CN106916955A - A kind of method of valuable metal in selective recovery lithium ion cell anode waste - Google Patents
A kind of method of valuable metal in selective recovery lithium ion cell anode waste Download PDFInfo
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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
- 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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- 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
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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
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- 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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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- 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
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- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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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
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- 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 kind of method of valuable metal in selective recovery lithium ion cell anode waste, comprise the following steps：Comprise the following steps：（1）Pretreatment,（2）Reduction acidleach,（3）Eddy flow electrodeposition nickel cobalt mixed powder,（4）Eddy flow electrodeposition manganese,（5）Lithium carbonate is precipitated.There is process is simple in selective recovery lithium ion cell anode waste of the invention, the characteristics of processing cost is low and selectively high to valuable metal recovery.
Description
Technical field
The present invention relates to novel energy resource material technology field, in particularly a kind of selective recovery lithium ion cell anode waste
The method of valuable metal.
Background technology
With extensive use of the lithium ion battery on power vehicle and energy storage material, the yield and demand of lithium ion battery
Amount will constantly increase severely, and from 2005 to 2015, the global annual production of lithium ion battery increased 1200%.And lithium from
Sub- battery is just constantly used in frontier, and its demand can still be increased considerably for 10 years in future.South Korea in 2017, Japan and
The lithium ion battery yield of China will account for more than the 90% of global yield.At present, China has become the maximum of lithium ion battery
One of production, consumption and exported country.
Due to electronic product update speed it is more and more faster, in addition lithium ion battery life-span typically only 1~3
Year, therefore, the waste material produced in the coming years will produce substantial amounts of waste lithium ion and its manufacture cell process.
And containing valuable metals such as nickel, cobalt, manganese, lithium, copper and aluminium in these discarded objects, wherein nickel cobalt manganese is considered as strategy metal,
Occupied an important position in following sustainable material and technology.The supply and demand of the metal needed for current these lithium ion batteries production
Contradiction is increasingly protruded in China.Therefore, if valuable metal that can be in selective recovery waste and old lithium ion battery, not only
It can be avoided to environment and the risk of human health, and the metal for substituting can be provided for each metal industry, reduced to state
The interdependency of outer metals resources, promotes sustainable development and the industrial upgrading of lithium ion battery industry.
Conventional anode material for lithium-ion batteries mainly has cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt manganese three in the market
First positive electrode and LiFePO4 etc..For the recovery of such as Ni, Co, the Mn of valuable metal in positive electrode, study both at home and abroad.
The method being widely used at present be by anode waste active material be added in sulfuric acid, nitric acid, hydrochloric acid and using hydrogen peroxide as
Reducing agent, leaches to the valuable metal in anode waste first；Then the separation of valuable metal is carried out by extraction, or again
Various valuable metals are made to reach the effect being separately recovered by adding various precipitating reagents.So will necessarily result in the increasing of cost recovery
Plus extend with process cycle.
As the A of Chinese invention patent CN 106169624 disclose a kind of lithium ion battery ternary material recovery method, wherein
Propose anode pole piece through peracid is molten, regulation pH, sintering obtains MnO after oxidizerx/ C composite, add ammonium oxalate after
Sintering obtains NiO/Co3O4Mixing material, it is eventually adding NaCO3 and obtains lithium carbonate.This method is divided again by separating valuable metals
Do not reclaim, not only need a large amount of supplementary product onsumptions, and reaction time is more long.
The wet recycle recovery lithium ion cell anode waste being related at present can be separately recovered and utilize valuable metal, again
Lithium salts and other metal ions are obtained, but it is not strong to be primarily due to be separately recovered the selectivity of valuable metal, it is therefore desirable to it is cumbersome
Removal of impurities operation just can guarantee that the purity of product, and this can cause auxiliary material consumption big, and long processing period, processing cost are higher etc.
