CN108767353A - The method for producing rich lithium net liquid from waste lithium ion cell anode active material - Google Patents
The method for producing rich lithium net liquid from waste lithium ion cell anode active material Download PDFInfo
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- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
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Abstract
The invention discloses a kind of methods producing rich lithium net liquid from waste lithium ion cell anode active material, belong to waste and old lithium ion battery material recovery technical field, and rich lithium net liquid is produced specifically from the reduction sulphuric leachate of positive electrode active materials.The lithium sulfate solution for the low lithium of high sodium that positive electrode active materials are obtained after reducing leaching, leachate removal of impurities, li-contained phosphate enriched substance is obtained with phosphoric acid or phosphate sinker；Calcium chloride solution Selectively leaching lithium of the li-contained phosphate enriched substance less than theoretical requirement, obtains rich lithium net liquid and the calcium slag of phosphorus containing lithium；Rich lithium net liquid produces the products such as battery-level lithium carbonate or lithium chloride through the conventional methods such as precipitating or crystallizing, and the calcium slag of phosphorus containing lithium is through sulfuric acid leaching and neutralizes obtained solution and returns to sinker and recycles.This method is not necessarily to pre-concentration, directly can produce rich lithium net liquid from the solution of the low lithium of high sodium, and low energy consumption, at low cost, the lithium rate of recovery is high.
Description
Technical field
The invention belongs to waste and old lithium ion battery material recovery technical fields, and in particular to a kind of from waste and old lithium ion battery
The method of the rich lithium net liquid of positive electrode active materials production.
Background technology
Lithium ion battery is high because of operating voltage and than energy, discharging voltage balance, light weight and small, cycle life
It is long, in addition the advantages that memory-less effect, it is widely used in the necks such as portable device, electric vehicle, redundant electrical power, satellite
Domain.With lithium ion battery technology progress, yield increases, and discarded amount is also increasing year by year.Lithium ion battery scraps the time limit one
As be 3~5 years, not yet on a large scale, the rate of recovery is low for recovery system at present, and most waste and old lithium ion batteries are not located effectively
Reason not only pollutes environment, but also wastes a large amount of useful resources.Therefore, waste lithium cell Industry of recycling and reusing resources urgently promotes.
Common lithium ion battery lithium-containing materials have positive electrode and electrolyte, tertiary cathode material main currently on the market
It is mainly lithium hexafluoro phosphate to have cobalt acid lithium, lithium nickelate, LiMn2O4, nickel cobalt manganese and nickel cobalt lithium anode material, electrolyte.For anode
The recycling of valuable metal in material, study both at home and abroad it is more, most conventional methods be reduction the acid-hatching of young eggs i.e. in acidleach system add
Enter reducing agent appropriate to be leached, acid system includes inorganic acid and part organic acid, and reducing agent has sulfur dioxide, dioxygen
Water, most widely used leached as reducing agent, using sulfuric acid using hydrogen peroxide, is obtained containing components such as lithium, cobalt, nickel, manganese
Leachate.Processing for leachate is substantially divided to two kinds of routes, and one is purification of leaching liquor removal of impurities de-iron, aluminium etc. is harmful miscellaneous
Matter, then Direct precipitation prepare the presoma of positive electrode, presoma returns again to battery enterprise and is utilized, the precipitation method production before
It is short to drive body technology flow, but product marketing is narrow, can meet battery material production use, and acid-base neutralization after also needing allotment ingredient
Reagent consumption it is larger, presoma washs repeatedly, causes leaching requirement very big, and the sodium ion of liquid is higher after precipitation, lithium concentration compared with
It is low, cause lithium to recycle high energy consumption.After another scheme is the impurity except iron, aluminium etc. purified to leachate, liquid after purification is continued
Extraction and separation are carried out, nickel salt, cobalt salt are prepared, lithium salts product are recycled from the raffinate after extraction nickel, cobalt, because of lithium concentration in raffinate
It is low and contain a large amount of sodium ion, to prepare lithium carbonate product, carbonate is used again after need to being enriched with using evaporation and concentration mode
Precipitation, low concentration lithium salt solution evaporation and concentration energy consumption is higher, since sodium ions content is higher in raffinate, causes concentration process big
Sodium salt crystal precipitation and lithium salts entrainment loss are measured, and causes postorder lithium salts product high containing sodium, need to further purify can just obtain electricity
Pond grade product.And the solubility product of lithium carbonate is larger, the rate of recovery of carbonate sinker is relatively low, and lithium rate of deposition is less than 80%, after precipitation
Night still reaches 2g/L or more containing lithium.In addition, transport high using a large amount of prices preserves the reduction such as difficult hydrogen peroxide when due to leaching
Agent causes the comprehensive utilization of waste lithium ion cell anode material of high cost.
