CN109852801A - The recovery method of cobalt and lithium in anode material for lithium-ion batteries - Google Patents
The recovery method of cobalt and lithium in anode material for lithium-ion batteries Download PDFInfo
- Publication number
- CN109852801A CN109852801A CN201811643567.5A CN201811643567A CN109852801A CN 109852801 A CN109852801 A CN 109852801A CN 201811643567 A CN201811643567 A CN 201811643567A CN 109852801 A CN109852801 A CN 109852801A
- Authority
- CN
- China
- Prior art keywords
- lithium
- acid
- cobalt
- recovery method
- dipping
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides the recovery methods of cobalt and lithium in a kind of anode material for lithium-ion batteries.The recovery method includes: step S1, carries out dipping to anode material for lithium-ion batteries using faintly acid material and forms the first dipping system, wherein the pH value of faintly acid material is between 4~6；Step S2 is separated by solid-liquid separation the first dipping system, obtains the first Solid separate and the isolate of liquid containing lithium；Step S3 carries out dipping to the first Solid separate using highly acid material and forms the second dipping system, and the pH value of middle strong acidity material is less than or equal to 1；And step S4, the second dipping system is separated by solid-liquid separation, the second Solid separate and the isolate of liquid containing cobalt are obtained.By controlling the pH value of dipping system, so that lithium ion and cobalt ions are impregnated into respectively in different leachates, so as to avoid the intersection of two kinds of metals, finally obtained cobalt product and lithium product purity are higher.
Description
Technical field
The present invention relates to lithium ion battery recycling fields, in particular to cobalt in a kind of anode material for lithium-ion batteries
With the recovery method of lithium.
Background technique
Lithium ion battery has many advantages, such as that light weight, energy density are big, without memory and be widely used, due to lithium ion
The increase of battery usage amount and service life are limited, and the trend increased year by year is also presented in learies.Anode of lithium ion battery material
In material nickel element content be 5%~10% (w), cobalt element content be 5%~20% (w) lithium content be 5%~7% (w).Cobalt
It is metal and one of the development of the national economy and the indispensable important source material of national defense construction of resource scarcity, the storage of China's geology
About 870,000 tons of amount, but lean ore is more, the cobalt mineralss of independent mineralization only account for 5%, every year need to be from external import cobalt about 1000~1200
Ton.With the increase of lithium battery usage amount, the price of lithium also gradually increases.If in waste and old lithium ion battery these are valuable
Metal is recycled, and will largely alleviate the problem of China's non-ferrous metal scarcity, it " is turned waste into wealth ", but also solves
Determined environmental pollution the problem of.The recycling and reusing of waste and old lithium ion battery will have very big in the society of this energy shortage
Development prospect.Either from environmental protection, or from reduce industrial cost, realize that effective use of resource etc. is seen, lithium from
The project emerging as one that recycle of sub- battery is all of great significance to national even All Around The World.
The prior art is usually to carry out a step leaching to the positive electrode of pre-treatment, dissolves the metallic elements such as lithium cobalt all
In leachate, then the ion of leachate is separated again, other metals member may be mingled with during the separation process in this way
Element causes separation to be not thorough, and the solution made is impure, causes the precipitated product finally obtained impure, so that under product qualities
Drop.
Summary of the invention
The main purpose of the present invention is to provide the recovery methods of cobalt and lithium in a kind of anode material for lithium-ion batteries, with solution
The impure problem of the product that recovery method certainly in the prior art obtains.
To achieve the goals above, according to an aspect of the invention, there is provided in a kind of anode material for lithium-ion batteries
The recovery method of cobalt and lithium, comprising: step S1 carries out dipping to anode material for lithium-ion batteries using faintly acid material and forms the
One dipping system, wherein the pH value of faintly acid material is between 4~6；Step S2 is separated by solid-liquid separation the first dipping system,
Obtain the first Solid separate and the isolate of liquid containing lithium；Step S3 carries out the first Solid separate using highly acid material
Dipping forms the second dipping system, and the pH value of middle strong acidity material is less than or equal to 1；And step S4, to the second dipping system
It is separated by solid-liquid separation, obtains the second Solid separate and the isolate of liquid containing cobalt.
Further, in above-mentioned steps S1, faintly acid material includes: acetic acid, Acetic acid-sodium acetate mixture, oxalic acid, phosphoric acid
It is disodium hydrogen-citric acid mixture, citric acid-sodium hydroxide-hydrochloric acid mixture, any in citric acid-sodium citrate mixture
It is a kind of.
