CN106505270B - The method of Call Provision and lithium from lithium ion battery positive plate - Google Patents
The method of Call Provision and lithium from lithium ion battery positive plate Download PDFInfo
- Publication number
- CN106505270B CN106505270B CN201610856995.0A CN201610856995A CN106505270B CN 106505270 B CN106505270 B CN 106505270B CN 201610856995 A CN201610856995 A CN 201610856995A CN 106505270 B CN106505270 B CN 106505270B
- Authority
- CN
- China
- Prior art keywords
- lithium
- cobalt
- positive plate
- sinker
- battery positive
- 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.)
- Active
Links
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- 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
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention provides it is a kind of simply and efficiently from old and useless battery positive plate Call Provision and lithium method.The method of the Call Provision from lithium ion battery positive plate and lithium according to the present invention, which is characterized in that including following process：Ammonium sulfate calcining process：The positive plate of waste lithium cell is mixed, high-temperature roasting with ammonium sulfate, obtains reduction roasting slag；Sieve process：Reduction roasting slag is sieved while vibrating using vibrating screening machine, aluminium foil is separated off, obtains the reducing slag containing cobalt and lithium；Acidleach process：Aluminium foil is separated off from reduction roasting slag, is leached with dilute sulfuric acid, the sulfate liquor for filtering containing cobalt and lithium；Clean process：With the pH of sodium carbonate regulating solution, it is filtered to remove precipitation, obtains cobalt lithium sulfuric acid mixed salt solution；Heavy cobalt process：Sodium hydroxide is added in cobalt lithium sulfuric acid mixed salt solution, control pH value of solution is 7.5 ~ 9.5, and precipitation is obtained by filtration, and is eluted with 85 ~ 95 DEG C of deionized waters, drying, then the cobalt hydroxide after drying is placed in reduction furnace, leads to H2Reduction, obtains cobalt powder；Sinker process：By lithium-containing solution salt acid for adjusting pH to 7 ~ 8, excessive sinker agent is added, obtains lithium salts product.
Description
Technical field
The invention belongs to resource circulation utilizations and technical field of wet metallurgy, and in particular to from waste lithium cell positive plate
The method of Call Provision and lithium.
Technical background
At present from used Li ion cell positive plate separating and recovering cobalt, lithium metal method be usually first by applying waste lithium ionic
Battery disassemble etc. pretreatment and obtains the positive plate containing active material, then using the techniques such as organic solvent, high temperature or soda acid point
From aluminium foil, the positive electrode containing cobalt acid lithium is obtained, leaching, chemical precipitation, extraction and separation or ion is taken to hand over successively later
It the methods of changes and to obtain the metallic compound containing cobalt and lithium, this method and process flow is longer.
In particular, in the method for existing recycling lithium, the rate of recovery generally only 60% or so of lithium, and purity is relatively low.
Especially for the higher waste and old lithium ion battery of lithium content, the problem is more serious.
To sum up, there are technological process length, place demands for the method for Call Provision and lithium in used Li ion cell positive plate at present
Greatly, the features such as energy consumption is higher, therefore cause low recycled in its entirety efficiency, high expensive, be difficult to improve economic benefit and industrialization valence
Value.
Invention content
The present invention is to carry out to solve the above-mentioned problems, and it is an object of the present invention to provide one kind is simply and efficiently from waste and old electricity
The method of Call Provision and lithium in the positive plate of pond.