In addition, K, Na, Ca, Mg are usual impurities in the production of LITHIUM BATTERY lithium salts, since they are close with the chemical property of Li,
It is difficult to remove in lithium salts production, is the difficult point in lithium salts purification research.
Invention content
The purpose of the invention is to overcome existing waste lithium ion cell anode material synthetical recovery lithium and lithium salts to purify
Difficult point in technology and deficiency, it is special standby be from the high sodium of waste lithium ion cell anode active material synthetical recovery process output,
The deficiency in lithium technology is recycled in the lithium sulfate solution of low lithium, it is proposed that produced from waste lithium ion cell anode active material rich
The method of lithium net liquid, this technology precipitates lithium using phosphate precipitation directly from low concentration lithium solution, calcium replaces enriching lithium, nothing
Low concentration lithium solution need to be concentrated, and phosphate precipitating agent can be recycled, low energy consumption, the lithium rate of recovery is high, at low cost.This
The purpose of invention is achieved through the following technical solutions.
The method for producing rich lithium net liquid from waste lithium ion cell anode active material, which is characterized in that including following step
Suddenly：
(1) waste lithium ion cell anode active material is cleaned through sulfuric acid leaching, leachate, obtains lithium sulfate solution；
The sulfuric acid leaching is sulfate reduction leaching or reduction roasting --- sulfuric acid leaching.
(2) the mixture sinker of phosphoric acid or phosphate or the two is added into step (1) obtained lithium sulfate solution, obtains
To li-contained phosphate enriched substance；
(3) the obtained li-contained phosphate enriched substance of step (2) is sized mixing with water, and appropriate leaching agent is added and is soaked
Go out, filtered after leaching, obtain rich lithium net liquid and phosphorus calcium slag, the leaching agent is calcium chloride, the one or both in milk of lime
Mixture.
Further, the mixture addition of phosphoric acid or phosphate or the two in step (1) is that lithium all precipitates in solution
1~1.2 times of required phosphoric acid or phosphate theoretical amount, to improve the precipitate recovery rate of lithium；Calcium chloride or milk of lime in step (2)
Or the mixture addition of the two all leaches required calcium theoretical amount less than the lithium in li-contained phosphate enriched substance, is theoretical amount
0.8~1 times, to Selectively leaching lithium, and the divalent such as calcium, magnesium, iron, aluminium and trivalent ion impurity are stayed in phosphorus calcium slag, it is real
The separation of the existing impurity such as lithium and calcium, magnesium and the purity for improving rich lithium net liquid.
Preferably, the phosphate described in step (2) is sodium phosphate.
Further, the method for producing rich lithium net liquid from waste lithium ion cell anode active material, further includes step
(4)：By the obtained phosphorus calcium slag sulfuric acid leaching of step (3), one or both in leachate sodium carbonate, sodium hydroxide
Return to step (2) recycles after mixture neutralizes.To solve the problems, such as phosphoric acid or phosphatic cycle and improve the rate of recovery of lithium.