Further, in above-mentioned steps S1, the solid-to-liquid ratio of the first dipping system is 1:20~1:100, the preferably first dipping
The temperature of system is 30~80 DEG C, and the time further preferably impregnated is 10~60min.
Further, in above-mentioned steps S3, highly acid material includes strong acid, and strong acid is selected from sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid
In the mixture of any one or more；It is preferred that the molar concentration of strong acid is 1~5mol.L-1。
Further, in above-mentioned steps S3, second dipping system solid-to-liquid ratio be 1:10~1:50, further preferred second
The temperature of dipping system is 30~80 DEG C, and the time more preferably impregnated is 20~120min.
Further, above-mentioned highly acid material further includes reducing agent, the volume fraction of reducing agent preferably in highly acid material
It is 0.5~5%, further preferred reducing agent is H2O2, sodium thiosulfate, any one or more in sodium sulfite.
Further, above-mentioned recovery method further include: cobalt liquid isolate and/or the isolate of liquid containing lithium and saturation will be contained
Sodium carbonate liquor is mixed, and hybrid reaction system is formed；Hybrid reaction system is heated, cobalt carbonate and carbon are respectively obtained
Sour lithium.
Further, above-mentioned hybrid reaction system is heated to 60~100 DEG C and kept the temperature, preferably 5~30min of heat preservation.
Further, above-mentioned anode material for lithium-ion batteries is powdered, and recovery method further includes putting to lithium battery
Powdered anode material for lithium-ion batteries is obtained after electricity, dismantling, removing.
Further, above-mentioned steps S2 and step S4 using filtering and washing by the way of realize separation of solid and liquid.
It applies the technical scheme of the present invention, the above-mentioned recovery method of the application, by controlling the pH value of dipping system, so that lithium
Ion and cobalt ions are impregnated into respectively in different leachates, so as to avoid the intersection of two kinds of metals, finally obtained cobalt
Product and lithium product purity are higher.
Specific embodiment
It should be noted that in the absence of conflict, the features in the embodiments and the embodiments of the present application can phase
Mutually combination.Below in conjunction with embodiment, the present invention will be described in detail.
As the application background technique is analyzed, a step extract technology of the prior art to press from both sides in the leachate after separation
Miscellaneous other metals, and then cause the product finally obtained impure, in order to solve this problem, this application provides a kind of lithium-ion electrics
The recovery method of cobalt and lithium in the positive electrode of pond, which includes: step S1, using faintly acid material to lithium ion battery
Positive electrode carries out dipping and forms the first dipping system, and wherein the pH value of faintly acid material is between 4~6；Step S2, to first
Dipping system is separated by solid-liquid separation, and the first Solid separate and the isolate of liquid containing lithium are obtained；Step S3 utilizes highly acid material
Dipping is carried out to the first Solid separate and forms the second dipping system, the pH value of middle strong acidity material is less than or equal to 1；And step
Rapid S4 is separated by solid-liquid separation the second dipping system, obtains the second Solid separate and the isolate of liquid containing cobalt.
The above-mentioned recovery method of the application, by controlling the pH value of dipping system, so that lithium ion and cobalt ions are immersed respectively
Stain is into different leachates, and so as to avoid the intersection of two kinds of metals, finally obtained cobalt product and lithium product purity are higher.
Specifically:
First anode material for lithium-ion batteries (cobalt acid lithium) is soaked between 4~6 with the pH value of control faintly acid material
Out, lithium is leached at this time, and cobalt will not be dissolved, and is because cobalt ions can not move freely, lithium ion can be certainly in gap
By moving, therefore H+Replaceable Li out+.Then the pH value for controlling highly acid material, which is less than or equal to the lattice that 1 destroys cobalt acid lithium, makes cobalt
Ion release.
In a preferred embodiment of the present application, in above-mentioned steps S1, faintly acid material includes: acetic acid, acetic acid-acetic acid
Sodium mixture, oxalic acid, disodium hydrogen phosphate-citric acid mixture, citric acid-sodium hydroxide-hydrochloric acid mixture, citric acid-lemon
Any one in sour sodium mixture.Using the faintly acid material comprising above-mentioned organic acid, so that the pH value of the first dipping system
It is easy to control and will not introduce other impurity that should not be removed.The ratio of each ingredient is not specially limited in above-mentioned each mixture.