The present invention to achieve the goals above, uses following scheme：
The present invention provides a kind of method of the Call Provision from lithium ion battery positive plate and lithium, which is characterized in that packet
Include following process：Ammonium sulfate calcining process：According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.0 ~ 2.5 into
Row mixing, then high-temperature roasting obtains reduction roasting slag, comprising aluminium foil and contains cobalt, lithium metal element in the reduction roasting slag
Sulfate；Sieve process：Reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium
Foil obtains the reducing slag containing cobalt and lithium；Acidleach process：The reducing slag of the lithium containing cobalt is leached into a period of time with dilute sulfuric acid, is filtered out
The sulfate liquor containing cobalt and lithium is obtained after filter residue；Clean process：The pH to 5.0 ~ 5.5 of sulfate liquor is adjusted with sodium carbonate,
Make copper ion, iron ion and aluminium ion precipitation, is filtered to remove precipitation, obtains cobalt lithium sulfuric acid mixed salt solution, the cobalt lithium sulfate
Copper ion, iron ion and aluminum ions content are in 20mg/L or less in mixed solution；Heavy cobalt process：Temperature is added in sodium hydroxide
Degree is in 65 ~ 75 DEG C of cobalt lithium sulfuric acid mixed salt solution, control pH value of solution is 7.5 ~ 9.5, and lithium-containing solution and hydrogen-oxygen is obtained by filtration
Change cobalt precipitation, then, cobalt hydroxide precipitation is then placed in 85 ~ 95 DEG C of deionized water elution to remove soluble impurity
It is dried in baking oven, then the cobalt hydroxide after drying is placed in reduction furnace, lead to H2Reduction, obtains cobalt powder；Sinker process：Lithium will be contained
Solution salt acid for adjusting pH to 7 ~ 8 is added excessive sinker agent and carrys out sinker, obtains lithium salts product, wherein sinker agent is sodium fluoride
With any one in sodium phosphate.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In ammonium sulfate calcining process, for calcination temperature at 550 ~ 650 DEG C, roasting time is 4 ~ 7h.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：It is the dilute sulfuric acid with 0.5 ~ 2mol/L by liquid-solid ratio 5 ~ 8 in acidleach process：1 in temperature 55 ~ 70 DEG C will contain
The reducing slag of cobalt lithium leaches 1 ~ 2h, and here, liquid-solid ratio refers to the volume of dilute sulfuric acid and the mass ratio of reducing slag.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：Wherein, in heavy cobalt process, cobalt hydroxide precipitation is oven-dried at 300 ~ 500 DEG C, the cobalt hydroxide after drying
Logical H23 ~ 6 h are restored, the flow of hydrogen is 8 ~ 10m3/h。
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：Be by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio it is 1 in ammonium sulfate calcining process：2.2
~ 2.5 are mixed.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In acidleach process, a concentration of 0.5 ~ 1mol/L of dilute sulfuric acid.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In sinker process, using sodium fluoride as sinker agent, the mole of the sodium fluoride of addition is
1.3 times or more of elemental lithium mole in lithium-containing solution, temperature is at 55 DEG C ~ 70 DEG C when sinker.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In sinker process, using sodium fluoride as sinker agent, the mole of the sodium fluoride of addition is
1.3 ~ 1.5 times of elemental lithium mole in lithium-containing solution.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In sinker process, using sodium phosphate as sinker agent, the mole of the sodium phosphate of addition is
1.5 times or more of elemental lithium mole in lithium-containing solution, temperature is at 55 DEG C ~ 70 DEG C when sinker.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In sinker process, using sodium phosphate as sinker agent, the mole of the sodium phosphate of addition is
1.5 times or more of elemental lithium mole in lithium-containing solution, temperature is at 55 DEG C ~ 70 DEG C when sinker.
Further, the method for the Call Provision from lithium ion battery positive plate and lithium provided by the invention can also have
There are following characteristics：In sinker process, using sodium phosphate as sinker agent, the mole of the sodium phosphate of addition is
1.5 ~ 1.7 times of elemental lithium mole in lithium-containing solution.
The effect of invention
The method of the Call Provision from lithium ion battery positive plate and lithium provided by the invention, roasts by using ammonium sulfate
It is golden to the cobalt and lithium that contain in positive plate to burn process, screening process, acidleach process, removal of impurities process, heavy cobalt process and sinker process
Belong to element to be recycled, the technological process of separating and recovering cobalt and lithium from used Li ion cell positive plate can not only be shortened, and
And the rate of recovery of lithium can also be improved in the case of the rate of recovery for ensureing cobalt and higher purity, the primary recovery of lithium reaches
80 ~ 93%, organic efficiency is high, simple for process, has considerable economic value, is very suitable for extensive industrialization.
