ni-MH battery waste material high-temperature be pyrolyzed product be mainly dilval, only as production some conjunction
The raw material of gold, its economic worth is relatively low.Further, since the high price rare earth in slag can not be reclaimed effectively, the wasting of resources is extremely tight
Weight, pyrogenic process power consumption is high, pollution is big;Wet processing technique is mainly combination acidleach and organic solvent extraction is processed.Acidleach makes
Metallic element in electrode material dissolves and is transferred in solution, controls appropriate condition to make the leaching rate of target metal ions
Close to 100%, then extraction and recovery respective metal phase.The advantage of Wet technique is temperature that need not be very high, and energy consumption is low, treatment
Efficiency and recovery product purity are higher, while also avoiding producing pernicious gas.Conventional wet metallurgical technology comparative maturity and effect
Rate is higher, but there is the raffinate after long flow path, complex operation, extraction and easily cause the significant deficiencies such as secondary pollution.In addition, in order to
The capacity of Ni-MH battery is improved, each Ni-MH battery life producer improves its electrode material formula, the nickel that different manufacturers are produced one after another
Hydrogen battery is also different in composition, and this brings certain difficulty to the recycling of waste nickel hydrogen battery.
The content of the invention
Defect and deficiency it is an object of the invention to be directed to prior art, there is provided one kind is returned from waste nickel hydrogen battery
The method for receiving valuable metal, by the method for Pressure hydrometallurgy, the technique study waste nickel such as Aided Machine Physical, magnetic method
The technique of valuable metal recovery treatment in hydrogen battery, is suitable to that treatment is complicated using Pressure hydrometallurgy technology and difficulty selects the smelting to have
The characteristics of non-ferrous metal resource, realize the comprehensive utilization of resource.
To achieve the above object, the technical solution adopted by the present invention is:
A kind of method that valuable metal is reclaimed from waste nickel hydrogen battery, comprises the concrete steps that:
1st, the physical arrangement and chemical composition to waste nickel hydrogen battery are analyzed, and specify battery composition and every kind of metal
Content and its existence form of the element in battery various pieces;
2nd, by waste nickel hydrogen battery through disassembling, it is broken after sieve, realize that collector is separated with active material, using vacuum
Distillation technique, the vapour pressure low-melting-point metal high in waste nickel hydrogen battery is reclaimed;
3rd, after waste nickel hydrogen battery is processed through vacuum distillation, its residue uses magnetic separation process, and sorting is tapped a blast furnace, nickel, cobalt etc.
Precious metals in waste nickel hydrogen battery are further reclaimed by ferromagnetic material, and to iron in waste nickel hydrogen battery,
Nickel, the magnetic separator reason of cobalt are studied with rule;
4th, using the waste and old Ni-H cell electrode material of pressurized acid leaching, active material leaching process dynamics is studied, is soaked with nickel
Extracting rate, cobalt leaching rate are Two indices, leaching condition (concentration of sulfuric acid, solution temperature, leaching using orthogonal experiment to electrode material
Go out time and solid-to-liquid ratio) optimize research;
5th, valence state and its characteristic are had according to metal ion in electrode material leachate, using extraction and chemical precipitation method
Separation and recovery rare earth element, studies the novel ion liquid extractant of environment-friendly and green, and it is that precipitating reagent is separated to study with sulfuric acid, oxalic acid
Rare earth ion;
6th, after recovering rare earth element, a small amount of Mn in filtrate2+、Fe2+、Al3+、Mg2+Deng metal ion, appropriate method is selected
Foreign ion is processed, nickel sulfate, cobalt sulfate solution in filtrate, add ammoniacal liquor, alkali lye etc., control reaction condition to prepare electricity
Pond positive electrode material precursor Ni0.8Co0.2(OH)2。
Compared with prior art, beneficial effects of the present invention are:The method that the present invention passes through Pressure hydrometallurgy, auxiliary machine
The technique of valuable metal recovery treatment in the technique study waste nickel hydrogen battery such as tool Physical, magnetic method, using Pressure hydrometallurgical process smelting
Gold process technology is suitable to the characteristics for the treatment of is complicated to select smelting nonferrous metal resource with difficulty, realizes the comprehensive utilization of resource.
Brief description of the drawings
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
The accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is flow chart of the invention.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, below in conjunction with accompanying drawing and specific implementation
Mode, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to explain this
Invention, is not intended to limit the present invention.
Referring to Fig. 1, this specific embodiment uses following technical scheme:One kind reclaims valuable gold from waste nickel hydrogen battery
The method of category, comprises the concrete steps that:
1st, the physical arrangement and chemical composition to waste nickel hydrogen battery are analyzed, and specify battery composition and every kind of metal
Content and its existence form of the element in battery various pieces;
2nd, by waste nickel hydrogen battery through disassembling, it is broken after sieve, realize that collector is separated with active material, using vacuum
Distillation technique, the vapour pressure low-melting-point metal high in waste nickel hydrogen battery is reclaimed;
3rd, after waste nickel hydrogen battery is processed through vacuum distillation, its residue uses magnetic separation process, and sorting is tapped a blast furnace, nickel, cobalt etc.