In order to improve the leaching rate of lithium, in preferably above-mentioned steps S1, the solid-to-liquid ratio of the first dipping system is 1:20~1:
100.In addition, the temperature of the preferably first dipping system is 30~80 DEG C in order to improve the leaching efficiency of lithium.In order to accelerate process,
The time further preferably impregnated is 10~60min.
In the application another kind preferred embodiment, in above-mentioned steps S3, above-mentioned highly acid material includes strong acid, strong acid
The mixture of any one or more in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid.It can be by using above-mentioned highly acid material
The pH value of two dipping systems is quickly adjusted to 1 hereinafter, improving the leaching efficiency of cobalt in turn.Realizing the mesh for adjusting above-mentioned pH value
On the basis of, in order to reduce the dosage of highly acid material, the preferably molar concentration of strong acid is 1-5mol.L-1。
Similarly, in order to improve the leaching rate of cobalt, in preferably above-mentioned steps S3, the solid-to-liquid ratio of the second dipping system is 1:
10-1:50.In order to further speed up the leaching of cobalt, the temperature of further preferred second dipping system is 30-80 DEG C, is more preferably soaked
The time of stain is 20~120min.
Additionally, it is preferred that above-mentioned highly acid material further includes reducing agent, Co can be made using reducing agent3+It is reduced into Co2+, from
And cobalt ions is enable to be easier to dissolve out.
In order to make the effect of above-mentioned reducing agent and the effect synergy of strong acid, the body of reducing agent preferably in highly acid material
Fraction is 0.5~5%, and further preferred reducing agent is H2O2, sodium thiosulfate, any one or more in sodium sulfite.
In the application another kind embodiment, above-mentioned recovery method further include: cobalt liquid isolate and/or liquid containing lithium will be contained
Body isolate is mixed with saturated sodium carbonate solution, forms hybrid reaction system；Hybrid reaction system is heated, respectively
Obtain cobalt carbonate and lithium carbonate.Cobalt and lithium is made to be separately converted to corresponding carbonate by the above process, and carbonate is pure
It spends higher.
In order to accelerate the conversion of above-mentioned cobalt and lithium, hybrid reaction system is preferably heated to 60~100 DEG C and is kept the temperature, preferably
Keep the temperature 5~30min.
In addition, preferably above-mentioned anode material for lithium-ion batteries is powder in order to enable above-mentioned pickling efficiency further increases
Shape, above-mentioned recovery method further include discharged lithium battery, disassembled, remove after obtain powdered lithium ion cell positive material
Material.
In addition, there are many modes being separated by solid-liquid separation in above-mentioned steps S2 and step S4, in order to reduce separation costs and mention
High separating effect, preferably above-mentioned steps S2 and step S4 realize separation of solid and liquid by the way of filtering and washing.
Below with reference to embodiment and comparative example, the beneficial effect of the application is further illustrated.
Embodiment 1
(1) waste lithium cell is obtained into lithium cobaltate cathode powder after self discharge, dismantling, removing.
(2) cobalt acid lithium powder is added in the three-necked bottle equipped with Acetic acid-sodium acetate solution according to the solid-to-liquid ratio of 1:20, vinegar
Acid-sodium acetate solution pH is 4.5, then carries out continuing stirring, reaction temperature is 50 DEG C, reaction time 30min.
(3) reaction product of step (2) is filtered, washed, it is stand-by to obtain the filtrate containing lithium ion.It is surveyed with ICP and contains lithium
The content of lithium ion and cobalt ions in the filtrate of ion, obtains there was only lithium ion in solution, and no cobalt ions exists.
(4) H is added in above-mentioned filter residue2SO4+H2O2Mixed solution, H2SO4Molar concentration be 2mol.L-1, addition
H2O2Volume fraction be 0.5%, solid-to-liquid ratio 1:30, reaction temperature be 60 DEG C, reaction time 60min.It is completed wait react
Afterwards, the solution containing cobalt ions is filtered to obtain.The content that lithium ion and cobalt ions in the solution containing cobalt ions are measured with ICP, obtains solution
In only cobalt ions, no lithium ion exist.
(5) it will be separately added into saturated sodium carbonate solution in the resulting solution containing lithium ion and the solution containing cobalt ions, instead
Answering temperature is 80 DEG C, reaction time 30min.It filters, wash while hot after being generated without precipitating, drying obtained lithium carbonate and carbonic acid
Cobalt.