Further, in some embodiments, to reduce sulfuric acid leaching cost, the sulfate reduction leaching described in step (1)
Go out, is that mixture is made in dispensing in proportion by waste lithium ion cell anode active material and the concentrated sulfuric acid and solid reductant, mixes
It closes material and obtains solid clinker through slaking reaction, solid clinker water or dilute sulfuric acid pulp are leached, be then separated by solid-liquid separation and obtain sulphur
Acid leaching liquor.To be one or more in coal dust, coke powder, powdered carbon, preferably fixed carbon content is not less than the solid reductant used
50% coal dust.It is 100~350 DEG C of the temperature of slaking reaction, 0.5~8h of curing time, preferably 150~300 DEG C of curing temperature, ripe
Change 1~4h of time.Appropriate hydrogen peroxide can be supplemented when solid clinker pulp leaches to improve the leaching rate of the useful elements such as lithium,
Hydrogen peroxide addition is calculated as the 1%~10% of waste lithium ion cell anode active material quality by hydrogen peroxide quality.
Further, the leachate removal of impurities described in step (1) is to remove sulphuric leachate through sulfide precipitation or extraction
The impurity such as cobalt, nickel, manganese, copper obtain the lithium sulfate solution of the low lithium of high sodium containing sodium >=30g/L, containing lithium≤10g/L.Preferably
Leachate impurity-removing method is：It is that sulphuric leachate successively neutralized hydrolysis is removed into iron, P204 extractions except copper-manganese, P507 extractions remove
After cobalt, P204 extractions remove nickel, the lithium sulfate solution of the low lithium of high sodium is obtained.
Preferably, the li-contained phosphate enriched substance described in step (3) is sized mixing leaching with water, be by waste and old lithium ion battery just
Pole active material is sized mixing with calcium chloride solution to be leached, and wherein calcium chloride concentration is 0.5mol/L~6.5mol/L, liquid stereoplasm
Amount is than being 2:1~10:1, extraction time is 2~12 hours, and temperature is 20~100 DEG C.
The present invention provides economical in a kind of active material from waste lithium ion cell anode, environmentally friendly, high efficiente callback lithium
Method, advantage and effect are：For positive electrode active materials through reducing leaching, removal of impurities and recycling nickel cobalt copper after obtained height
Sodium, low lithium solution directly use calcium phosphate precipitation lithium, avoid the lithium solution pre-concentration work needed for conventional carbonate precipitation method
Sequence, low energy consumption, and the rate of deposition of lithium is up to 95% or more, and the rate of deposition of conventional carbonate precipitation method lithium is less than 80%；It adopts
With less than theoretical requirement calcium chloride or milk of lime li-contained phosphate enriched substance is leached, realize lithium and calcium, magnesium etc. it is miscellaneous
The separation of matter obtains the low rich lithium net liquid of the impurity contents such as calcic, magnesium, sodium, is conducive to subsequent production LITHIUM BATTERY lithium salts or chemical industry produces
Product, and by phosphorus calcium slag sulfuric acid leaching, realizing phosphatic cycle and improving the rate of recovery of lithium；In sulfuric acid leaching, adopt
Post curing is directly mixed with carbonaceous solids reducing agent, the concentrated sulfuric acid with by anode active material of waste lithium battery, then water logging avoids
Using or go back original reagents, the carbonaceous solids reducing agent such as the hydrogen peroxide that only needs to add expensive and inconvenient storage and transportation on a small quantity it is inexpensive easily
, advantageously reduce synthetical recovery cost, and since slaking reaction carries out under higher temperature environment, rapid reaction, completely, have
With element recovery rate height.Phosphate sinker, the calcium chloride of the present invention leaches, the side of the rich lithium net liquid of phosphorus calcium slag acidleach cycle production
Method is not only suitable for recycling lithium in applying waste lithium ionic positive electrode, it can also be used to be enriched with, return from other low concentration lithium salt solutions
The rich lithium net liquid of midwifery production.
Description of the drawings
Fig. 1 is the principle flow chart of the method for the present invention.