Shortcoming limits the value of large-batch industrial.And because the specific aim of recovery method is too strong, reclaims product and be only used for weight
It is new to use in the field of synthesizing lithium ion battery, cause current recovery method restricted too big.
The content of the invention
Main purpose of the invention there are provided valuable gold in a kind of selective recovery lithium ion cell anode waste
The method of category, with process is simple, processing cost is low and selectively high to valuable metal recovery the characteristics of.
The present invention can be achieved through the following technical solutions：
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, institute
Lithium ion battery is stated for nickle cobalt lithium manganate battery, cobalt acid lithium battery, lithium manganate battery, lithium nickelate battery and/or iron manganese phosphate for lithium
One or more mixing of battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:3-6 additions 0.5-5mol/L's is sour molten
Liquid, reducing agent is added according to 1-4 times of cobalt nickel manganese total mole number, and lower stirring reaction 2-4 hours at 30-90 °C, speed of agitator is
100-500r/min, then carries out separation of solid and liquid, obtains the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 2.0-5.0, using eddy flow electricity
Product technology therefrom carries out electrodeposition, and current density is 300-600A/m2, electrolytic deposition process is not heated, when the concentration of nickel and cobalt is below
After 0.5g/L, stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid；
（4）Eddy flow electrodeposition manganese, only works as step（1）In lithium ion battery for lithium manganate battery, nickle cobalt lithium manganate battery or comprising
This step operation is carried out when lithium manganate battery, nickle cobalt lithium manganate battery, in step（3）In first deposition liquid in keep electric current it is close
Degree, after the concentration of manganese is less than 0.5g/L, stops electrodeposition, carries out separation of solid and liquid, collects electrodeposition manganese and the second filtrate；
（5）Lithium carbonate is precipitated, by step（3）First deposition liquid or step（4）In the second filtrate using precipitating reagent adjust pH
Value, obtains lithium carbonate.
Further, step（1）Middle particle diameter≤100 micron by broken anode waste.
Further, step（2）Described in acid solution be one or more in sulfuric acid, hydrochloric acid, and/or nitric acid
Mixed solution.
Further, the reducing agent is the one kind in hydrogen peroxide, oxalic acid, sodium pyrosulfite, sulfur dioxide or hydrazine hydrate
Or two or more mixtures.
Further, step（3）Described in nickel cobalt mixed powder be nickel powder and cobalt powder mixture, eddy flow electrodeposition nickel cobalt end
Point is below 0.1g/L for the concentration of cobalt ions and nickel ion.
Further, step（4）Described in eddy flow electrodeposition manganese terminal for manganese ion concentration be less than 0.1g/L.
Further, step（5）In, the precipitating reagent is ammonium hydrogen carbonate and/or sodium carbonate, the endpoint pH of precipitation process
It is 9-12.
The method of valuable metal has following beneficial technology in selective recovery lithium ion cell anode waste of the present invention
Effect：
The mode of Whote-wet method is employed in the present invention, there is provided a kind of circulation and stress lithium ion cell anode waste of high selectivity
Method, eddy flow electrodeposition is prepared for nickel cobalt powder, electrolytic manganese, lithium carbonate product, reduce removal of impurities during recycling and
The processing cost of high energy consumption, improves the quality of product, and is separately recovered the demand that valuable metal more meets market.And positive pole
Waste material can come from useless pole piece and leftover pieces in the positive electrode, or cell fabrication processes of scrap lithium ion battery or
The waste material and leftover pieces produced during production tertiary cathode material, effectively reduce its manufacturing cost.
Specific embodiment
In order that those skilled in the art will better understand the technical solution of the present invention, with reference to embodiment and to this
Invention product is described in further detail.
