CN106505270A - 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
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- CN106505270A CN106505270A CN201610856995.0A CN201610856995A CN106505270A CN 106505270 A CN106505270 A CN 106505270A CN 201610856995 A CN201610856995 A CN 201610856995A CN 106505270 A CN106505270 A CN 106505270A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
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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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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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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- 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
- 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
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- Y02W30/84—Recycling of batteries or fuel cells
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Abstract
The invention provides a kind of simply and efficiently from the method for Call Provision and lithium in old and useless battery positive plate.Call Provision from lithium ion battery positive plate involved in the present invention and the method for lithium, it is characterised in that including following operation：Ammonium sulfate calcining process：The positive plate of waste lithium cell is mixed with ammonium sulfate, high-temperature roasting, obtain reduction roasting slag；Screening operation：Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain the reducing slag containing cobalt and lithium；Acidleach operation：Aluminium foil is separated off from reduction roasting slag, is leached with dilute sulfuric acid, is filtered the sulfate liquor that must contain cobalt and lithium；Remove impurity operation：With the pH of sodium carbonate regulating solution, precipitation is filtered to remove, obtains cobalt lithium sulphuric acid mixed salt solution；Heavy cobalt operation：Sodium hydroxide is added in cobalt lithium sulphuric acid mixed salt solution, control pH value of solution for 7.5 ~ 9.5, is filtrated to get precipitation, with 85 ~ 95 DEG C of deionized water drip washing, drying, then by drying after cobalt hydroxide be placed in reduction furnace, logical H2Reduction, obtains cobalt powder；Sinker operation：By lithium-containing solution salt acid for adjusting pH to 7 ~ 8, excessive sinker agent is added, lithium salts product is obtained.
Description
Technical field
The invention belongs to resource circulation utilization and technical field of wet metallurgy, and in particular to from waste lithium cell positive plate
Call Provision and the method for lithium.
Technical background
Method from separating and recovering cobalt, lithium metal in used Li ion cell positive plate is usually first by applying waste lithium ionic at present
Battery such as carries out disassembling at the positive plate that pretreatment obtains containing active substance, 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, take leaching, chemical precipitation, extract and separate or ion to hand over afterwards successively
The metallic compound that method obtains containing cobalt and lithium such as change, this method technological process is longer.
Particularly, in the existing method for reclaiming lithium, the response rate typically 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, in current used Li ion cell positive plate there is technological process length, place demand in the method for Call Provision and lithium
Greatly, the features such as energy consumption is higher, thus results in low recycled in its entirety efficiency, high expensive, is difficult to increase economic efficiency and industrialization valency
Value.
Content of the invention
The present invention is carried out to solve the above problems, it is therefore intended that provide one kind 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 these goals, employs below scheme：
A kind of method that the present invention provides Call Provision from lithium ion battery positive plate and lithium, it is characterised in that include with
Lower operation：Ammonium sulfate calcining process：It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.0 ~ 2.5 are mixed
Close, then high-temperature roasting obtains reduction roasting slag, comprising aluminium foil and the sulfur containing cobalt, lithium metal element in the reduction roasting slag
Hydrochlorate；Screening operation：Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain
To the reducing slag containing cobalt and lithium；Acidleach operation：The reducing slag containing cobalt lithium is leached a period of time with dilute sulfuric acid, after filtering out filtering residue
Obtain the sulfate liquor containing cobalt and lithium；Remove impurity operation：With sodium carbonate adjust sulfate liquor pH to 5.0 ~ 5.5, make copper from