Fig. 1 is in order to illustrate more clearly of embodiments of the present invention, it should be apparent that, for ordinary skill people
For member, without creative efforts, other drawings may also be obtained based on these drawings.
Specific implementation mode
Further explanation is made to the present invention below in conjunction with Fig. 1.
The method of the rich lithium net liquid of slave waste lithium ion cell anode active material production of the present invention, by applying waste lithium ionic electricity
Pond positive electrode active materials are through sulfuric acid leaching, and after leachate removes the impurity such as de-iron, aluminium, manganese, cobalt, nickel respectively, phosphoric acid or phosphoric acid is added
Sodium sinker obtains li-contained phosphate enriched substance, the calcium chloride of li-contained phosphate 0.8~1 times of theoretical amount of enrichment or milk of lime leaching
Go out, obtain rich lithium net liquid and phosphorus calcium slag, rich lithium net liquid can be used for conventional method production battery-level lithium carbonate or other lithium salts products.
In some embodiments, calcium chloride or milk of lime leach the phosphorus calcium slag of output after li-contained phosphate enriched substance, can
Step is returned after further using sulfuric acid leaching, leachate that the mixture of sodium carbonate, one or both in sodium hydroxide is used to neutralize again
Suddenly (2) recycle, to solve the problems, such as phosphoric acid or phosphatic cycle and improve the rate of recovery of lithium.
To reduce production cost, in some embodiments, when sulfuric acid leaching, using by waste lithium cell positive-active material
Material directly mixes post curing in proportion with carbonaceous solids reducing agent, the concentrated sulfuric acid, and then water logging, infusion is removed through precipitating and extracting
Miscellaneous, phosphate sinker, li-contained phosphate enriched substance are leached through calcium chloride or milk of lime, obtain rich lithium net liquid.
The method of the present invention is further described with nonlimiting examples below, to help to understand the present invention's
Content and its advantage, and not as limiting the scope of the present invention, protection scope of the present invention is determined by claims.
Embodiment 1
Take that 200g is nickeliferous 28.3%, ternary cell positive material of cobalt 10.63%, manganese 11.75% and lithium 6.50%, by it
Middle acid mine mass ratio 2：1, hydrogen peroxide volume mass is than 1：1, leach solid-liquid quality and volume ratio 1：10, extraction time 1h carries out sulphur
Sour reducing leaching；Leachate adjusts pH value by 30%NaOH solution and removes iron, except liquid cleans by 5 grades of P204 adverse currents after iron, 5 grades
P507 adverse current extraction cobalts, 6 grades of P204 adverse current extraction nickel；Extraction nickel raffinate is added doubly by the theoretical amount 1.2 of wherein lithium molal quantity plus sodium phosphate,
Under the conditions of 90 DEG C, solid isolated li-contained phosphate is stirred to react after 1h, lithium rate of deposition 96%, liquid 0.01g/ containing lithium after sinker
L；Li-contained phosphate enriched substance is leached through 200g/L calcium chloride solutions, 90 DEG C, extraction time 2h of extraction temperature, leaches solid-liquid quality
With volume ratio 1：8, lithium leaching rate 98%, lithium concentration is about 25g/L in leachate containing lithium.
Embodiment 2
Take that 200g is nickeliferous 28.3%, ternary cell positive material of cobalt 10.63%, manganese 11.75% and lithium 6.50%, anode
Material and anthracite mass ratio 6：1,600 DEG C of calcination temperature, roasting clinker is leached with dilute sulfuric acid, leaches solid-liquid quality and volume ratio
1：10, extraction time 1h is leached；Leachate adjusts pH value by 30%NaOH solution and removes iron, except liquid passes through 5 grades after iron
P204 adverse currents clean, 5 grades of P507 adverse current extraction cobalts, 6 grades of P204 adverse current extraction nickel；Extract theoretical amount of the nickel raffinate by wherein lithium molal quantity
1.2 add doubly plus sodium phosphate, under the conditions of 90 DEG C, are stirred to react 1.5h, lithium rate of deposition 96.5%, separation of solid and liquid obtains phosphoric acid containing lithium
Salt enriched substance, li-contained phosphate enriched substance are leached through 300g/L calcium chloride solutions, 90 DEG C, extraction time 1.5h of extraction temperature, leaching
Go out solid-liquid quality and volume ratio 1：5, lithium leaching rate 98.5%, lithium concentration is about 22.5g/L in leachate containing lithium.