Embodiment 1
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, pass through
Particle diameter≤100 micron of broken anode waste are crossed, the lithium ion battery is nickle cobalt lithium manganate battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:6 add 2.75mol/L with sulfuric acid group
Into acid solution, the reducing agent being made up of hydrogen peroxide is added according to 1 times of cobalt nickel manganese total mole number, in 90 °C of lower stirring reactions 3
Hour, speed of agitator is 100r/min, then carries out separation of solid and liquid, obtains the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 5.0, using eddy flow electrodeposition skill
Art therefrom carries out electrodeposition, and current density is 450A/m2, electrolytic deposition process is not heated, after the concentration of nickel and cobalt is below 0.5g/L,
Stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid.In this step, institute
It is nickel powder and the mixture of cobalt powder to state nickel cobalt mixed powder, and eddy flow electrodeposition nickel cobalt terminal is low for the concentration of cobalt ions and nickel ion
In 0.1g/L；The terminal of the eddy flow electrodeposition manganese is less than 0.1g/L for the concentration of manganese ion.
（4）Eddy flow electrodeposition manganese, in step（3）In first deposition liquid in keep current density, when the concentration of manganese is less than
After 0.1g/L, stop electrodeposition, carry out separation of solid and liquid, collect electrodeposition manganese and the second filtrate；
（5）Lithium carbonate is precipitated, will be rapid（4）In the second filtrate using precipitating reagent adjust pH value, obtain lithium carbonate.In this step
In, the precipitating reagent is ammonium hydrogen carbonate, and the endpoint pH of precipitation process is 9.
Embodiment 2
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, pass through
Particle diameter≤100 micron of broken anode waste are crossed, the lithium ion battery is nickle cobalt lithium manganate battery, cobalt acid lithium battery and manganese
Acid lithium battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:4.5 add 0.5mol/L with hydrochloric acid group
Into acid solution, add oxalic acid as reducing agent according to 4 times of cobalt nickel manganese total mole number, in 35 °C of lower stirring reactions 2 hours, stir
Mix rotating speed is 500r/min, then carries out separation of solid and liquid, obtains the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 3.5, using eddy flow electrodeposition skill
Art therefrom carries out electrodeposition, and current density is 300A/m2, electrolytic deposition process is not heated, after the concentration of nickel and cobalt is below 0.1g/L,
Stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid.In this step, institute
It is nickel powder and the mixture of cobalt powder to state nickel cobalt mixed powder.
（4）Eddy flow electrodeposition manganese, in step（3）In first deposition liquid in keep current density, when the concentration of manganese is less than
After 0.1g/L, stop electrodeposition, carry out separation of solid and liquid, collect electrodeposition manganese and the second filtrate；
（5）Lithium carbonate is precipitated, by step（4）In the second filtrate using precipitating reagent adjust pH value, obtain lithium carbonate.In this step
In, the precipitating reagent is sodium carbonate, and the endpoint pH of precipitation process is 12.
Embodiment 3
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, pass through
Particle diameter≤100 micron of broken anode waste are crossed, the lithium ion battery is cobalt acid lithium battery and lithium nickelate battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:What 3 addition 5mol/L were constituted with nitric acid
Acid solution, the reducing agent constituted with sodium pyrosulfite is added according to 2.5 times of cobalt nickel manganese total mole number, in 90 °C of lower stirring reactions
3 hours, speed of agitator was 100r/min, then carried out separation of solid and liquid, obtained the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 5.0, using eddy flow electrodeposition skill
Art therefrom carries out electrodeposition, and current density is 450A/m2, electrolytic deposition process is not heated, after the concentration of nickel and cobalt is below 0.5g/L,
Stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid.In this step, institute
It is nickel powder and the mixture of cobalt powder to state nickel cobalt mixed powder, and eddy flow electrodeposition nickel cobalt terminal is low for the concentration of cobalt ions and nickel ion
In 0.1g/L.
（4）Lithium carbonate is precipitated, by step（3）First deposition liquid using precipitating reagent adjust pH value, obtain lithium carbonate.Herein
In step, the precipitating reagent is ammonium hydrogen carbonate and sodium carbonate, and the endpoint pH of precipitation process is 11.