Son, iron ion and aluminium ion precipitation, is filtered to remove precipitation, obtains cobalt lithium sulphuric acid mixed salt solution, and the cobalt lithium sulfate mixing is molten
In liquid, copper ion, iron ion and aluminum ions content are in below 20mg/L；Heavy cobalt operation：It is 65 that sodium hydroxide is added temperature
In ~ 75 DEG C of cobalt lithium sulphuric acid mixed salt solution, it is 7.5 ~ 9.5 to control pH value of solution, is filtrated to get lithium-containing solution and cobalt hydroxide is heavy
Form sediment, then, cobalt hydroxide precipitation is then placed in baking oven so as to remove soluble impurity with 85 ~ 95 DEG C of deionized water drip washing
Dry, then by drying after cobalt hydroxide be placed in reduction furnace, lead to H2Reduction, obtains cobalt powder；Sinker operation：Lithium-containing solution is used
Salt acid for adjusting pH is added excessive sinker agent to carry out sinker, obtains lithium salts product to 7 ~ 8, and wherein, sinker agent is sodium fluoride and phosphoric acid
Any one in sodium.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In ammonium sulfate calcining process, at 550 ~ 650 DEG C, roasting time is 4 ~ 7h to sintering temperature.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In acidleach operation, it is by liquid-solid ratio 5 ~ 8 with the dilute sulfuric acid of 0.5 ~ 2mol/L：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 Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：Wherein, in heavy cobalt operation, cobalt hydroxide precipitation is oven-dried at 300 ~ 500 DEG C, the cobalt hydroxide after drying
Logical H23 ~ 6 h of reduction, the flow of hydrogen is 8 ~ 10m3/h.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In ammonium sulfate calcining process, it is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio to be：2.2
~ 2.5 are mixed.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In acidleach operation, the concentration of dilute sulfuric acid is 0.5 ~ 1mol/L.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In sinker operation, in the case of using sodium fluoride as sinker agent, the mole of the sodium fluoride of addition is
More than 1.3 times of elemental lithium mole in lithium-containing solution, during sinker, temperature is at 55 DEG C ~ 70 DEG C.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In sinker operation, in the case of 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 Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In sinker operation, in the case of using sodium phosphate as sinker agent, the mole of the sodium phosphate of addition is
More than 1.5 times of elemental lithium mole in lithium-containing solution, during sinker, temperature is at 55 DEG C ~ 70 DEG C.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In sinker operation, in the case of using sodium phosphate as sinker agent, the mole of the sodium phosphate of addition is
More than 1.5 times of elemental lithium mole in lithium-containing solution, during sinker, temperature is at 55 DEG C ~ 70 DEG C.
Further, the Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided can also have
There are following characteristics：In sinker operation, in the case of 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 and effect
Call Provision from lithium ion battery positive plate and the method for lithium that the present invention is provided, by adopting ammonium sulfate roasting work
Sequence, screening operation, acidleach operation, remove impurity operation, heavy cobalt operation and sinker operation are to the cobalt that contains in positive plate and lithium metal unit
Element is reclaimed, and can not only shorten the technological process from separating and recovering cobalt and lithium in used Li ion cell positive plate, but also
Can improve the response rate of lithium in the case where the response rate and higher purity of cobalt is ensured, the primary recovery of lithium reaches 80 ~
93%, organic efficiency is high, simple for process, with considerable economic worth, is especially suitable for extensive industrialization.
Also, by the method for the present invention, have effectively achieved the synthesis of valuable metal lithium, cobalt and aluminum in waste lithium cell
Reclaim, solve the deficiency that existing recovery process is present, it is to avoid the pollution to environment.
Description of the drawings
Process charts of the Fig. 1 for the embodiment of the present invention.
Specific embodiment
Below in conjunction with accompanying drawing to the method for Call Provision from lithium ion battery positive plate according to the present invention and lithium
Specific embodiment is described in detail.
The positive plate of the waste lithium cell employed in following examples is all to put waste and old cobalt acid lithium battery remaining capacity
Complete, then disassemble what taking-up was obtained.