Embodiment 3
Take that 200g is nickeliferous 28.3%, ternary cell positive material of cobalt 10.63%, manganese 11.75% and lithium 6.50%, it will just
Pole material, the concentrated sulfuric acid, anthracite mix in proportion, and wherein sulphuric acid is by sulfuric acid and positive electrode mass ratio 2：1, anthracite
Additive amount is the 20% of positive electrode quality, 300 DEG C of calcination temperature, roasting time 2h；Curing material is gone out with water logging, leaches solid-liquid matter
Amount and volume ratio 1：5,1% hydrogen peroxide is added, the leaching rate of extraction time 1h, nickel cobalt lithium are more than 95%, and leachate passes through
30%NaOH solution adjusts pH value and removes iron, except liquid cleans by 5 grades of P204 adverse currents after iron, 5 grades of P507 adverse current extraction cobalts, and 6 grades of P204
Adverse current extraction nickel；Extraction nickel raffinate is added doubly by the theoretical amount 1.2 of wherein lithium molal quantity plus sodium phosphate, and under the conditions of 90 DEG C, stirring is anti-
1h, lithium rate of deposition 95.5%, mixed ore pulp is answered to obtain li-contained phosphate enriched substance through being separated by solid-liquid separation, li-contained phosphate enriched substance is used
Calcium chloride solution leaches lithium, and calcium chloride addition is lithium all leaches required calcium theoretical amount in li-contained phosphate enriched substance 0.9
It calculates again, 90 DEG C, extraction time 2h of extraction temperature, lithium leaching rate 90%, lithium concentration is about 25g/L in leachate containing lithium.
Embodiment 4
Take that 200g is nickeliferous 28.3%, ternary cell positive material of cobalt 10.63%, manganese 11.75% and lithium 6.50%, it will just
Pole material, the concentrated sulfuric acid, anthracite mix in proportion, and wherein sulphuric acid is by sulfuric acid and positive electrode mass ratio 2：1, anthracite
Additive amount is the 20% of positive electrode quality, 300 DEG C of calcination temperature, roasting time 2h；Curing material is gone out with water logging, leaches solid-liquid matter
Amount and volume ratio 1：5,1% hydrogen peroxide is added, the leaching rate of extraction time 1h, nickel cobalt lithium are more than 95%, and leachate passes through
30%NaOH solution adjusts pH value and removes iron, except liquid is calculated by 1.2 times of theoretical amounts of nickel cobalt manganese copper ion total mole number after iron, addition
Vulcanized sodium powder, nickel cobalt concentration is less than 0.005g/L in liquid after precipitation；Liquid presses 1.2 times of the theoretical amount of wherein lithium molal quantity after precipitation
Addition sodium phosphate is stirred to react 1.5h under the conditions of 90 DEG C, Gu isolated li-contained phosphate enriched substance, lithium rate of deposition 95%；
Li-contained phosphate enriched substance leaches lithium with calcium chloride solution, and calcium chloride addition is that lithium all leaches in li-contained phosphate enriched substance
0.8 times of calculating of required calcium theoretical amount, 90 DEG C, extraction time 2h of extraction temperature, lithium leaching rate 80%.