Embodiment 2
(1) waste lithium cell is obtained into lithium cobaltate cathode powder after self discharge, dismantling, removing.
(2) cobalt acid lithium powder is added in the three-necked bottle being equipped with according to the solid-to-liquid ratio of 1:50, Acetic acid-sodium acetate solution
PH is 5.0, then carries out continuing stirring, reaction temperature is 80 DEG C, reaction time 20min.
(3) reaction product of step (2) is filtered, washs, it is stand-by obtains the filtrate containing lithium ion.Solution is surveyed with ICP
The content of middle lithium ion and cobalt ions, obtains there was only lithium ion in solution, and no cobalt ions exists.
(4) H is added in above-mentioned filter residue2SO4+H2O2Solution, H2SO4Molar concentration be 3mol.L-1, the H of addition2O2's
Volume fraction is 1%, solid-to-liquid ratio 1:20, and reaction temperature is 80 DEG C, reaction time 40min.To after the reaction was completed, filter
Solution containing cobalt ions.The content that lithium ion and cobalt ions in solution are measured with ICP, obtain in solution only have cobalt ions, no lithium from
Son exists.
(5) sodium carbonate liquor of saturation will be separately added into the resulting solution containing lithium ion and the solution containing cobalt ions,
Reaction temperature is 60 DEG C, reaction time 30min.It filters, wash while hot after being generated without precipitating, drying obtained lithium carbonate and carbon
Sour cobalt.
Embodiment 3
The difference from embodiment 1 is that the pH of Acetic acid-sodium acetate solution is 6.0.
Embodiment 4
The difference from embodiment 1 is that the pH of Acetic acid-sodium acetate solution is 4.0.
Embodiment 5
The difference from embodiment 1 is that step (2) impregnates cobalt acid lithium powder using oxalic acid.
Embodiment 6
The difference from embodiment 1 is that cobalt acid lithium powder is added to according to the solid-to-liquid ratio of 1:100 equipped with vinegar by step (2)
In acid-sodium acetate solution three-necked bottle.
Embodiment 7
The difference from embodiment 1 is that the reaction temperature of step (2) is 30 DEG C.
Embodiment 8
The difference from embodiment 1 is that the reaction time of step (2) is 10min.
Embodiment 9
The difference from embodiment 1 is that the reaction time of step (2) is 60min.
Embodiment 10
The difference from embodiment 1 is that H is added in above-mentioned filter residue in step (4)2SO4+H2O2Mixed solution, H2SO4Rub
Your concentration is 5mol.L-1。
Embodiment 11
The difference from embodiment 1 is that H is added in above-mentioned filter residue in step (4)2SO4+H2O2Mixed solution, H2SO4Rub
Your concentration is 1mol.L-1。
Embodiment 12
The difference from embodiment 1 is that solid-to-liquid ratio is 1:10 in step (4).
Embodiment 13
The difference from embodiment 1 is that solid-to-liquid ratio is 1:50 in step (4).
Embodiment 14
The difference from embodiment 1 is that reaction temperature is 30 DEG C in step (4).
Embodiment 15
The difference from embodiment 1 is that the reaction time is 20min in step (4).
Embodiment 16
The difference from embodiment 1 is that the reaction time is 120min in step (4).
Embodiment 17
The difference from embodiment 1 is that H in step (4)2O2Volume fraction be 5%.
Embodiment 18
The difference from embodiment 1 is that the sulfuric acid in step (4) replaces with nitric acid.
Embodiment 19
The difference from embodiment 1 is that the H in step (4)2O2Replace with sodium thiosulfate, the volume point of sodium thiosulfate
Number is 1%.
Embodiment 20
The difference from embodiment 1 is that the reaction temperature in step (5) is 100 DEG C, reaction time 5min.
Embodiment 21
(1) waste lithium cell is obtained into lithium cobaltate cathode powder after self discharge, dismantling, removing.
(2) cobalt acid lithium powder is added in the three-necked bottle equipped with Acetic acid-sodium acetate solution according to the solid-to-liquid ratio of 1:20, vinegar
Acid-sodium acetate solution pH is 4.5, then carries out continuing stirring, reaction temperature is 90 DEG C, reaction time 30min.
(3) reaction product of step (2) is filtered, washed, it is stand-by to obtain the filtrate containing lithium ion.It is surveyed with ICP and contains lithium
The content of lithium ion and cobalt ions in the filtrate of ion, obtains there was only lithium ion in solution, and no cobalt ions exists.