<Embodiment one>
As shown in figure 1, the present embodiment one provide Call Provision from lithium ion battery positive plate and lithium method, including with
Lower operation：
1. ammonium sulfate calcining process：
It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.5 are mixed, then roasting at 650 DEG C
4h, obtains the reduction roasting slag of the sulfate comprising aluminium foil and containing metallic elements such as cobalt, lithiums；
2. operation is sieved：
Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain containing cobalt and lithium
Reducing slag, cobalt content 45.4wt.% in reducing slag, lithium content 6.2wt.%；
3. acidleach operation：
Liquid-solid ratio 6 is pressed with the dilute sulfuric acid of 2mol/L：1（L / kg）The reducing slag containing cobalt lithium is leached under the conditions of temperature 70 C
1h, filters out filtering residue（The amount of filtering residue is little）Sulfate liquor containing cobalt and lithium is obtained afterwards, and in solution, cobalt content is 30.54g/L,
Lithium content is 4.7g/L；
4. remove impurity operation：
The pH of sulfate liquor is adjusted to 5.0 with sodium carbonate, copper ion, iron ion and aluminium ion precipitation is made, is filtered to remove these
Precipitation, obtains cobalt lithium sulphuric acid mixed salt solution, copper ion, iron ion and aluminum ions content in the cobalt lithium sulphuric acid mixed salt solution
It is followed successively by respectively：5mg/L, 12mg/L, 17mg/L；
5. cobalt operation sunk：
It is that it is 9.5 to control pH value of solution, is filtrated to get and contains in 65 DEG C of cobalt lithium sulphuric acid mixed salt solution by sodium hydroxide addition temperature
Lithium solution and cobalt hydroxide precipitation, in lithium-containing solution, lithium content is 4.5g/L, and cobalt content is 10mg/L；
Then, cobalt hydroxide is precipitated with 85 DEG C of deionized water drip washing 5 times, so as to remove soluble impurity, is then placed in baking oven
In, 80 DEG C baking 4h, then by drying after cobalt hydroxide be placed in reduction furnace, 300 DEG C of logical H26 h are reduced, the flow of hydrogen is 8m3/
H, obtains cobalt powder；
6. sinker operation：
By lithium-containing solution salt acid for adjusting pH to 7, sodium fluoride is added, the mole of sodium fluoride is elemental lithium mole in lithium-containing solution
1.5 times of amount, during sinker, temperature obtains lithium fluoride product at 70 DEG C.
In the present embodiment one, the response rate of cobalt can reach 97.5%, and product purity can reach 99%；The response rate of lithium can
To reach 91%, product purity reaches 98%.
<Embodiment two>
As shown in figure 1, the present embodiment two provide Call Provision from lithium ion battery positive plate and lithium method, including with
Lower operation：
1. ammonium sulfate calcining process：
It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.0 are mixed, then roasting at 550 DEG C
7h, obtains the reduction roasting slag of the sulfate comprising aluminium foil and containing metallic elements such as cobalt, lithiums；
2. operation is sieved：
Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain containing cobalt and lithium
Reducing slag, cobalt content 48.9wt.% in reducing slag, lithium content 7.2wt.%；
3. acidleach operation：
Liquid-solid ratio 8 is pressed with the dilute sulfuric acid of 1mol/L：1（L / kg）The reducing slag containing cobalt lithium is leached under the conditions of temperature 60 C
2h, filters out filtering residue（The amount of filtering residue is little）Sulfate liquor containing cobalt and lithium is obtained afterwards, and in solution, cobalt content is 20.26g/L,
Lithium content is 3.2g/L；
4. remove impurity operation：
The pH of sulfate liquor is adjusted to 5.0 with sodium carbonate, copper ion, iron ion and aluminium ion precipitation is made, is filtered to remove these
Precipitation, obtains cobalt lithium sulphuric acid mixed salt solution, copper ion, iron ion and aluminum ions content in the cobalt lithium sulphuric acid mixed salt solution
It is followed successively by respectively：5mg/L, 7mg/L, 10mg/L；
5. cobalt operation sunk：
It is that it is 7.5 to control pH value of solution, is filtrated to get and contains in 75 DEG C of cobalt lithium sulphuric acid mixed salt solution by sodium hydroxide addition temperature
Lithium solution and cobalt hydroxide precipitation, in lithium-containing solution, lithium content is 2.9g/L, and cobalt content is 25mg/L；
Then, cobalt hydroxide is precipitated with 90 DEG C of deionized water drip washing 4 times, so as to remove soluble impurity, is then placed in baking oven
In, 95 DEG C baking 4h, then by drying after cobalt hydroxide be placed in reduction furnace, 400 DEG C of logical H24 h are reduced, the flow of hydrogen is 9m3/
H, obtains cobalt powder；
6. sinker operation：
By lithium-containing solution salt acid for adjusting pH to 7.5, sodium fluoride is added, the mole of sodium fluoride is that elemental lithium rubs in lithium-containing solution
1.3 times of that amount, during sinker, temperature obtains lithium fluoride product at 70 DEG C.