Example 5
The ternary cell positive material of nickeliferous 28.3%, cobalt 10.63%, manganese 11.75% and lithium 6.50% is taken, by wherein sour
Mine mass ratio 2：1, hydrogen peroxide volume mass is than 1：1, leach solid-liquid quality and volume ratio 1：10, extraction time 1h is leached；
Leachate adjusts pH value by 30%NaOH solution and removes iron, except liquid adds theoretical amount 1.2 according to nickel cobalt copper manganese ion summation after iron
Times vulcanized sodium powder, nickel cobalt concentration is less than 0.005g/L in liquid after precipitation；Liquid presses the theoretical amount of wherein lithium molal quantity after precipitation
1.2 add doubly plus sodium phosphate be stirred to react 1.5h under the conditions of 90 DEG C, Gu isolated li-contained phosphate enriched substance, lithium rate of deposition
95%, li-contained phosphate enriched substance leaches lithium with calcium chloride solution, and calcium chloride addition is that lithium is complete in li-contained phosphate enriched substance
Portion leaches 0.8 times of calculating of required calcium theoretical amount, and 90 DEG C, extraction time 2h of extraction temperature, lithium is obtained by filtration in lithium leaching rate 80%
The rich lithium net liquid that concentration is about 25g/L and the phosphorus calcium slag containing a small amount of lithium；The calcium slag of phosphorus containing lithium is leached through 200g/L sulfuric acid solutions,
After liquid is separated by filtration after leaching, addition sodium carbonate is neutralized, and obtained sodium radio-phosphate,P-32 solution returns to sinker and uses.
Embodiment 6
The ternary cell positive material of nickeliferous 28.3%, cobalt 10.63%, manganese 11.75% and lithium 6.50% is taken, by wherein sour
Mine mass ratio 2：1, hydrogen peroxide volume mass is than 1：1, leach solid-liquid quality and volume ratio 1：10, extraction time 1h is leached；
Leachate adjusts pH value by 30%NaOH solution and removes iron, and except liquid cleans by 5 stage countercurrents after iron, 5 stage countercurrents extract cobalt, and 6 grades inverse
Stream extraction nickel；The phosphorus that extraction nickel raffinate is added doubly the sour powder that phosphorates, while being incorporated in example 5 by the theoretical amount 1.2 of wherein lithium molal quantity
Acid sodium solution is precipitated, 90 DEG C of precipitation temperature, and sedimentation time 1h consolidates isolated li-contained phosphate enriched substance, lithium rate of deposition
95.5%, li-contained phosphate enriched substance is leached through 200g/L calcium chloride solutions, 90 DEG C, extraction time 2h of extraction temperature, is leached solid
Liquid quality and volume ratio 1：8, lithium leaching rate 98%.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on above description specific embodiment.To those skilled in the art, any to the equivalent modifications that carry out of the present invention and to replace
In generation, is also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by equivalent change and repair
Change, all covers within the scope of the present invention.
Claims (10)
1. the method for producing rich lithium net liquid from waste lithium ion cell anode active material, which is characterized in that include the following steps：
(1) waste lithium ion cell anode active material is cleaned through sulfuric acid leaching, leachate, obtains lithium sulfate solution；It is described
Sulfuric acid leaching is sulfate reduction leaching or reduction roasting --- sulfuric acid leaching；
(2) the mixture sinker of phosphoric acid or phosphate or the two is added into step (1) obtained lithium sulfate solution, is contained
Lithium phosphate enriched substance；
(3) the obtained li-contained phosphate enriched substance of step (2) is sized mixing with water, and appropriate leaching agent is added and leaches, after leaching
Filtering obtains rich lithium net liquid and phosphorus calcium slag, the mixture of one or both of the leaching agent for calcium chloride, in milk of lime.
2. according to the method described in claim 1, it is characterized in that, phosphoric acid or phosphate described in step (2) or the two it is mixed
The addition for closing object is 1~1.2 times by phosphoric acid needed for lithium in lithium sulfate solution all precipitation or phosphate theoretical amount；Step
(3) addition of leaching agent described in is less than the lithium in li-contained phosphate enriched substance and all leaches required calcium theoretical amount, for theory
0.8~1 times of amount.
3. method according to claim 1 or 2, which is characterized in that step (2) described phosphate is sodium phosphate.