Precious metals in waste nickel hydrogen battery are further reclaimed by ferromagnetic material, and to iron in waste nickel hydrogen battery,
Nickel, the magnetic separator reason of cobalt are studied with rule;
4th, using the waste and old Ni-H cell electrode material of pressurized acid leaching, active material leaching process dynamics is studied, is soaked with nickel
Extracting rate, cobalt leaching rate are Two indices, leaching condition (concentration of sulfuric acid, solution temperature, leaching using orthogonal experiment to electrode material
Go out time and solid-to-liquid ratio) optimize research;
5th, valence state and its characteristic are had according to metal ion in electrode material leachate, using extraction and chemical precipitation method
Separation and recovery rare earth element, studies the novel ion liquid extractant of environment-friendly and green, and it is that precipitating reagent is separated to study with sulfuric acid, oxalic acid
Rare earth ion;
6th, after recovering rare earth element, a small amount of Mn in filtrate2+、Fe2+、Al3+、Mg2+Deng metal ion, appropriate method is selected
Foreign ion is processed, nickel sulfate, cobalt sulfate solution in filtrate, add ammoniacal liquor, alkali lye etc., control reaction condition to prepare electricity
Pond positive electrode material precursor Ni0.8Co0.2(OH)2。
This specific embodiment is that one kind is used with waste nickel hydrogen battery as research object, to the physics of waste nickel hydrogen battery
Structure and chemical composition are analyzed, and carry out valuable gold in a series of recovery waste nickel hydrogen battery on Pressure hydrometallurgy method
The technical study of category, it is intended to develop valuable metal recovery treatment technology in efficient, economic, environment-friendly waste nickel hydrogen battery;
Research is carried out in four steps, and for the analysis result of the chemical composition of electrode material, different metallic elements are taken not
Same separation method, is reclaimed firstly, for vapour pressure low-melting-point metal high using vacuum distillation technique;Secondly, for iron, nickel,
The ferromagnetic materials such as cobalt are reclaimed using magnetic separation process;Again, for substantial amounts of rare earth element and a small amount of nickel, cobalt using pressurization acid
Lixiviation process, for filtrate in a large amount of rare earth elements rare earth carbonate is obtained using extraction, can further smelt into rare earth conjunction
Gold, or obtain rare-earth salts using the precipitation method;Again, a small amount of Mn in the filtrate after being reclaimed for rare earth element2+、Fe2+、Al3+、
Mg2+Deng foreign ion, removed using the precipitation method, nickel sulfate, cobaltous sulfate are further prepared into Ni in filtrate0.8Co0.2(OH)2, it is real
The technical process of existing " minimizing, recycling, resource ".
The advantage of this specific embodiment:On the basis of forefathers study, valuable metal is returned in carrying out waste nickel hydrogen battery
The research of receipts, develops efficient, economic, environment-friendly recycling technology.From the principle of " minimizing, recycling, resource "
Set out, study the recovery of waste nickel hydrogen battery middle rare earth, reach environmental protection, make full use of the purpose of waste resource;And study
Waste nickel hydrogen battery positive and negative pole material is separately processed, and matrix is carried out first and is separated with active material, then remakes advanced treating, real
Existing electrode active material is separated with Ni substrate, simplifies the flow that Ni-MH battery is reclaimed, and is improved and is reclaimed quality.From waste and old ni-mh electricity
From the point of view of Pooled resourcesization research, existing recovery and treatment method often focuses on the recovery of a small number of one-components, lacks to waste and old ni-mh
Battery carries out the consideration of valuable component synthetical recovery.The method that this specific embodiment passes through Pressure hydrometallurgy, Aided Machine
The technique of valuable metal recovery treatment in the technique study waste nickel hydrogen battery such as Physical, magnetic method, using Pressure hydrometallurgy
Technology is suitable to the characteristics for the treatment of is complicated to select smelting nonferrous metal resource with difficulty, realizes the comprehensive utilization of resource.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of without departing substantially from spirit or essential attributes of the invention, the present invention can be in other specific forms realized.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires to be limited rather than described above, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.Any reference in claim should not be considered as the claim involved by limitation.
Moreover, it will be appreciated that although the present specification is described in terms of embodiments, not each implementation method is only wrapped
Containing an independent technical scheme, this narrating mode of specification is only that for clarity, those skilled in the art should
Specification an as entirety, the technical scheme in each embodiment can also be formed into those skilled in the art through appropriately combined
May be appreciated other embodiment.