In the present embodiment two, the response rate of cobalt can reach 95%, and product purity can reach 99%；The response rate of lithium can be with
80% is reached, product purity reaches 98.5%.
<Embodiment three>
As shown in figure 1, the present embodiment three provide Call Provision from lithium ion battery positive plate and lithium method, including with
Lower operation：
1. ammonium sulfate calcining process：
It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.2 are mixed, then roasting at 550 DEG C
6h, obtains the reduction roasting slag of the sulfate comprising aluminium foil and containing metallic elements such as cobalt, lithiums；
2. operation is sieved：
Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain containing cobalt and lithium
Reducing slag, cobalt content 47.3wt.% in reducing slag, lithium content 6.8wt.%；
3. acidleach operation：
Liquid-solid ratio 5 is pressed with the dilute sulfuric acid of 1mol/L：1（L / kg）The reducing slag that cobalt lithium will be contained under the conditions of 65 DEG C of temperature is leached
2h, filters out filtering residue（The amount of filtering residue is little）Sulfate liquor containing cobalt and lithium is obtained afterwards, and in solution, cobalt content is 28.74g/L,
Lithium content is 4.5g/L；
4. remove impurity operation：
The pH of sulfate liquor is adjusted to 5.5 with sodium carbonate, copper ion, iron ion and aluminium ion precipitation is made, is filtered to remove these
Precipitation, obtains cobalt lithium sulphuric acid mixed salt solution, copper ion, iron ion and aluminum ions content in the cobalt lithium sulphuric acid mixed salt solution
It is followed successively by respectively：3mg/L, 2mg/L, 6mg/L；
5. cobalt operation sunk：
It is that it is 8.5 to control pH value of solution, is filtrated to get and contains in 70 DEG C of cobalt lithium sulphuric acid mixed salt solution by sodium hydroxide addition temperature
Lithium solution and cobalt hydroxide precipitation, in lithium-containing solution, lithium content is 4.3g/L, and cobalt content is 29mg/L；
Then, cobalt hydroxide is precipitated with 90 DEG C of deionized water drip washing 4 times, so as to remove soluble impurity, is then placed in baking oven
In, 90 DEG C baking 3h, then by drying after cobalt hydroxide be placed in reduction furnace, 500 DEG C of logical H23 h are reduced, the flow of hydrogen is 9m3/
H, obtains cobalt powder；
6. sinker operation：
By lithium-containing solution salt acid for adjusting pH to 8, sodium phosphate is added, the mole of sodium phosphate is elemental lithium mole in lithium-containing solution
1.7 times of amount, during sinker, temperature obtains lithium phosphate product at 55 DEG C.
In the present embodiment three, the response rate of cobalt can reach 96.5%, and product purity can reach 99%；The response rate of lithium can
To reach 93%, product purity reaches 98%.