4. method according to claim 1 or 2, which is characterized in that further include step (4)：
(4) by the obtained phosphorus calcium slag sulfuric acid leaching of step (3), one kind or two in leachate sodium carbonate, sodium hydroxide
Return to step (2) recycles after the mixture of person neutralizes.
5. it is by waste and old lithium according to the method described in claim 1, it is characterized in that, sulfate reduction described in step (1) is leached
Mixture is made in dispensing in proportion for ion battery positive electrode active materials and the concentrated sulfuric acid and solid reductant, and mixture is through slaking reaction
Solid clinker is obtained, solid clinker water or dilute sulfuric acid pulp are leached, is then separated by solid-liquid separation and obtains sulphuric leachate；It is described solid
Body reducing agent is one or more in coal dust, coke powder, powdered carbon, and preferably fixed carbon content is not less than 50% coal dust.
6. according to the method described in claim 5, it is characterized in that, the condition of the slaking reaction is：Curing temperature 100~
350 DEG C, 0.5~8h of curing time, preferably 150~300 DEG C of curing temperature, 1~4h of curing time.
7. according to the method described in claim 5, it is characterized in that, when the solid clinker pulp leaches, appropriate dioxygen is supplemented
Water, hydrogen peroxide addition are calculated as the 1%~10% of waste lithium ion cell anode active material quality by hydrogen peroxide quality.
8. according to the method described in claim 1, it is characterized in that, described in step (1) leachate removal of impurities, be by sulfuric acid leaching
Liquid removes cobalt, nickel, manganese, copper impurity through sulfide precipitation or extraction, obtains the low lithium of high sodium containing sodium >=30g/L, containing lithium≤10g/L
Lithium sulfate solution.
9. according to the method described in claim 8, it is characterized in that, described in step (1) leachate removal of impurities, be by sulfuric acid leaching
Neutralized hydrolysis removes copper-manganese to liquid except iron, P204 are extracted successively, P507 is extracted after removing nickel except cobalt, P204 extractions, obtains the low lithium of high sodium
Lithium sulfate solution.
10. according to the method described in claim 1, it is characterized in that, li-contained phosphate enriched substance water tune described in step (3)
Slurry leaches, and is that waste lithium ion cell anode active material is sized mixing to leach with calcium chloride solution, wherein calcium chloride concentration
For 0.5mol/L~6.5mol/L, it is 2 that liquid, which consolidates mass ratio,:1~10:1, extraction time is 2~12 hours, and temperature is 20~100
℃。
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| CN110828926A (en) * | 2019-09-26 | 2020-02-21 | 北京矿冶科技集团有限公司 | Method for cooperatively recovering metal and graphite from anode and cathode materials of waste lithium ion battery |
| CN111170343A (en) * | 2019-12-23 | 2020-05-19 | 北京矿冶科技集团有限公司 | Method for recovering and producing lithium hydroxide from waste lithium ion battery |
| CN111254294A (en) * | 2020-03-11 | 2020-06-09 | 中南大学 | Method for selectively extracting lithium from waste lithium ion battery powder and recovering manganese dioxide through electrolytic separation |
| KR102205442B1 (en) * | 2020-05-26 | 2021-01-20 | 주식회사 에코프로이노베이션 | Method for recovering valuable metals using lithium carbonate from waste electrode materials of lithium-ion batteries |
| CN112250120A (en) * | 2020-12-21 | 2021-01-22 | 矿冶科技集团有限公司 | Method for preparing ternary precursor and lithium carbonate by using waste lithium ion battery black powder and nickel cobalt sulfide ore in synergy mode and application |
| CN115141933A (en) * | 2022-06-28 | 2022-10-04 | 广东邦普循环科技有限公司 | Method for purifying ternary lithium battery recycling leaching solution |
| CN115882098A (en) * | 2022-12-22 | 2023-03-31 | 广东邦普循环科技有限公司 | Method and application of processing battery black powder and producing regenerated graphite negative electrode |
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