Claims (1)
1. the method that valuable metal is reclaimed from waste nickel hydrogen battery, it is characterised in that:Its step is:
(1), the physical arrangement and chemical composition to waste nickel hydrogen battery are analyzed, and specify battery composition and every kind of metal unit
Content and its existence form of the element in battery various pieces;
(2), by waste nickel hydrogen battery through disassembling, it is broken after sieve, realize that collector is separated with active material, using vacuum steaming
Technique is evaporated, the vapour pressure low-melting-point metal high in waste nickel hydrogen battery is reclaimed;
(3) after, waste nickel hydrogen battery is processed through vacuum distillation, its residue uses magnetic separation process, the iron such as sorting is tapped a blast furnace, nickel, cobalt
Precious metals in waste nickel hydrogen battery are further reclaimed by magnetisable material, and to iron in waste nickel hydrogen battery, nickel,
The magnetic separator reason of cobalt is studied with rule;
(4), using the waste and old Ni-H cell electrode material of pressurized acid leaching, active material leaching process dynamics is studied, is leached with nickel
Rate, cobalt leaching rate are Two indices, leaching condition (concentration of sulfuric acid, solution temperature, leaching using orthogonal experiment to electrode material
Time and solid-to-liquid ratio) optimize research;
(5) valence state and its characteristic, are had according to metal ion in electrode material leachate, using extraction and chemical precipitation method point
From recovering rare earth element, the novel ion liquid extractant of environment-friendly and green is studied, research separates dilute with sulfuric acid, oxalic acid as precipitating reagent
Native ion;
(6), after recovering rare earth element, a small amount of Mn in filtrate2+、Fe2+、Al3+、Mg2+Deng metal ion, appropriate method pair is selected
Foreign ion is processed, nickel sulfate, cobalt sulfate solution in filtrate, adds ammoniacal liquor, alkali lye etc., control reaction condition to prepare battery
Positive electrode material precursor Ni0.8Co0.2(OH)2。
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Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108963371A (en) * | 2018-07-13 | 2018-12-07 | 赣州寒锐新能源科技有限公司 | A method of recycling valuable metal from waste and old lithium ion battery |
CN109402396A (en) * | 2018-10-23 | 2019-03-01 | 昆明理工大学 | A kind of waste lithium cell positive electrode pressure leaching method |
CN109473747A (en) * | 2018-09-11 | 2019-03-15 | 天能电池集团有限公司 | A kind of waste and old lithium ion battery dismantling recovery method |
CN110767954A (en) * | 2019-09-16 | 2020-02-07 | 天齐锂业(江苏)有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
CN111321296A (en) * | 2018-12-13 | 2020-06-23 | 有研工程技术研究院有限公司 | Method for recovering vanadium and nickel from waste petroleum catalyst |
CN111334666A (en) * | 2020-03-31 | 2020-06-26 | 中国科学院金属研究所 | Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste |
CN111410240A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院金属研究所 | Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste |
CN112251604A (en) * | 2020-10-10 | 2021-01-22 | 昆明理工大学 | Method for recovering valuable metals from comprehensive recovery slag of waste lithium cobaltate batteries |
CN112680592A (en) * | 2019-10-17 | 2021-04-20 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
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CN106229577A (en) * | 2016-08-23 | 2016-12-14 | 金川集团股份有限公司 | The method that the mixing of a kind of waste nickel hydrogen battery both positive and negative polarity material is leached |
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CN101886178A (en) * | 2010-07-28 | 2010-11-17 | 江门市长优实业有限公司 | Comprehensive recovery method for nickel-hydrogen waste battery |
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108963371A (en) * | 2018-07-13 | 2018-12-07 | 赣州寒锐新能源科技有限公司 | A method of recycling valuable metal from waste and old lithium ion battery |
CN109473747A (en) * | 2018-09-11 | 2019-03-15 | 天能电池集团有限公司 | A kind of waste and old lithium ion battery dismantling recovery method |
CN109402396A (en) * | 2018-10-23 | 2019-03-01 | 昆明理工大学 | A kind of waste lithium cell positive electrode pressure leaching method |
CN111321296A (en) * | 2018-12-13 | 2020-06-23 | 有研工程技术研究院有限公司 | Method for recovering vanadium and nickel from waste petroleum catalyst |
CN110767954A (en) * | 2019-09-16 | 2020-02-07 | 天齐锂业(江苏)有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
CN110767954B (en) * | 2019-09-16 | 2021-01-22 | 天齐锂业(江苏)有限公司 | Method for carrying out distillation defluorination on lithium ion battery powder by mixed acid and synergistic valuable metal leaching |
CN112680592A (en) * | 2019-10-17 | 2021-04-20 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
CN112680592B (en) * | 2019-10-17 | 2023-03-21 | 株式会社神户制钢所 | Pretreatment method for Ni/Co recovery |
CN111334666A (en) * | 2020-03-31 | 2020-06-26 | 中国科学院金属研究所 | Method for comprehensively utilizing valuable elements in ultrasonic leaching high-temperature alloy waste |
CN111410240A (en) * | 2020-03-31 | 2020-07-14 | 中国科学院金属研究所 | Method for preparing nickel-cobalt hydroxide battery grade raw material by using high-temperature alloy waste |
CN112251604A (en) * | 2020-10-10 | 2021-01-22 | 昆明理工大学 | Method for recovering valuable metals from comprehensive recovery slag of waste lithium cobaltate batteries |
CN112251604B (en) * | 2020-10-10 | 2022-06-28 | 昆明理工大学 | Method for recovering valuable metals from comprehensive recovery slag of waste lithium cobalt oxide batteries |
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