Embodiment 4
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, pass through
Particle diameter≤100 micron of broken anode waste are crossed, the lithium ion battery is cobalt acid lithium battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:5 add 4mol/L with sulfuric acid, hydrochloric acid and
The acid solution of nitric acid composition, adds with hydrogen peroxide, oxalic acid, sodium pyrosulfite and hydrazine hydrate according to 3 times of cobalt nickel manganese total mole number
The reducing agent of composition, in 70 °C of lower stirring reactions 2.4 hours, speed of agitator was 200r/min, then carries out separation of solid and liquid, is obtained
First filtrate and filter residue；
（3）Eddy flow electrodeposition cobalt powder, rate-determining steps（2）In the first filtrate pH value be 3.0, therefrom entered using eddy flow electrodeposition technology
Row electrodeposition, current density is 400A/m2, electrolytic deposition process is not heated, and after the concentration of nickel and cobalt is below 0.5g/L, stops electricity
Product, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtains the first deposition liquid.In this step, the cobalt powder
Expect to be cobalt powder, eddy flow electrodeposition cobalt powder terminal is less than 0.1g/L for the concentration of cobalt ions.
（4）Lithium carbonate is precipitated, by step（3）First deposition liquid using precipitating reagent adjust pH value, obtain lithium carbonate.Herein
In step, the precipitating reagent is ammonium hydrogen carbonate and sodium carbonate, and the endpoint pH of precipitation process is 9.
Embodiment 5
The invention discloses a kind of method of valuable metal in selective recovery lithium ion cell anode waste, including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, pass through
Particle diameter≤100 micron of broken anode waste are crossed, the lithium ion battery is cobalt acid lithium battery, lithium manganate battery and manganese phosphate
Lithium iron battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:4 add 3mol/L with sulfuric acid, hydrochloric acid and
The acid solution of nitric acid composition, adds with hydrogen peroxide, oxalic acid, sodium pyrosulfite, sulfur dioxide according to 2 times of cobalt nickel manganese total mole number
The reducing agent constituted with hydrazine hydrate, in 40 °C of lower stirring reactions 3 hours, speed of agitator was 200r/min, then carries out solid-liquid point
From obtaining the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 3.0, using eddy flow electrodeposition skill
Art therefrom carries out electrodeposition, and current density is 550A/m2, electrolytic deposition process is not heated, after the concentration of nickel and cobalt is below 0.1g/L,
Stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid.In this step, institute
It is nickel powder and the mixture of cobalt powder to state nickel cobalt mixed powder.
（4）Eddy flow electrodeposition manganese, in step（3）In first deposition liquid in keep current density, when the concentration of manganese is less than
After 0.5g/L, stop electrodeposition, carry out separation of solid and liquid, collect electrodeposition manganese and the second filtrate；
（5）Lithium carbonate is precipitated, by step（4）The second filtrate using precipitating reagent adjust pH value, obtain lithium carbonate.In this step
In, the precipitating reagent is ammonium hydrogen carbonate and sodium carbonate, and the endpoint pH of precipitation process is 11.
In the present invention, the selective current potential of different valuable metals is as shown in the table, and valuable metal recovery has been effectively ensured
Selectivity is higher, with preferable Selective Separation, recycle prospect.
| Metal | Co2+/Co | Ni2+/Ni | Mn2+/Mn | Cu2+/Cu | Fe3+/Fe2+ | Al3+/Al | Li+/Li |
| /V | -0.277 | -0.257 | -1.17 | 0.35 | 0.77 | -1.67 | -3.04 |
The above, only presently preferred embodiments of the present invention not makees any formal limitation to the present invention；It is all
The those of ordinary skill of the industry can shown in by specification and the above and swimmingly implement the present invention；But, it is all to be familiar with
Professional and technical personnel without departing from the scope of the present invention, makes using disclosed above technology contents
A little variation, modification and evolution equivalent variations, be Equivalent embodiments of the invention；Meanwhile, it is all according to reality of the invention
Variation, modification and evolution of any equivalent variations that matter technology is made to above example etc., still fall within technology of the invention
Within the protection domain of scheme.