Also, method through the invention has effectively achieved the synthesis of valuable metal lithium, cobalt and aluminium in waste lithium cell
Recycling solves deficiency existing for existing recovery process, avoids the pollution to environment.
Description of the drawings
Fig. 1 is the process flow chart of the embodiment of the present invention.
Specific implementation mode
Below in conjunction with attached drawing to the method for the Call Provision of the present invention from lithium ion battery positive plate and lithium
Specific embodiment is described in detail.
The positive plate of waste lithium cell employed in following embodiment is all to put waste and old cobalt acid lithium battery remaining capacity
Complete, then dismantling taking-up obtains.
<Embodiment one>
As shown in Figure 1, the present embodiment one provide slave lithium ion battery positive plate in Call Provision and lithium method, packet
Include following process：
1. ammonium sulfate calcining process：
According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.5 are mixed, and are then roasted at 650 DEG C
4h is burnt, the reduction roasting slag for including aluminium foil and the sulfate containing metallic elements such as cobalt, lithiums is obtained；
2. sieving process：
Reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium foil, obtains containing cobalt
With the reducing slag of lithium, cobalt content 45.4wt.%, lithium content 6.2wt.% in reducing slag；
3. acidleach process：
Liquid-solid ratio 6 is pressed with the dilute sulfuric acid of 2mol/L：1（L / kg）The reducing slag of the lithium containing cobalt is soaked under the conditions of temperature 70 C
Go out 1h, filters out filter residue（The amount of filter residue is seldom）The sulfate liquor containing cobalt and lithium is obtained afterwards, and cobalt content is 30.54g/ in solution
L, lithium content 4.7g/L；
4. clean process：
The pH to 5.0 that sulfate liquor is adjusted with sodium carbonate makes copper ion, iron ion and aluminium ion precipitation, is filtered to remove
These precipitations, obtain cobalt lithium sulfuric acid mixed salt solution, copper ion in the cobalt lithium sulfuric acid mixed salt solution, iron ion and aluminum ions
Content is followed successively by respectively：5mg/L, 12mg/L, 17mg/L；
5. heavy cobalt process：
Sodium hydroxide is added in the cobalt lithium sulfuric acid mixed salt solution that temperature is 65 DEG C, control pH value of solution is 9.5, is filtered
It is precipitated to lithium-containing solution and cobalt hydroxide, lithium content is 4.5g/L, cobalt content 10mg/L in lithium-containing solution；
Then, cobalt hydroxide is precipitated and is eluted 5 times with 85 DEG C of deionized waters, to remove soluble impurity, is then placed in
In baking oven, 80 DEG C of baking 4h, then the cobalt hydroxide after drying is placed in reduction furnace, 300 DEG C of logical H2Restore 6 h, the flow of hydrogen
For 8m3/ h, obtains cobalt powder；
6. sinker process：
By lithium-containing solution salt acid for adjusting pH to 7, sodium fluoride is added, the mole of sodium fluoride is elemental lithium in lithium-containing solution
1.5 times of mole, temperature obtains lithium fluoride product at 70 DEG C when sinker.
The rate of recovery of cobalt can reach 97.5% in the present embodiment one, and product purity can reach 99%；The rate of recovery of lithium can
To reach 91%, product purity reaches 98%.