(4) H is added in above-mentioned filter residue2SO4+H2O2Mixed solution, H2SO4Molar concentration be 2mol.L-1, addition
H2O2Volume fraction be 0.5%, solid-to-liquid ratio 1:30, reaction temperature be 60 DEG C, reaction time 150min.It is completed wait react
Afterwards, the solution containing cobalt ions is filtered to obtain.The content that lithium ion and cobalt ions in the solution containing cobalt ions are measured with ICP, obtains solution
In only cobalt ions, no lithium ion exist.
(5) it will be separately added into saturated sodium carbonate solution in the resulting solution containing lithium ion and the solution containing cobalt ions, instead
Answering temperature is 80 DEG C, reaction time 30min.It filters, wash while hot after being generated without precipitating, drying obtained lithium carbonate and carbonic acid
Cobalt.
Comparative example 1
(1) discharge treatment is carried out to waste and old cobalt acid lithium battery first, can get the positive plate of battery after disassembling.It will just
Pole piece is put into Muffle furnace and calcines, and the temperature of calcining is 400 DEG C, and calcining time is 3 hours, finally can get black cobalt acid lithium powder
End；
(2) mixed liquor equipped with sulfuric acid, citric acid and hydrogen peroxide is added by the solid-to-liquid ratio of 10g/L in cobalt acid lithium powder
In three-necked flask, citric acid and H2SO4Concentration is 2.0mol.L-1, H2O2Concentration is 2vol.%, is then placed in three-necked flask
It is reacted in magnetic stirring apparatus with microwave and heating function, reaction temperature is 40 DEG C, microwave power 400w, when reaction
Between be 3 hours, in magnetic stirring apparatus mixing speed be 50r/min；
(3) concentration is added in the solution obtained to step (2) reaction is that 1.0M oxalic acid is reacted, reaction temperature 40
DEG C, the reaction time is 3 hours, generates cobalt oxalate precipitation；Cobalt oxalate purity is that 98%, ICP detection discovery is wherein mingled with part
Lithium ion.
(4) after generating without precipitating, it is 1.0mol.L that concentration is added thereto-1Sodium carbonate, reaction temperature be 40 DEG C, instead
It is 5 hours between seasonable, generates lithium carbonate precipitating.
During the various embodiments described above carry out, using the content of cobalt and lithium in ICP detection cobalt acid lithium powder, in each filtrate
The content and cobalt carbonate of cobalt and lithium and the weight and purity of lithium carbonate, and then calculate leaching rate, the leaching rate of cobalt, lithium of lithium
The rate of recovery, the rate of recovery of cobalt, the purity of lithium carbonate and cobalt carbonate, the results are shown in Table 1.
Table 1
By the comparison to this programme embodiment and comparative example, the carbonate product of the resulting cobalt lithium of this programme can be obtained
Purity is higher.It is dissolved in comparative example with a step dissolution method, obtains the solution of the lithium containing cobalt, then cobalt is precipitated, finally to lithium
It is precipitated.The lithium ion of sub-fraction can be mingled with when precipitating to cobalt in this way, the cobalt oxalate made is impure.And it is our
Case first obtains pure solution, is then precipitated again, avoids sediment and is mingled with to other ions, and resulting sediment purity is more
It is high.
It can be seen from the above description that the above embodiments of the present invention realized the following chievements:
The above-mentioned recovery method of the application, by controlling the pH value of dipping system, so that lithium ion and cobalt ions are immersed respectively
Stain is into different leachates, and so as to avoid the intersection of two kinds of metals, finally obtained cobalt product and lithium product purity are higher.
Specifically:
First anode material for lithium-ion batteries (cobalt acid lithium) is carried out between 4~6 with the pH value of control the first dipping system
It leaches, lithium is leached at this time, and cobalt will not be dissolved, and is because cobalt ions can not move freely, lithium ion can in gap
Free movement, therefore H+Replaceable Li out+.Then the pH value of the second dipping of control system, which is less than or equal to 1 destruction lattice, makes cobalt ions
Dissolution.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. the recovery method of cobalt and lithium in a kind of anode material for lithium-ion batteries characterized by comprising
Step S1 carries out dipping to anode material for lithium-ion batteries using faintly acid material and forms the first dipping system, wherein institute
The pH value of faintly acid material is stated between 4~6；
Step S2 is separated by solid-liquid separation the first dipping system, obtains the first Solid separate and the isolate of liquid containing lithium；
Step S3 carries out dipping to first Solid separate using highly acid material and forms the second dipping system, wherein institute
The pH value for stating highly acid material is less than or equal to 1；And
Step S4 is separated by solid-liquid separation the second dipping system, obtains the second Solid separate and the isolate of liquid containing cobalt.