<Example IV>
As shown in figure 1, the present embodiment four provide Call Provision from lithium ion battery positive plate and lithium method, including with
Lower operation：
1. ammonium sulfate calcining process：
It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.4 are mixed, then roasting at 600 DEG C
5h, obtains the reduction roasting slag of the sulfate comprising aluminium foil and containing metallic elements such as cobalt, lithiums；
2. operation is sieved：
Reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain containing cobalt and lithium
Reducing slag, cobalt content 46.5wt.% in reducing slag, lithium content 6.5wt.%；
3. acidleach operation：
Liquid-solid ratio 8 is pressed with the dilute sulfuric acid of 0.5mol/L：1（L / kg）The reducing slag that cobalt lithium will be contained under the conditions of 65 DEG C of temperature is leached
2h, filters out filtering residue（The amount of filtering residue is little）Sulfate liquor containing cobalt and lithium is obtained afterwards, and in solution, cobalt content is 22.48g/L,
Lithium content is 3.5g/L；
4. remove impurity operation：
The pH of sulfate liquor is adjusted to 5.5 with sodium carbonate, copper ion, iron ion and aluminium ion precipitation is made, is filtered to remove these
Precipitation, obtains cobalt lithium sulphuric acid mixed salt solution, copper ion, iron ion and aluminum ions content in the cobalt lithium sulphuric acid mixed salt solution
It is followed successively by respectively：6mg/L, 3mg/L, 7mg/L；
5. cobalt operation sunk：
It is that it is 9.0 to control pH value of solution, is filtrated to get and contains in 75 DEG C of cobalt lithium sulphuric acid mixed salt solution by sodium hydroxide addition temperature
Lithium solution and cobalt hydroxide precipitation, in lithium-containing solution, lithium content is 3.4g/L, and cobalt content is 19mg/L；
Then, cobalt hydroxide is precipitated with 95 DEG C of deionized water drip washing 3 times, so as to remove soluble impurity, is then placed in baking oven
In, 90 DEG C baking 3h, then by drying after cobalt hydroxide be placed in reduction furnace, 450 DEG C of logical H2Reduction 4h, the flow of hydrogen is 10m3/
H, obtains cobalt powder；
6. sinker operation：
By lithium-containing solution salt acid for adjusting pH to 8, sodium phosphate is added, the mole of sodium phosphate is elemental lithium mole in lithium-containing solution
1.5 times of amount, during sinker, temperature obtains lithium phosphate product at 60 DEG C.
In the present embodiment four, the response rate of cobalt can reach 97.5%, and product purity can reach 99%；The response rate of lithium can
To reach 85%, product purity reaches 98.5%.
In above-described embodiment one to four, in lithium-containing solution, the concentration of lithium ion can adopt atomic absorption spectrophotometer
Or ICP tests（Atomic emission spectrometry）Detected etc. means, further according to measurement result plus sinker agent（Sodium fluoride or phosphorus
Sour sodium）.The present invention can also be detected to the concentration of lithium ion using other means of testing.
In addition, in above-described embodiment one to four, in the vibrating screen classifier of employing, the aperture of sieve aperture could be arranged to 2 ~
5cm, can adopt linear vibrating screen, and frequency is 960 beats/min.The present invention can also adopt other types of vibrating screen classifier
To be vibrated and be sieved, as long as aluminium foil can will be separated off.
The effect of embodiment and effect：
The Call Provision from lithium ion battery positive plate provided according to the present embodiment and the method for lithium, by adopting ammonium sulfate
Calcining process, screening operation, acidleach operation, remove impurity operation, heavy cobalt operation and sinker operation are to the cobalt that contains in positive plate and lithium
Metallic element is reclaimed, and can not only shorten the technological process from separating and recovering cobalt and lithium in used Li ion cell positive plate,
But also the response rate of lithium can be improved in the case where the response rate and higher purity of cobalt is ensured, the response rate of cobalt can reach
To 95 ~ 97.5%, purity reaches 99%, and the primary recovery of lithium reaches 80 ~ 93%, and purity reaches more than 98%, and organic efficiency is high, pure
Degree is high, simple for process, with considerable economic worth, is especially suitable for extensive industrialization.
Also, by this method, the synthetical recovery of valuable metal lithium, cobalt and aluminum in waste lithium cell is have effectively achieved,
Solve the deficiency that existing recovery process is present, it is to avoid the pollution to environment.
Above example is only the illustration done by technical solution of the present invention.Involved in the present invention from waste and old lithium
In ion battery positive plate, the method for Call Provision and lithium is not merely defined in content described in the embodiment above, but
It is defined by claim limited range.It is any that those skilled in the art of the invention are done on the basis of the embodiment
Modification is supplemented or equivalence replacement, all in the claimed scope of the claim of the present invention.