<Embodiment two>
As shown in Figure 1, the present embodiment two provide slave lithium ion battery positive plate in Call Provision and lithium method, packet
Include following process：
1. ammonium sulfate calcining process：
According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.0 are mixed, and are then roasted at 550 DEG C
7h is burnt, the reduction roasting slag for including aluminium foil and the sulfate containing metallic elements such as cobalt, lithiums is obtained；
2. sieving process：
Reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium foil, obtains containing cobalt
With the reducing slag of lithium, cobalt content 48.9wt.%, lithium content 7.2wt.% in reducing slag；
3. acidleach process：
Liquid-solid ratio 8 is pressed with the dilute sulfuric acid of 1mol/L：1（L / kg）The reducing slag of the lithium containing cobalt is soaked under the conditions of temperature 60 C
Go out 2h, filters out filter residue（The amount of filter residue is seldom）The sulfate liquor containing cobalt and lithium is obtained afterwards, and cobalt content is 20.26g/ in solution
L, lithium content 3.2g/L；
4. clean process：
The pH to 5.0 that sulfate liquor is adjusted with sodium carbonate makes copper ion, iron ion and aluminium ion precipitation, is filtered to remove
These precipitations, obtain cobalt lithium sulfuric acid mixed salt solution, copper ion in the cobalt lithium sulfuric acid mixed salt solution, iron ion and aluminum ions
Content is followed successively by respectively：5mg/L, 7mg/L, 10mg/L；
5. heavy cobalt process：
Sodium hydroxide is added in the cobalt lithium sulfuric acid mixed salt solution that temperature is 75 DEG C, control pH value of solution is 7.5, is filtered
It is precipitated to lithium-containing solution and cobalt hydroxide, lithium content is 2.9g/L, cobalt content 25mg/L in lithium-containing solution；
Then, cobalt hydroxide is precipitated and is eluted 4 times with 90 DEG C of deionized waters, to remove soluble impurity, is then placed in
In baking oven, 95 DEG C of baking 4h, then the cobalt hydroxide after drying is placed in reduction furnace, 400 DEG C of logical H2Restore 4 h, the flow of hydrogen
For 9m3/ h, obtains cobalt powder；
6. sinker process：
By lithium-containing solution salt acid for adjusting pH to 7.5, sodium fluoride is added, the mole of sodium fluoride is lithium member in lithium-containing solution
1.3 times of plain mole, temperature obtains lithium fluoride product at 70 DEG C when sinker.
The rate of recovery of cobalt can reach 95% in the present embodiment two, and product purity can reach 99%；The rate of recovery of lithium can be with
Reach 80%, product purity reaches 98.5%.
<Embodiment three>
As shown in Figure 1, the present embodiment three provide slave lithium ion battery positive plate in Call Provision and lithium method, packet
Include following process：
1. ammonium sulfate calcining process：
According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.2 are mixed, and are then roasted at 550 DEG C
6h is burnt, the reduction roasting slag for including aluminium foil and the sulfate containing metallic elements such as cobalt, lithiums is obtained；
2. sieving process：
Reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium foil, obtains containing cobalt
With the reducing slag of lithium, cobalt content 47.3wt.%, lithium content 6.8wt.% in reducing slag；
3. acidleach process：
Liquid-solid ratio 5 is pressed with the dilute sulfuric acid of 1mol/L：1（L / kg）The reducing slag of the lithium containing cobalt is soaked under the conditions of 65 DEG C of temperature
Go out 2h, filters out filter residue（The amount of filter residue is seldom）The sulfate liquor containing cobalt and lithium is obtained afterwards, and cobalt content is 28.74g/ in solution
L, lithium content 4.5g/L；
4. clean process：
The pH to 5.5 that sulfate liquor is adjusted with sodium carbonate makes copper ion, iron ion and aluminium ion precipitation, is filtered to remove
These precipitations, obtain cobalt lithium sulfuric acid mixed salt solution, copper ion in the cobalt lithium sulfuric acid mixed salt solution, iron ion and aluminum ions
Content is followed successively by respectively：3mg/L, 2mg/L, 6mg/L；
5. heavy cobalt process：
Sodium hydroxide is added in the cobalt lithium sulfuric acid mixed salt solution that temperature is 70 DEG C, control pH value of solution is 8.5, is filtered
It is precipitated to lithium-containing solution and cobalt hydroxide, lithium content is 4.3g/L, cobalt content 29mg/L in lithium-containing solution；
Then, cobalt hydroxide is precipitated and is eluted 4 times with 90 DEG C of deionized waters, to remove soluble impurity, is then placed in
In baking oven, 90 DEG C of baking 3h, then the cobalt hydroxide after drying is placed in reduction furnace, 500 DEG C of logical H2Restore 3 h, the flow of hydrogen
For 9m3/ h, obtains cobalt powder；
6. sinker process：
By lithium-containing solution salt acid for adjusting pH to 8, sodium phosphate is added, the mole of sodium phosphate is elemental lithium in lithium-containing solution
1.7 times of mole, temperature obtains lithium phosphate product at 55 DEG C when sinker.