2. recovery method according to claim 1, which is characterized in that in the step S1, the faintly acid material includes:
Acetic acid, Acetic acid-sodium acetate mixture, oxalic acid, disodium hydrogen phosphate-citric acid mixture, citric acid-sodium hydroxide-mixed in hydrochloric acid
Any one in object, citric acid-sodium citrate mixture.
3. recovery method according to claim 1, which is characterized in that in the step S1, the first dipping system
Solid-to-liquid ratio is 1:20~1:100, and the temperature of the preferably described first dipping system is 30~80 DEG C, the further preferred dipping
Time is 10~60min.
4. recovery method according to claim 1, which is characterized in that in the step S3, the highly acid material includes
Strong acid, the mixture of any one or more of the strong acid in sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid；It is preferred that the strong acid
Molar concentration is 1~5mol.L-1。
5. recovery method according to claim 1, which is characterized in that in the step S3, the second dipping system
Solid-to-liquid ratio is 1:10~1:50, and the temperature of the further preferably described second dipping system is 30~80 DEG C, the more preferable dipping
Time be 20~120min.
6. recovery method according to any one of claim 1 to 5, which is characterized in that the highly acid material further includes
Reducing agent, the volume fraction of reducing agent described in the preferably described highly acid material are 0.5~5%, the further preferred reduction
Agent is H2O2, sodium thiosulfate, any one or more in sodium sulfite.
7. recovery method according to claim 1, which is characterized in that the recovery method further include:
The isolate of liquid containing cobalt and/or the liquid containing lithium isolate are mixed with saturated sodium carbonate solution, formed
Hybrid reaction system；
The hybrid reaction system is heated, cobalt carbonate and lithium carbonate are respectively obtained.
8. recovery method according to claim 7, which is characterized in that the hybrid reaction system is heated to 60~100
DEG C and keep the temperature, preferably heat preservation 5~30min.
9. recovery method according to claim 1, which is characterized in that the anode material for lithium-ion batteries be it is powdered,
The recovery method further include discharged lithium battery, disassembled, remove after obtain the powdered lithium ion cell positive
Material.
10. recovery method according to claim 1, which is characterized in that the step S2's and step S4 used
The mode of filter and washing realizes the separation of solid and liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811643567.5A CN109852801A (en) | 2018-12-29 | 2018-12-29 | The recovery method of cobalt and lithium in anode material for lithium-ion batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811643567.5A CN109852801A (en) | 2018-12-29 | 2018-12-29 | The recovery method of cobalt and lithium in anode material for lithium-ion batteries |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109852801A true CN109852801A (en) | 2019-06-07 |
Family
ID=66893481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811643567.5A Pending CN109852801A (en) | 2018-12-29 | 2018-12-29 | The recovery method of cobalt and lithium in anode material for lithium-ion batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109852801A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114317970A (en) * | 2021-11-30 | 2022-04-12 | 广东邦普循环科技有限公司 | Recovery method of waste lithium cobalt oxide battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1688065A (en) * | 2005-04-25 | 2005-10-26 | 武汉理工大学 | Method for separating and recovering cobalt from waste lithium ion cell |
| CN1973399A (en) * | 2004-06-21 | 2007-05-30 | 丰田自动车株式会社 | Method of disposing of lithium battery |
| CN102101701A (en) * | 2010-12-31 | 2011-06-22 | 湖南邦普循环科技有限公司 | Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite |
| WO2012111895A1 (en) * | 2011-02-17 | 2012-08-23 | 한국지질자원연구원 | Method for manufacturing a valuable-metal sulfuric-acid solution from a waste battery, and method for manufacturing a positive electrode active material |
| CN107978814A (en) * | 2017-07-04 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method of Selective Separation lithium in material from waste lithium ion cell anode |
-
2018
- 2018-12-29 CN CN201811643567.5A patent/CN109852801A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1973399A (en) * | 2004-06-21 | 2007-05-30 | 丰田自动车株式会社 | Method of disposing of lithium battery |