Claims (7)
1. in a kind of selective recovery lithium ion cell anode waste valuable metal method, it is characterised in that including following step
Suddenly：
（1）Pretreatment：Disassemble waste and old lithium ion battery to take out positive plate and crush, obtain lithium ion cell anode waste, institute
Lithium ion battery is stated for nickle cobalt lithium manganate battery, cobalt acid lithium battery, lithium manganate battery, lithium nickelate battery and/or iron manganese phosphate for lithium
One or more mixing of battery；
（2）Reduction acidleach：In step（1）In the anode waste that obtains according to solid-to-liquid ratio 1:3-6 additions 0.5-5mol/L's is sour molten
Liquid, reducing agent is added according to 1-4 times of cobalt nickel manganese total mole number, and lower stirring reaction 2-4 hours at 30-90 °C, speed of agitator is
100-500r/min, then carries out separation of solid and liquid, obtains the first filtrate and filter residue；
（3）Eddy flow electrodeposition nickel cobalt mixed powder, rate-determining steps（2）In the first filtrate pH value be 2.0-5.0, using eddy flow electricity
Product technology therefrom carries out electrodeposition, and current density is 300-600A/m2, electrolytic deposition process is not heated, when the concentration of nickel and cobalt is below
After 0.5g/L, stop electrodeposition, the collection of electrodeposition nickel cobalt mixed powder is carried out using magnetic means, obtain the first deposition liquid；
（4）Eddy flow electrodeposition manganese, only works as step（1）In lithium ion battery for lithium manganate battery, nickle cobalt lithium manganate battery or comprising
This step operation is carried out when lithium manganate battery, nickle cobalt lithium manganate battery, in step（3）In first deposition liquid in keep electric current it is close
Degree, after the concentration of manganese is less than 0.5g/L, stops electrodeposition, carries out separation of solid and liquid, collects electrodeposition manganese and the second filtrate；
（5）Lithium carbonate is precipitated, by step（3）First deposition liquid or step（4）In the second filtrate using precipitating reagent adjust pH
Value, obtains lithium carbonate.
2. in selective recovery lithium ion cell anode waste according to claim 1 valuable metal method, its feature
It is：Step（1）Middle particle diameter≤100 micron by broken anode waste.
3. in selective recovery lithium ion cell anode waste according to claim 1 and 2 valuable metal method, it is special
Levy and be：Step（2）Described in acid solution for one or more the mixing in sulfuric acid, hydrochloric acid, and/or nitric acid it is molten
Liquid.
4. in selective recovery lithium ion cell anode waste according to claim 3 valuable metal method, its feature
It is：The reducing agent be hydrogen peroxide, oxalic acid, sodium pyrosulfite, sulfur dioxide or hydrazine hydrate in one or more
Mixture.
5. in selective recovery lithium ion cell anode waste according to claim 4 valuable metal method, its feature
It is：Step（3）Described in nickel cobalt mixed powder be nickel powder and cobalt powder mixture, further, eddy flow electrodeposition nickel cobalt terminal
For the concentration of cobalt ions and nickel ion is below 0.1g/L.
6. in selective recovery lithium ion cell anode waste according to claim 4 valuable metal method, its feature
It is：Step（4）Described in eddy flow electrodeposition manganese terminal for manganese ion concentration be less than 0.1g/L.
7. in the selective recovery lithium ion cell anode waste according to claim 5 or 6 valuable metal method, it is special
Levy and be：Step（5）In, the precipitating reagent is ammonium hydrogen carbonate and/or sodium carbonate, and the endpoint pH of precipitation process is 9-12.