The rate of recovery of cobalt can reach 96.5% in the present embodiment three, and product purity can reach 99%；The rate of recovery of lithium can
To reach 93%, product purity reaches 98%.
<Example IV>
As shown in Figure 1, the present embodiment four provide slave lithium ion battery positive plate in Call Provision and lithium method, packet
Include following process：
1. ammonium sulfate calcining process：
According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.4 are mixed, and are then roasted at 600 DEG C
5h is burnt, the reduction roasting slag for including aluminium foil and the sulfate containing metallic elements such as cobalt, lithiums is obtained；
2. sieving process：
Reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium foil, obtains containing cobalt
With the reducing slag of lithium, cobalt content 46.5wt.%, lithium content 6.5wt.% in reducing slag；
3. acidleach process：
Liquid-solid ratio 8 is pressed with the dilute sulfuric acid of 0.5mol/L：1（L / kg）By the reducing slag of the lithium containing cobalt under the conditions of 65 DEG C of temperature
2h is leached, filter residue is filtered out（The amount of filter residue is seldom）The sulfate liquor containing cobalt and lithium is obtained afterwards, and cobalt content is in solution
22.48g/L, lithium content 3.5g/L；
4. clean process：
The pH to 5.5 that sulfate liquor is adjusted with sodium carbonate makes copper ion, iron ion and aluminium ion precipitation, is filtered to remove
These precipitations, obtain cobalt lithium sulfuric acid mixed salt solution, copper ion in the cobalt lithium sulfuric acid mixed salt solution, iron ion and aluminum ions
Content is followed successively by respectively：6mg/L, 3mg/L, 7mg/L；
5. heavy cobalt process：
Sodium hydroxide is added in the cobalt lithium sulfuric acid mixed salt solution that temperature is 75 DEG C, control pH value of solution is 9.0, is filtered
It is precipitated to lithium-containing solution and cobalt hydroxide, lithium content is 3.4g/L, cobalt content 19mg/L in lithium-containing solution；
Then, cobalt hydroxide is precipitated and is eluted 3 times with 95 DEG C of deionized waters, to remove soluble impurity, is then placed in
In baking oven, 90 DEG C of baking 3h, then the cobalt hydroxide after drying is placed in reduction furnace, 450 DEG C of logical H24h is restored, the flow of hydrogen is
10m3/ h, obtains cobalt powder；
6. sinker process：
By lithium-containing solution salt acid for adjusting pH to 8, sodium phosphate is added, the mole of sodium phosphate is elemental lithium in lithium-containing solution
1.5 times of mole, temperature obtains lithium phosphate product at 60 DEG C when sinker.
The rate of recovery of cobalt can reach 97.5% in the present embodiment four, and product purity can reach 99%；The rate of recovery of lithium can
To reach 85%, product purity reaches 98.5%.
In above-described embodiment one to four, atomic absorption spectrophotometer may be used in the concentration of lithium ion in lithium-containing solution
Either ICP tests（Atomic emission spectrometry）Etc. means be detected, further according to measurement result plus sinker agent（Sodium fluoride or phosphorus
Sour sodium）.The present invention can also be detected the concentration of lithium ion using other means of testing.
In addition, in above-described embodiment one to four, in the vibrating screening machine of use, the aperture of sieve pore could be provided as 2 ~
5cm, may be used linear vibrating screen, and frequency is 960 beats/min.The present invention can also use other types of vibrating screening machine
It is vibrated and is sieved, as long as aluminium foil can will be separated off.