| CN1688065A (en) * | 2005-04-25 | 2005-10-26 | 武汉理工大学 | Method for separating and recovering cobalt from waste lithium ion cell |
| CN102101701A (en) * | 2010-12-31 | 2011-06-22 | 湖南邦普循环科技有限公司 | Method for recovering cobalt and lithium from waste lithium cobaltite and preparing lithium cobaltite |
| WO2012111895A1 (en) * | 2011-02-17 | 2012-08-23 | 한국지질자원연구원 | Method for manufacturing a valuable-metal sulfuric-acid solution from a waste battery, and method for manufacturing a positive electrode active material |
| CN107978814A (en) * | 2017-07-04 | 2018-05-01 | 中国科学院过程工程研究所 | A kind of method of Selective Separation lithium in material from waste lithium ion cell anode |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114317970A (en) * | 2021-11-30 | 2022-04-12 | 广东邦普循环科技有限公司 | Recovery method of waste lithium cobalt oxide battery |
| WO2023098167A1 (en) * | 2021-11-30 | 2023-06-08 | 广东邦普循环科技有限公司 | Method for recovering waste lithium cobalt oxide battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lv et al. | A sustainable process for metal recycling from spent lithium-ion batteries using ammonium chloride | |
| Zhuang et al. | Recovery of valuable metals from LiNi0. 5Co0. 2Mn0. 3O2 cathode materials of spent Li-ion batteries using mild mixed acid as leachant | |
| CN109935922A (en) | A method of recycling valuable metal from waste and old lithium ion battery material | |
| Nan et al. | Recovery of metal values from a mixture of spent lithium-ion batteries and nickel-metal hydride batteries | |
| CN106848471A (en) | A kind of nitration mixture of waste lithium ion cell anode material is leached and recovery method | |
| CN108832215A (en) | A kind of method of selective recovery anode material for lithium-ion batteries | |
| CN103526016B (en) | A kind of method of raw material containing lead hydrometallurgic recovery | |
| Yang et al. | An advanced strategy of “metallurgy before sorting” for recycling spent entire ternary lithium-ion batteries | |
| CN106611841B (en) | A method of nickel-cobalt-manganese ternary material precursor is prepared using nickel cobalt slag charge | |
| CN109022803A (en) | The recovery method of elemental lithium during a kind of waste phosphoric acid lithium iron battery is positive | |
| CN114195112A (en) | Recovery method of waste lithium iron phosphate battery | |
| CN106591584A (en) | Method of recovering cobalt and lithium from anode material of spent cobalt acid lithium battery | |
| CN107742760A (en) | Method for extracting lithium from waste lithium ion battery | |
| CN107083484A (en) | A kind of method that metal is reclaimed from waste lithium cell | |
| Wu et al. | Selective recovery of lithium from spent lithium iron phosphate batteries using oxidation pressure sulfuric acid leaching system | |
| CN108011149A (en) | A kind of method of the Call Provision nickel lithium from discarded power battery | |
| Ma et al. | Reaction mechanism of antibiotic bacteria residues as a green reductant for highly efficient recycling of spent lithium-ion batteries | |
| Wang et al. | Ammonia leaching of valuable metals from spent lithium ion batteries in NH3-(NH4) 2SO4-Na2SO3 system | |
| CN109167118A (en) | The method of comprehensive utilization of ferric phosphate lithium cell electrode material | |
| CN108264068A (en) | A kind of method for recycling lithium in waste material containing lithium battery | |
| Luo et al. | Recycling of waste lithium-ion batteries via a one-step process using a novel deep eutectic solvent | |
| CN109852801A (en) | The recovery method of cobalt and lithium in anode material for lithium-ion batteries | |
| CN105039724A (en) | Smelting furnace soot treatment method | |
| CN110468281A (en) | Valuable metal separation and recovery method in a kind of waste and old cobalt acid lithium battery | |
| Srivastava et al. | A comprehensive review of the reclamation of resources from spent lithium-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20190627 Address after: 101102 Beijing Tongzhou District Huanyu Road No.3 Building No.14, 3 Floors Applicant after: Sander New Energy Technology Development Co., Ltd. Applicant after: Thornton Amperex Technology Limited Address before: Unit 402, Fuqing Huayuan Commercial and Residential Building, Bayi Town, Linzhi City, Tibet Autonomous Region Applicant before: Sound Group Co.,Ltd. Applicant before: Thornton Amperex Technology Limited |
|
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190607 |