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108384955A (en) * | 2018-03-20 | 2018-08-10 | 中国科学院过程工程研究所 | A method of from selectively carrying lithium in waste material containing lithium battery |
| CN108470951A (en) * | 2018-03-09 | 2018-08-31 | 中南大学 | The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium ion battery |
| CN109439904A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A method of the leaching valuable metal from waste lithium cell positive electrode |
| CN109585962A (en) * | 2018-11-30 | 2019-04-05 | 成都尤尼瑞克科技有限公司 | A kind of method of the waste and old positive electrode of resource utilization lithium battery |
| CN110257631A (en) * | 2019-06-14 | 2019-09-20 | 广西师范大学 | A kind of method of lithium and other metals in separating waste, worn lithium ion cell positive |
| CN110629034A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering cobalt and nickel from tungsten waste recovery slag |
| CN111118297A (en) * | 2019-06-11 | 2020-05-08 | 中国科学院过程工程研究所 | Method and device for selectively extracting lithium |
| CN111519031A (en) * | 2020-04-29 | 2020-08-11 | 江苏北矿金属循环利用科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder |
| CN112054261A (en) * | 2020-07-28 | 2020-12-08 | 昆明理工大学 | Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis |
| CN112251776A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering metal from waste lithium battery positive electrode material |
| CN114132909A (en) * | 2021-12-07 | 2022-03-04 | 自贡同发荣新材料有限公司 | Method for recycling pure metal salt from retired manganese iron phosphate lithium battery waste |
| CN115386727A (en) * | 2022-07-21 | 2022-11-25 | 珠海格力绿色再生资源有限公司 | Valuable metal recovery method for lithium battery |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108470951A (en) * | 2018-03-09 | 2018-08-31 | 中南大学 | The recovery method of valuable metal in a kind of waste and old nickel-cobalt-manganese ternary lithium ion battery |
| CN108384955A (en) * | 2018-03-20 | 2018-08-10 | 中国科学院过程工程研究所 | A method of from selectively carrying lithium in waste material containing lithium battery |
| CN109439904A (en) * | 2018-09-20 | 2019-03-08 | 广东佳纳能源科技有限公司 | A method of the leaching valuable metal from waste lithium cell positive electrode |
| CN109585962A (en) * | 2018-11-30 | 2019-04-05 | 成都尤尼瑞克科技有限公司 | A kind of method of the waste and old positive electrode of resource utilization lithium battery |
| CN111118297A (en) * | 2019-06-11 | 2020-05-08 | 中国科学院过程工程研究所 | Method and device for selectively extracting lithium |
| CN110257631A (en) * | 2019-06-14 | 2019-09-20 | 广西师范大学 | A kind of method of lithium and other metals in separating waste, worn lithium ion cell positive |
| CN110629034A (en) * | 2019-09-16 | 2019-12-31 | 厦门钨业股份有限公司 | Method for recovering cobalt and nickel from tungsten waste recovery slag |
| CN111519031A (en) * | 2020-04-29 | 2020-08-11 | 江苏北矿金属循环利用科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder |
| CN112054261A (en) * | 2020-07-28 | 2020-12-08 | 昆明理工大学 | Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis |
| CN112054261B (en) * | 2020-07-28 | 2021-10-08 | 昆明理工大学 | Method for recovering waste lithium battery positive electrode through mechanical activation assisted spray pyrolysis |
| CN112251776A (en) * | 2020-10-22 | 2021-01-22 | 中钢集团南京新材料研究院有限公司 | Method for recovering metal from waste lithium battery positive electrode material |
| CN114132909A (en) * | 2021-12-07 | 2022-03-04 | 自贡同发荣新材料有限公司 | Method for recycling pure metal salt from retired manganese iron phosphate lithium battery waste |
| CN115386727A (en) * | 2022-07-21 | 2022-11-25 | 珠海格力绿色再生资源有限公司 | Valuable metal recovery method for lithium battery |
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