The effect of embodiment：
According to the method for the Call Provision from lithium ion battery positive plate and lithium provided in this embodiment, by using sulphur
Sour ammonium calcining process, screening process, acidleach process, removal of impurities process, heavy cobalt process and sinker process are to the cobalt that contains in positive plate
It is recycled with lithium metal element, the technique stream of separating and recovering cobalt and lithium from used Li ion cell positive plate can not only be shortened
Journey, but also the rate of recovery of lithium, the rate of recovery energy of cobalt can be improved in the case of the rate of recovery for ensureing cobalt and higher purity
Enough reach 95 ~ 97.5%, purity reaches 99%, and the primary recovery of lithium reaches 80 ~ 93%, and purity reaches 98% or more, organic efficiency
High, purity height, it is simple for process, there is considerable economic value, be very suitable for extensive industrialization.
Also, by this method, the synthetical recovery of valuable metal lithium in waste lithium cell, cobalt and aluminium is had effectively achieved,
It solves deficiency existing for existing recovery process, avoids the pollution to environment.
Above example is only the illustration done to technical solution of the present invention.It is according to the present invention from waste and old lithium
The method of Call Provision and lithium is not merely defined in described content in the embodiment above in ion battery positive plate, but
It is subject to claim limited range.Those skilled in the art of the invention are done any on the basis of the embodiment
Modify or supplement or equivalence replacement, all in the claim range claimed of the present invention.
Claims (9)
1. a kind of method of the Call Provision from lithium ion battery positive plate and lithium, which is characterized in that including following process：
Ammonium sulfate calcining process：
According to mass ratio it is 1 by the positive plate of waste lithium cell and ammonium sulfate：2.0~2.5 are mixed, then high-temperature roasting,
Reduction roasting slag is obtained, includes aluminium foil and the sulfate containing cobalt, lithium metal element in the reduction roasting slag；
Sieve process：
The reduction roasting slag is sieved while vibrating using vibrating screening machine, is separated off aluminium foil, obtains containing cobalt
With the reducing slag of lithium；
Acidleach process：
Liquid-solid ratio 5~8 is pressed with the dilute sulfuric acid of 0.5~2mol/L：1 in 55~70 DEG C of temperature the reducing slag of the lithium containing cobalt is leached 1~
2h obtains the sulfate liquor containing cobalt and lithium after filtering out filter residue, and the liquid-solid ratio is that the volume of the dilute sulfuric acid is gone back with described
The mass ratio of former slag；
Clean process：
The pH to 5.0~5.5 that the sulfate liquor is adjusted with sodium carbonate makes copper ion, iron ion and aluminium ion precipitation, filtering
Precipitation is removed, cobalt lithium sulfuric acid mixed salt solution is obtained, copper ion in the cobalt lithium sulfuric acid mixed salt solution, iron ion and aluminum ions
Content is in 20mg/L or less；
Heavy cobalt process：
Temperature, which is added, in sodium hydroxide is in 65~75 DEG C of the cobalt lithium sulfuric acid mixed salt solution, control pH value of solution is 7.5~
9.5, lithium-containing solution and cobalt hydroxide precipitation is obtained by filtration,
Then, the cobalt hydroxide is precipitated with 85~95 DEG C of deionized water elution to remove soluble impurity, is then placed in
It is dried in baking oven, then the cobalt hydroxide after drying is placed in reduction furnace, lead to H2Reduction, obtains cobalt powder；
Sinker process：
By lithium-containing solution salt acid for adjusting pH to 7~8, excessive sinker agent is added and carrys out sinker, obtains lithium salts product,
Wherein, the sinker agent is any one in sodium fluoride and sodium phosphate.
2. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, in the ammonium sulfate calcining process, for calcination temperature at 550~650 DEG C, roasting time is 4~7h.
3. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, in the heavy cobalt process, the cobalt hydroxide precipitation is oven-dried at 300~500 DEG C, the hydrogen after drying
Cobalt oxide leads to H23~6h is restored, the flow of hydrogen is 8~10m3/h。
4. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, be by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio it is 1 in the ammonium sulfate calcining process：
2.2~2.5 are mixed.
5. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, in the acidleach process, a concentration of 0.5~1mol/L of dilute sulfuric acid.
6. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, in the sinker process, using sodium fluoride as the sinker agent, the sodium fluoride of addition rubs
Your amount is 1.3 times or more of elemental lithium mole in the lithium-containing solution, and temperature is at 55 DEG C~70 DEG C when sinker.
7. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 6, it is characterised in that：
Wherein, in the sinker process, using sodium fluoride as the sinker agent, the sodium fluoride of addition rubs
Your amount is 1.3~1.5 times of elemental lithium mole in the lithium-containing solution.
8. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 1, it is characterised in that：
Wherein, in the sinker process, using sodium phosphate as the sinker agent, the sodium phosphate of addition rubs
Your amount is 1.5 times or more of elemental lithium mole in the lithium-containing solution, and temperature is at 55 DEG C~70 DEG C when sinker.
9. the method for the Call Provision from lithium ion battery positive plate and lithium according to claim 8, it is characterised in that：
Wherein, in the sinker process, using sodium phosphate as the sinker agent, the sodium phosphate of addition rubs
Your amount is 1.5~1.7 times of elemental lithium mole in the lithium-containing solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610856995.0A CN106505270B (en) | 2016-09-28 | 2016-09-28 | The method of Call Provision and lithium from lithium ion battery positive plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610856995.0A CN106505270B (en) | 2016-09-28 | 2016-09-28 | The method of Call Provision and lithium from lithium ion battery positive plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106505270A CN106505270A (en) | 2017-03-15 |
| CN106505270B true CN106505270B (en) | 2018-07-27 |
Family
ID=58290087
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610856995.0A Active CN106505270B (en) | 2016-09-28 | 2016-09-28 | The method of Call Provision and lithium from lithium ion battery positive plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106505270B (en) |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI746818B (en) * | 2017-04-07 | 2021-11-21 | 比利時商烏明克公司 | Process for the recovery of lithium |
| CN106848471B (en) * | 2017-04-18 | 2021-11-09 | 中科过程（北京）科技有限公司 | Mixed acid leaching and recovery method of waste lithium ion battery anode material |
| CN107460315B (en) * | 2017-08-24 | 2019-10-25 | 中国有色集团刚果矿业有限公司 | A method of using copper, cobalt in nanofiltration membrane concentration and separation-neutralization precipitation recycling copper raffinate |
| CN107955879B (en) * | 2017-12-05 | 2019-08-30 | 广东省稀有金属研究所 | A kind of method of valuable element in recycling waste lithium ion battery electrode material |
| CN107994288B (en) * | 2017-12-14 | 2020-02-14 | 眉山顺应动力电池材料有限公司 | Method for recovering valuable metals in anode material of waste nickel cobalt lithium manganate ternary battery |
| DE102018102026A1 (en) * | 2018-01-30 | 2019-08-01 | Duesenfeld Gmbh | Process for recycling lithium batteries |
| CN108767354B (en) * | 2018-05-29 | 2021-02-26 | 中南大学 | Method for recovering valuable metals from waste lithium ion battery anode materials |
| CN110317954A (en) * | 2019-07-05 | 2019-10-11 | 湖南凯地众能科技有限公司 | A kind of technique of waste lithium cell recycling valuable metal |
| CN111036651A (en) * | 2019-12-26 | 2020-04-21 | 甘肃睿思科新材料有限公司 | Recovery system of positive electrode waste slurry of lithium battery |
| CN111206151B (en) * | 2020-01-13 | 2021-09-14 | 赣州有色冶金研究所有限公司 | Method for recovering valuable metals in ternary lithium ion power battery positive plate |
| CN112877548B (en) * | 2021-01-12 | 2022-11-25 | 中国科学院过程工程研究所 | Method for recovering valuable metals from waste lithium ion battery anode powder |
| CN112981110A (en) * | 2021-02-08 | 2021-06-18 | 中节能工程技术研究院有限公司 | Method for recovering anode material of waste lithium cobalt oxide battery |
| CN113881858B (en) * | 2021-09-08 | 2023-03-31 | 荆门市格林美新材料有限公司 | Method for recycling cobalt-containing waste |
| CN113921932B (en) * | 2021-12-14 | 2022-04-01 | 矿冶科技集团有限公司 | Precursor solution, preparation method thereof, positive electrode material and lithium ion battery |