Claims (10)
1. a kind of method of Call Provision from lithium ion battery positive plate and lithium, it is characterised in that including following operation：
Ammonium sulfate calcining process：
It is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio：2.0 ~ 2.5 are mixed, then high-temperature roasting, are obtained
Reduction roasting slag is arrived, comprising aluminium foil and the sulfate containing cobalt, lithium metal element in the reduction roasting slag；
Screening operation：
The reduction roasting slag is vibrated using vibrating screen classifier while sieved, be separated off aluminium foil, obtain containing cobalt
Reducing slag with lithium；
Acidleach operation：
The reducing slag containing cobalt lithium is leached a period of time with dilute sulfuric acid, the sulfate obtained after filtering out filtering residue containing cobalt and lithium is molten
Liquid；
Remove impurity operation：
The pH of the sulfate liquor is adjusted to 5.0 ~ 5.5 with sodium carbonate, copper ion, iron ion and aluminium ion precipitation is made, is filtered
Precipitation is removed, cobalt lithium sulphuric acid mixed salt solution is obtained, copper ion in the cobalt lithium sulphuric acid mixed salt solution, iron ion and aluminum ions
Content is in below 20mg/L；
Heavy cobalt operation：
Will sodium hydroxide add temperature be 7.5 in 65 ~ 75 DEG C of the cobalt lithium sulphuric acid mixed salt solution, control pH value of solution ~
9.5, lithium-containing solution and cobalt hydroxide precipitation is filtrated to get,
Then, the cobalt hydroxide is precipitated with 85 ~ 95 DEG C of deionized water drip washing so as to remove soluble impurity, is then placed in drying
In case dry, then by drying after cobalt hydroxide be placed in reduction furnace, lead to H2Reduction, obtains cobalt powder；
Sinker operation：
By lithium-containing solution salt acid for adjusting pH to 7 ~ 8, add excessive sinker agent to carry out sinker, obtain lithium salts product,
Wherein, the sinker agent is any one in sodium fluoride and sodium phosphate.
2. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the ammonium sulfate calcining process, at 550 ~ 650 DEG C, roasting time is 4 ~ 7h to sintering temperature.
3. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the acidleach operation, it is by liquid-solid ratio 5 ~ 8 with the dilute sulfuric acid of 0.5 ~ 2mol/L：1 in 55 ~ 70 DEG C of generals of temperature
Reducing slag containing cobalt lithium leaches 1 ~ 2h,
The liquid-solid ratio is the mass ratio of the volume with the reducing slag of the dilute sulfuric acid.
4. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the heavy cobalt operation, the cobalt hydroxide precipitation is oven-dried at 300 ~ 500 DEG C, the hydrogen after drying
Cobalt oxide leads to H23 ~ 6 h of reduction, the flow of hydrogen is 8 ~ 10m3/h.
5. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the ammonium sulfate calcining process, it is 1 by the positive plate of waste lithium cell and ammonium sulfate according to mass ratio to be：
2.2 ~ 2.5 are mixed.
6. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the acidleach operation, the concentration of dilute sulfuric acid is 0.5 ~ 1mol/L.
7. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the sinker operation, in the case of using sodium fluoride as the sinker agent, the sodium fluoride of addition rubs
Your amount is more than 1.3 times of elemental lithium mole in the lithium-containing solution, and during sinker, temperature is at 55 DEG C ~ 70 DEG C.
8. the method for Call Provision from lithium ion battery positive plate according to claim 7 and lithium, it is characterised in that：
Wherein, in the sinker operation, in the case of 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.
9. the method for Call Provision from lithium ion battery positive plate according to claim 1 and lithium, it is characterised in that：
Wherein, in the sinker operation, in the case of using sodium phosphate as the sinker agent, the sodium phosphate of addition rubs
Your amount is more than 1.5 times of elemental lithium mole in the lithium-containing solution, and during sinker, temperature is at 55 DEG C ~ 70 DEG C.
10. the method for Call Provision from lithium ion battery positive plate according to claim 9 and lithium, its feature exist
In：
Wherein, in the sinker operation, in the case of 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.
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