| CN116802332A (en) * | 2023-03-08 | 2023-09-22 | 广东邦普循环科技有限公司 | Method for recycling lithium in lithium waste battery leaching solution based on directional circulation and application of method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
| CN103178315A (en) * | 2011-12-23 | 2013-06-26 | 韦有照 | Resource recycling technology for waste lithium ion batteries |
-
2016
- 2016-09-28 CN CN201610856995.0A patent/CN106505270B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101942569A (en) * | 2010-10-28 | 2011-01-12 | 湖南邦普循环科技有限公司 | Method for recovering lithium from waste lithium ion battery and waste pole piece |
| CN103178315A (en) * | 2011-12-23 | 2013-06-26 | 韦有照 | Resource recycling technology for waste lithium ion batteries |
| CN102703706A (en) * | 2012-06-01 | 2012-10-03 | 奇瑞汽车股份有限公司 | Method for recovering valued metals from waste lithium cobaltate batteries |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106505270A (en) | 2017-03-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106505270B (en) | The method of Call Provision and lithium from lithium ion battery positive plate | |
| CN106910889B (en) | A method of regenerating positive active material from waste lithium iron phosphate battery | |
| CN106785177B (en) | A method of from the recycling of waste and old nickel-cobalt-manganese ternary lithium ion battery, preparation nickel cobalt manganese aluminium quaternary positive electrode | |
| CN107017443B (en) | A method of the comprehensively recovering valuable metal from waste and old lithium ion battery | |
| CN106848470B (en) | A method of it recycled from waste and old nickel-cobalt-manganese ternary lithium ion battery, prepare tertiary cathode material | |
| CN109234524B (en) | Method and system for comprehensively recovering valuable metals from waste ternary lithium batteries | |
| CN104241724B (en) | A kind of method for preparing battery-level lithium carbonate from lithium ion battery regenerant | |
| CN110527835B (en) | Method for recycling soft package full components of waste ternary lithium battery | |
| CN102560535B (en) | Method for recovering lead in waste lead-acid storage battery filler by using wet process | |
| CN107666022A (en) | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material | |
| CN109449523A (en) | A kind of comprehensive recovering process of waste and old lithium ion battery | |
| CN108486376A (en) | A method of leaching metal in waste lithium ion cell anode material | |
| CN110422891A (en) | A kind of method preparing nickel-cobalt-manganese ternary presoma, system and application | |
| CN109256596B (en) | Method and system for reversely preparing aluminum-doped ternary precursor | |
| KR102724564B1 (en) | Method for recovering valuable metals from spent lithium-ion batteries | |
| CN109148995B (en) | Common treatment method for low-cobalt high-manganese waste and waste lithium battery cathode material | |
| CN109256597A (en) | A kind of method and system recycling lithium and cobalt from waste and old cobalt acid lithium battery | |
| CN107419096B (en) | A kind of preparation method of waste lithium cell reclaiming tertiary cathode material | |
| CN110013822A (en) | A kind of method of waste and old lithium ion battery recycling co-production lithium adsorbent | |
| CN109207725A (en) | A kind of method and system recycling lithium and manganese from waste lithium manganese oxide battery | |
| CN101709374B (en) | Method for preparing precursors of lithium titanate and lithium iron phosphate by comprehensively using ilmenite | |
| CN106611841A (en) | Method for preparing nickel-cobalt-manganese ternary material precursor by using nickel-cobalt slag material | |
| CN106848473A (en) | A kind of selective recovery method of lithium in waste lithium iron phosphate battery | |
| Li et al. | Recovery of Fe, Mn, Ni and Co in sulfuric acid leaching liquor of spent lithium ion batteries for synthesis of lithium ion-sieve and NixCoyMn1-xy (OH) 2 | |
| CN110010991A (en) | The technique of cobalt acid lithium in a kind of recycling and regenerating waste used cobalt acid lithium battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |