CN108408745A - A kind of method that waste lithium cell prepares battery-level lithium carbonate - Google Patents
A kind of method that waste lithium cell prepares battery-level lithium carbonate Download PDFInfo
- Publication number
- CN108408745A CN108408745A CN201810280312.0A CN201810280312A CN108408745A CN 108408745 A CN108408745 A CN 108408745A CN 201810280312 A CN201810280312 A CN 201810280312A CN 108408745 A CN108408745 A CN 108408745A
- Authority
- CN
- China
- Prior art keywords
- added
- filtrate
- battery
- lithium
- solution
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/04—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/06—Sulfates
-
- 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
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0089—Treating solutions by chemical methods
- C22B15/0091—Treating solutions by chemical methods by cementation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Geology (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The present invention discloses a kind of method that waste lithium cell prepares battery-level lithium carbonate.Old and useless battery material or waste battery that recycling is returned are obtained into battery particle after disassembling broken sieving；By battery particle reducing leaching, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；Alkali readjustment pH is added in first filtrate, the second filtrate and the second filter residue then is obtained by filtration；Zinc powder reaction is added in second filtrate, and filtering obtains third filtrate and third filter residue, and the raffinate containing nickel cobalt magnesium lithium is obtained by extraction by P204 extractants in third filtrate, and after extracting nickel cobalt magnesium with P507 extractants, obtained raffinate is the solution containing lithium, sodium；Lithium raffinate will be contained, sodium hydroxide reaction is added, and obtain the 4th filtrate and the 4th filter residue；Complexing agent is added in 4th filtrate, ammonium hydrogen carbonate is then added, while crystal seed is added, then temperature reaction, obtains battery-level lithium carbonate.The present invention and the separation and recycling that can realize full constituent, the lithium rate of recovery are high.
Description
Technical field
The present invention relates to a kind of methods that waste lithium cell prepares battery-level lithium carbonate, belong at lithium battery material waste
Manage technical field.
Background technology
With the increasingly extensive application of lithium battery, the processing of discarded lithium battery is also increasingly subject to the concern of people, wherein containing
There are many valuable metals, recycling not only to have huge social benefit, also there is huge economic benefit.And with lithium from
The demand of the fast development of sub- battery, battery-level lithium carbonate also increasingly increases, and lithium is recycled from lithium battery waste material and is prepared
Battery-level lithium carbonate, that is, improve the utility value of inner battery waste, and reduces the pollution that raw ore mining belt is come.
Invention content
In view of this, the present invention provides a kind of method that waste lithium cell prepares battery-level lithium carbonate, flow is short, technique
Simply, and the separation and recycling of full constituent can be realized, the rate of recovery is high, and finally obtained product purity is high, added value of product
Greatly.
The present invention solves above-mentioned technical problem by following technological means：
A kind of method that waste lithium cell prepares battery-level lithium carbonate, is following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained by dismantling after-broken-sieving
Battery particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:3-10 addition bottom waters, addition acid for adjusting pH to 0.5-2.0,
50-90 DEG C of reaction temperature, reaction time 2-6 hour, while reducing agent is added, the mole that reducing agent is added is that trivalent metal rubs
0.5-4 times of that amount, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 4-5.5, and iron therein, aluminium, chromium ion is made to precipitate so that
In solution then the second filtrate and the second filter residue is obtained by filtration less than 10mg/L in the content of iron, aluminium, chromium；
4) it cleans, zinc powder is added in the second filtrate, and being 50-70 DEG C in temperature reacts 2-3 hours, and filtering obtains third filtrate
With third filter residue, third filtrate obtains the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese,
After extracting nickel cobalt magnesium with P507 extractants, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 60-80 DEG C, and adjust pH to the 9-11 of solution,
It is reacted 2-3 hours under the conditions of this, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, at 30-60 DEG C
Lower stirring is added, while it is 0.5-1 micron battery-level lithium carbonates as crystal seed that granularity, which is added, and addition is every liter of solution 5-10g,
It then heats to temperature to react 1-2 hours for 90-95 DEG C, filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
100-200 mesh sieve is crossed in the step (1) when sieving.
The reducing agent being added in the step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
In step (3) after readjustment pH to 4-5.5, it is 85-95 DEG C to be warming up to temperature, then passes to air and makes ferrous ion
It is fully oxidized to ferric iron, then proceedes to reaction 1-2 hours.
The granularity for the zinc powder being added in the step (4) is 100-150 mesh, and the molal quantity that zinc powder is added is in the second filtrate
1.1-1.2 times of nickel cobalt copper-manganese molal quantity, maintain be added zinc powder process pH be 3.5-4, P204 extractants extraction except iron, zinc,
Copper, manganese process extract for 8-10 stage countercurrents, and the volume flow ratio of P204 extractants and third filtrate is 1:3-5, having after extraction
Machine mutually passes through 5-6 stage countercurrents and washs, and cleaning solution return is extracted after being mixed with third filtrate, and cleaning solution uses 0.15-
The volume flow ratio of the sulfuric acid solution of 0.25mol/L, organic phase and cleaning solution after extraction is 1:0.1-0.15, P507 extractant
It when extracting the raffinate containing nickel cobalt magnesium lithium, is extracted using 8-10 stage countercurrents, P507 extractants and the raffinate containing nickel cobalt magnesium lithium
The volume flow ratio of liquid is 1:1-2, the organic phase after extraction are washed by 2-3 stage countercurrents, and cleaning solution returns and contains nickel cobalt magnesium
Extracted after the raffinate mixing of lithium, cleaning solution uses the sulfuric acid solution of 0.1-0.15mol/L, organic phase after extraction with wash
The volume flow ratio for washing liquid is 1:0.2-0.25.
It is filtered again after flocculant is added after completion of the reaction in the step (5), the amount that flocculant is added is per ton molten
30-40g flocculants, flocculant PAM is added in liquid.
Step (6) complexing agent is ammonium hydroxide, citric acid, tartaric acid, sulfosalicylic acid or EDTA, after complexing agent is added
A concentration of 0.1-0.2mol/L of complexing agent, the molal quantity of the ammonium hydrogen carbonate of addition are the 1.2- of lithium molal quantity in the 4th filtrate
1.3 again.
Pass through magnetic separation in the step (4), obtain cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder leads to after peracid dissolves
Enter ozone, obtain hydroxy cobalt oxide and nickel solution, hydroxy cobalt oxide is that 850-900 DEG C of calcining obtains battery in 2-4 hours in temperature
Grade cobaltosic oxide, nickel solution obtain nickel sulfate hexahydrate crystal by condensing crystallizing, and the sulfuric acid of 0.1-0.2mol/L is added in copper-manganese powder
Solution, obtains manganese solution and copper powder, and manganese solution obtains manganese sulfate crystal by condensing crystallizing.
P204 extractants after the washing are stripped by 5-6 stage countercurrents, and obtained strip liquor is obtained by condensing crystallizing
Technical grade sulfuric acid zinc, it is 50-51 to be concentrated into Baume degrees, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor returns mixed with the second filtrate
It closes, the P507 extractants after washing are stripped by 5-6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid by condensing crystallizing
Magnesium, it is 52-53 to be concentrated into Baume degrees, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
The 4th filter residue return to step (2) is dissolved.
In reduction of dissolved process, following reaction occurs by taking hydrogen peroxide as an example：
2LiMO2+6H++H2O2→2M2++4H2O+2Li++O2(metals such as M Ni, Co, Mn).
This patent realizes the recycling of full constituent, and flow is short, and the rate of recovery of lithium is high, has finally obtained LITHIUM BATTERY carbonic acid
Lithium, and the granule size of battery-level lithium carbonate is moderate, narrow particle size distribution, good fluidity is suitble to do anode material of lithium battery.
The beneficial effects of the invention are as follows：Flow is short, simple process and low cost, and can realize the separation of full constituent and return
It receives, the rate of recovery is high, and finally obtained product purity is high, and added value of product is big, realizes recycling for material.
Specific implementation mode
Below with reference to specific embodiment, the present invention is described in detail, prepared by a kind of waste lithium cell of the present embodiment
The method of battery-level lithium carbonate is following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained by dismantling after-broken-sieving
Battery particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:3-10 addition bottom waters, addition acid for adjusting pH to 0.5-2.0,
50-90 DEG C of reaction temperature, reaction time 2-6 hour, while reducing agent is added, the mole that reducing agent is added is that trivalent metal rubs
0.5-4 times of that amount, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 4-5.5, and iron therein, aluminium, chromium ion is made to precipitate so that
In solution then the second filtrate and the second filter residue is obtained by filtration less than 10mg/L in the content of iron, aluminium, chromium；
4) it cleans, zinc powder is added in the second filtrate, and being 50-70 DEG C in temperature reacts 2-3 hours, and filtering obtains third filtrate
With third filter residue, third filtrate obtains the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese,
After extracting nickel cobalt magnesium with P507 extractants, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 60-80 DEG C, and adjust pH to the 9-11 of solution,
It is reacted 2-3 hours under the conditions of this, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, at 30-60 DEG C
Lower stirring is added, while it is 0.5-1 micron battery-level lithium carbonates as crystal seed that granularity, which is added, and addition is every liter of solution 5-10g,
It then heats to temperature to react 1-2 hours for 90-95 DEG C, filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
100-200 mesh sieve is crossed in the step (1) when sieving.
The reducing agent being added in the step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
In step (3) after readjustment pH to 4-5.5, it is 85-95 DEG C to be warming up to temperature, then passes to air and makes ferrous ion
It is fully oxidized to ferric iron, then proceedes to reaction 1-2 hours.
The granularity for the zinc powder being added in the step (4) is 100-150 mesh, and the molal quantity that zinc powder is added is in the second filtrate
1.1-1.2 times of nickel cobalt copper-manganese molal quantity, maintain be added zinc powder process pH be 3.5-4, P204 extractants extraction except iron, zinc,
Copper, manganese process extract for 8-10 stage countercurrents, and the volume flow ratio of P204 extractants and third filtrate is 1:3-5, having after extraction
Machine mutually passes through 5-6 stage countercurrents and washs, and cleaning solution return is extracted after being mixed with third filtrate, and cleaning solution uses 0.15-
The volume flow ratio of the sulfuric acid solution of 0.25mol/L, organic phase and cleaning solution after extraction is 1:0.1-0.15, P507 extractant
It when extracting the raffinate containing nickel cobalt magnesium lithium, is extracted using 8-10 stage countercurrents, P507 extractants and the raffinate containing nickel cobalt magnesium lithium
The volume flow ratio of liquid is 1:1-2, the organic phase after extraction are washed by 2-3 stage countercurrents, and cleaning solution returns and contains nickel cobalt magnesium
Extracted after the raffinate mixing of lithium, cleaning solution uses the sulfuric acid solution of 0.1-0.15mol/L, organic phase after extraction with wash
The volume flow ratio for washing liquid is 1:0.2-0.25.
It is filtered again after flocculant is added after completion of the reaction in the step (5), the amount that flocculant is added is per ton molten
30-40g flocculants, flocculant PAM is added in liquid.
Step (6) complexing agent is ammonium hydroxide, citric acid, tartaric acid, sulfosalicylic acid or EDTA, after complexing agent is added
A concentration of 0.1-0.2mol/L of complexing agent, the molal quantity of the ammonium hydrogen carbonate of addition are the 1.2- of lithium molal quantity in the 4th filtrate
1.3 again.
Pass through magnetic separation in the step (4), obtain cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder leads to after peracid dissolves
Enter ozone, obtain hydroxy cobalt oxide and nickel solution, hydroxy cobalt oxide is that 850-900 DEG C of calcining obtains battery in 2-4 hours in temperature
Grade cobaltosic oxide, nickel solution obtain nickel sulfate hexahydrate crystal by condensing crystallizing, and the sulfuric acid of 0.1-0.2mol/L is added in copper-manganese powder
Solution, obtains manganese solution and copper powder, and manganese solution obtains manganese sulfate crystal by condensing crystallizing.
P204 extractants after the washing are stripped by 5-6 stage countercurrents, and obtained strip liquor is obtained by condensing crystallizing
Technical grade sulfuric acid zinc, it is 50-51 to be concentrated into Baume degrees, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor returns mixed with the second filtrate
It closes, the P507 extractants after washing are stripped by 5-6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid by condensing crystallizing
Magnesium, it is 52-53 to be concentrated into Baume degrees, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
The 4th filter residue return to step (2) is dissolved.
Embodiment 1
A kind of method that waste lithium cell prepares battery-level lithium carbonate, is following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained by dismantling after-broken-sieving
Battery particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:7 are added bottom water, acid for adjusting pH are added to 1.85, reaction is warm
80 DEG C of degree, 4 hours reaction time, while reducing agent is added, the mole that reducing agent is added is the 0.9 of trivalent metal mole
Times, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 4.8, makes iron therein, aluminium, chromium ion precipitation so that molten
In liquid then the second filtrate and the second filter residue is obtained by filtration less than 10mg/L in the content of iron, aluminium, chromium；
4) it cleans, zinc powder is added in the second filtrate, and being 65 DEG C in temperature reacts 2.7 hours, and filtering obtains third filtrate and the
Three filter residues, third filtrate obtain the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese, use
After P507 extractants extract nickel cobalt magnesium, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 72 DEG C, the pH to 10.5 of solution be adjusted, at this
It is reacted 2.5 hours under part, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, is stirred at 55 DEG C
Addition is mixed, while it is 0.8 micron of battery-level lithium carbonate as crystal seed that granularity, which is added, addition is every liter of solution 8g, is then heated up
It is 93 DEG C to temperature to react 1.5 hours, filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
150 mesh sieve is crossed in the step (1) when sieving.
The reducing agent being added in the step (2) is sulfur dioxide.
In step (3) after readjustment pH to 4.8, it is 89 DEG C to be warming up to temperature, then passes to air and so that ferrous ion is whole
It is oxidized to ferric iron, then proceedes to reaction 1.8 hours.
The granularity for the zinc powder being added in the step (4) is 125 mesh, and the molal quantity that zinc powder is added is nickel cobalt in the second filtrate
1.18 times of copper-manganese molal quantity, the pH for maintaining that zinc powder process is added are the extraction of 3.8, P204 extractants except iron, zinc, copper, manganese process
It is extracted for 9 stage countercurrents, the volume flow ratio of P204 extractants and third filtrate is 1:4.2, the organic phase after extraction is inverse by 6 grades
Stream washing, cleaning solution return are extracted after being mixed with third filtrate, and cleaning solution uses the sulfuric acid solution of 0.21mol/L, extraction
The volume flow ratio of organic phase and cleaning solution afterwards is 1:When 0.13, P507 extractant extracts the raffinate containing nickel cobalt magnesium lithium,
It is extracted using 9 stage countercurrents, the volume flow ratio of P507 extractants and the raffinate containing nickel cobalt magnesium lithium is 1:1.8, after extraction
Organic phase is washed by 3 stage countercurrents, and cleaning solution return is extracted after being mixed with the raffinate containing nickel cobalt magnesium lithium, and cleaning solution is adopted
With the sulfuric acid solution of 0.13mol/L, the volume flow ratio of organic phase and cleaning solution after extraction is 1:0.22.
It is filtered again after flocculant is added after completion of the reaction in the step (5), the amount that flocculant is added is per ton molten
35g flocculants, flocculant PAM is added in liquid.
Step (6) complexing agent is ammonium hydroxide, and a concentration of 0.15mol/L of complexing agent after complexing agent is added, addition
The molal quantity of ammonium hydrogen carbonate is 1.25 times of lithium molal quantity in the 4th filtrate.
Pass through magnetic separation in the step (4), obtain cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder leads to after peracid dissolves
Enter ozone, obtain hydroxy cobalt oxide and nickel solution, hydroxy cobalt oxide is that 880 DEG C of calcinings obtain four oxygen of LITHIUM BATTERY in 3 hours in temperature
Change three cobalts, nickel solution obtains nickel sulfate hexahydrate crystal by condensing crystallizing, and copper-manganese powder is added the sulfuric acid solution of 0.15mol/L, obtains
Manganese solution and copper powder, manganese solution obtain manganese sulfate crystal by condensing crystallizing.
P204 extractants after the washing are stripped by 5 stage countercurrents, and obtained strip liquor obtains work by condensing crystallizing
Industry level zinc sulfate, it is 50.5 to be concentrated into Baume degrees, and it is 13 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate, is washed
P507 extractants after washing are stripped by 5.8 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid magnesium by condensing crystallizing, dense
It is 52.5 to be reduced to Baume degrees, and it is 13 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
The 4th filter residue return to step (2) is dissolved.
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013, wherein：
| Index | D10 | D50 | D90 | D100 | Mobility |
| Numerical value | 3.5 micron | 5.8 micron | 9.1 micron | 9.8 micron | 15s/50g |
The purity 99.2% of obtained nickel sulfate hexahydrate crystal, the purity 99.1% of manganese sulfate crystal, the purity 99.2% of copper powder,
Technical grade sulfuric acid zinc purity is 98.8%, the purity 99.1% of magnesium sulfate.
Obtained battery-grade cobaltosic oxide detection data is as follows：
| Co | Na | Cd | Ni | Mn | Ca |
| 72.1% | 25ppm | 2ppm | 12ppm | 6ppm | 7ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Tap density |
| 2.7 micron | 5.6 micron | 8.7 micron | 8.4m2/g | 51ppm | 2.6g/mL |
The rate of recovery 99.5% of final lithium synthesis, nickel, cobalt, manganese and magnesium comprehensive recovery be respectively 99.1%, 99.1%,
98.7% and 98.3%.
Embodiment 2
A kind of method that waste lithium cell prepares battery-level lithium carbonate, is following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained by dismantling after-broken-sieving
Battery particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:6 are added bottom water, acid for adjusting pH are added to 1.32, reaction is warm
65 DEG C of degree, 4.2 hours reaction time, while reducing agent is added, the mole that reducing agent is added is the 1.8 of trivalent metal mole
Times, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 5.2, makes iron therein, aluminium, chromium ion precipitation so that molten
In liquid then the second filtrate and the second filter residue is obtained by filtration less than 10mg/L in the content of iron, aluminium, chromium；
4) it cleans, zinc powder is added in the second filtrate, and being 62 DEG C in temperature reacts 2.5 hours, and filtering obtains third filtrate and the
Three filter residues, third filtrate obtain the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese, use
After P507 extractants extract nickel cobalt magnesium, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 75 DEG C, the pH to 10.2 of solution be adjusted, at this
It is reacted 2.3 hours under part, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, is stirred at 45 DEG C
Addition is mixed, while it is 0.8 micron of battery-level lithium carbonate as crystal seed that granularity, which is added, addition is every liter of solution 8g, is then heated up
It is 93 DEG C to temperature to react 1.8 hours, filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
150 mesh sieve is crossed in the step (1) when sieving.
The reducing agent being added in the step (2) is sodium sulfite.
In step (3) after readjustment pH to 5.2, it is 92 DEG C to be warming up to temperature, then passes to air and so that ferrous ion is whole
It is oxidized to ferric iron, then proceedes to reaction 1.3 hours.
The granularity for the zinc powder being added in the step (4) is 125 mesh, and the molal quantity that zinc powder is added is nickel cobalt in the second filtrate
1.16 times of copper-manganese molal quantity, the pH for maintaining that zinc powder process is added are the extraction of 3.8, P204 extractants except iron, zinc, copper, manganese process
It is extracted for 10 stage countercurrents, the volume flow ratio of P204 extractants and third filtrate is 1:5, the organic phase after extraction is inverse by 6 grades
Stream washing, cleaning solution return are extracted after being mixed with third filtrate, and cleaning solution uses the sulfuric acid solution of 0.19mol/L, extraction
The volume flow ratio of organic phase and cleaning solution afterwards is 1:When 0.13, P507 extractant extracts the raffinate containing nickel cobalt magnesium lithium,
It is extracted using 9 stage countercurrents, the volume flow ratio of P507 extractants and the raffinate containing nickel cobalt magnesium lithium is 1:1.8, after extraction
Organic phase is washed by 3 stage countercurrents, and cleaning solution return is extracted after being mixed with the raffinate containing nickel cobalt magnesium lithium, and cleaning solution is adopted
With the sulfuric acid solution of 0.13mol/L, the volume flow ratio of organic phase and cleaning solution after extraction is 1:0.22.
It is filtered again after flocculant is added after completion of the reaction in the step (5), the amount that flocculant is added is per ton molten
38g flocculants, flocculant PAM is added in liquid.
Step (6) complexing agent is EDTA, and a concentration of 0.12mol/L of complexing agent after complexing agent is added, addition
The molal quantity of ammonium hydrogen carbonate is 1.23 times of lithium molal quantity in the 4th filtrate.
Pass through magnetic separation in the step (4), obtain cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder leads to after peracid dissolves
Enter ozone, obtain hydroxy cobalt oxide and nickel solution, hydroxy cobalt oxide is that 885 DEG C of calcinings obtain LITHIUM BATTERY four in 3.5 hours in temperature
Co 3 O, nickel solution obtain nickel sulfate hexahydrate crystal by condensing crystallizing, and copper-manganese powder is added the sulfuric acid solution of 0.15mol/L, obtains
To manganese solution and copper powder, manganese solution obtains manganese sulfate crystal by condensing crystallizing.
P204 extractants after the washing are stripped by 6 stage countercurrents, and obtained strip liquor obtains work by condensing crystallizing
Industry level zinc sulfate, it is 50.6 to be concentrated into Baume degrees, and it is 12 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate, is washed
P507 extractants after washing are stripped by 6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid magnesium by condensing crystallizing, are concentrated
It is 52.3 to Baume degrees, it is 13 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
The 4th filter residue return to step (2) is dissolved.
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013, wherein：
| Index | D10 | D50 | D90 | D100 | Mobility |
| Numerical value | 3.8 micron | 5.8 micron | 9.2 micron | 9.7 micron | 16s/50g |
The purity 99.1% of obtained nickel sulfate hexahydrate crystal, the purity 99.1% of manganese sulfate crystal, the purity 99.2% of copper powder,
Technical grade sulfuric acid zinc purity is 98.7%, the purity 99.1% of magnesium sulfate.
Obtained battery-grade cobaltosic oxide detection data is as follows：
| Co | Na | Cd | Ni | Mn | Ca |
| 72.1% | 22ppm | 1ppm | 13ppm | 8ppm | 9ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Tap density |
| 2.7 micron | 5.7 micron | 8.8 micron | 8.2m2/g | 59ppm | 2.58g/mL |
The rate of recovery 99.6% of final lithium synthesis, nickel, cobalt, manganese and magnesium comprehensive recovery be respectively 99.2%, 99.1%,
98.3% and 98.8%.
Embodiment 3
A kind of method that waste lithium cell prepares battery-level lithium carbonate, is following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained by dismantling after-broken-sieving
Battery particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:5.5 are added bottom water, and acid for adjusting pH is added to 1.85, reacts
83 DEG C of temperature, 4.5 hours reaction time, while reducing agent is added, the mole that reducing agent is added is trivalent metal mole
1.8 times, reaction, which finishes, to be filtered, and the first filtrate and the first filter residue are obtained；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 5.3, makes iron therein, aluminium, chromium ion precipitation so that molten
In liquid then the second filtrate and the second filter residue is obtained by filtration less than 10mg/L in the content of iron, aluminium, chromium；
4) it cleans, zinc powder is added in the second filtrate, and being 65 DEG C in temperature reacts 2.8 hours, and filtering obtains third filtrate and the
Three filter residues, third filtrate obtain the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese, use
After P507 extractants extract nickel cobalt magnesium, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 72 DEG C, the pH to 10.7 of solution be adjusted, at this
It is reacted 2.8 hours under part, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, is stirred at 55 DEG C
Addition is mixed, while it is 0.8 micron of battery-level lithium carbonate as crystal seed that granularity, which is added, addition is every liter of solution 8.5g, is then risen
Temperature to temperature is 93 DEG C and reacts 1.8 hours that filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
175 mesh sieve is crossed in the step (1) when sieving.
The reducing agent being added in the step (2) is zinc powder.
In step (3) after readjustment pH to 5.3, it is 94 DEG C to be warming up to temperature, then passes to air and so that ferrous ion is whole
It is oxidized to ferric iron, then proceedes to reaction 1.8 hours.
The granularity for the zinc powder being added in the step (4) is 125 mesh, and the molal quantity that zinc powder is added is nickel cobalt in the second filtrate
1.15 times of copper-manganese molal quantity, the pH for maintaining that zinc powder process is added are the extraction of 3.8, P204 extractants except iron, zinc, copper, manganese process
It is extracted for 8 stage countercurrents, the volume flow ratio of P204 extractants and third filtrate is 1:4.3, the organic phase after extraction is inverse by 6 grades
Stream washing, cleaning solution return are extracted after being mixed with third filtrate, and cleaning solution uses the sulfuric acid solution of 0.18mol/L, extraction
The volume flow ratio of organic phase and cleaning solution afterwards is 1:When 0.13, P507 extractant extracts the raffinate containing nickel cobalt magnesium lithium,
It is extracted using 10 stage countercurrents, the volume flow ratio of P507 extractants and the raffinate containing nickel cobalt magnesium lithium is 1:1.2, after extraction
Organic phase is washed by 3 stage countercurrents, and cleaning solution return is extracted after being mixed with the raffinate containing nickel cobalt magnesium lithium, and cleaning solution is adopted
With the sulfuric acid solution of 0.12mol/L, the volume flow ratio of organic phase and cleaning solution after extraction is 1:0.22.
It is filtered again after flocculant is added after completion of the reaction in the step (5), the amount that flocculant is added is per ton molten
33g flocculants, flocculant PAM is added in liquid.
Step (6) complexing agent is sulfosalicylic acid, and a concentration of 0.11mol/L of complexing agent after complexing agent is added,
The molal quantity of the ammonium hydrogen carbonate of addition is 1.27 times of lithium molal quantity in the 4th filtrate.
Pass through magnetic separation in the step (4), obtain cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder leads to after peracid dissolves
Enter ozone, obtain hydroxy cobalt oxide and nickel solution, hydroxy cobalt oxide is that 885 DEG C of calcinings obtain LITHIUM BATTERY four in 3.2 hours in temperature
Co 3 O, nickel solution obtain nickel sulfate hexahydrate crystal by condensing crystallizing, and copper-manganese powder is added the sulfuric acid solution of 0.14mol/L, obtains
To manganese solution and copper powder, manganese solution obtains manganese sulfate crystal by condensing crystallizing.
P204 extractants after the washing are stripped by 6 stage countercurrents, and obtained strip liquor obtains work by condensing crystallizing
Industry level zinc sulfate, it is 50.3 to be concentrated into Baume degrees, and it is 13 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate, is washed
P507 extractants after washing are stripped by 6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid magnesium by condensing crystallizing, are concentrated
It is 52.5 to Baume degrees, it is 14 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
The 4th filter residue return to step (2) is dissolved.
Finally obtained lithium carbonate meets the requirement of professional standard YS/T 582-2013, wherein：
| Index | D10 | D50 | D90 | D100 | Mobility |
| Numerical value | 3.8 micron | 6.1 micron | 9.3 micron | 9.9 micron | 15s/50g |
The purity 99.1% of obtained nickel sulfate hexahydrate crystal, the purity 99.1% of manganese sulfate crystal, the purity 99.1% of copper powder,
Technical grade sulfuric acid zinc purity is 98.9%, the purity 99.1% of magnesium sulfate.
Obtained battery-grade cobaltosic oxide detection data is as follows：
| Co | Na | Cd | Ni | Mn | Ca |
| 72.2% | 22ppm | 1ppm | 11ppm | 7ppm | 8ppm |
| D10 | D50 | D90 | BET | Sulfate radical | Tap density |
| 2.8 micron | 5.7 micron | 8.6 micron | 8.2m2/g | 43ppm | 2.55g/mL |
The rate of recovery 99.6% of final lithium synthesis, nickel, cobalt, manganese and magnesium comprehensive recovery be respectively 99.2%, 99.1%,
98.8% and 98.3%.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (10)
1. a kind of method that waste lithium cell prepares battery-level lithium carbonate, which is characterized in that be following steps：
1) it pre-processes, recycling old and useless battery material back or waste battery is obtained into battery by dismantling after-broken-sieving
Particle；
2) by battery particle reducing leaching, according to solid-to-liquid ratio 1:Bottom water is added in 3-10, and acid for adjusting pH is added to 0.5-2.0, reaction
50-90 DEG C of temperature, reaction time 2-6 hour, while reducing agent is added, the mole that reducing agent is added is trivalent metal mole
0.5-4 times, reaction is finished and is filtered, and obtains the first filtrate and the first filter residue；
3) iron aluminium is removed, alkali, which is added, in the first filtrate adjusts back pH to 4-5.5, so that iron therein, aluminium, chromium ion is precipitated so that solution
Middle iron, aluminium, chromium content be less than 10mg/L, the second filtrate and the second filter residue is then obtained by filtration；
4) it cleans, zinc powder is added in the second filtrate, and being 50-70 DEG C in temperature reacts 2-3 hour, filters, obtains third filtrate and the
Three filter residues, third filtrate obtain the raffinate containing nickel cobalt magnesium lithium after the extraction of P204 extractants is except iron, zinc, copper, manganese, use
After P507 extractants extract nickel cobalt magnesium, obtained raffinate is the solution containing lithium, sodium；
5) deep impurity-removing will contain lithium raffinate and sodium hydroxide is added at 60-80 DEG C, and pH to the 9-11 of solution be adjusted, at this
It is reacted 2-3 hours under part, filters, obtain the 4th filtrate and the 4th filter residue；
6) battery-level lithium carbonate is prepared, complexing agent is added in the 4th filtrate, ammonium hydrogen carbonate is then added, is stirred at 30-60 DEG C
Addition is mixed, while it is 0.5-1 micron battery-level lithium carbonates as crystal seed that granularity, which is added, addition is every liter of solution 5-10g, then
It is warming up to temperature to react 1-2 hours for 90-95 DEG C, filtration washing, drying sieving is packaged to be battery-level lithium carbonate.
2. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
100-200 mesh sieve is crossed in step (1) when sieving.
3. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
The reducing agent being added in step (2) is sulfur dioxide, hydrogen peroxide, sodium sulfite, iron powder or zinc powder.
4. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：Step
(3) in after readjustment pH to 4-5.5, it is 85-95 DEG C to be warming up to temperature, then passes to air and ferrous ion is made to be fully oxidized to three
Valence iron then proceedes to reaction 1-2 hours.
5. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
The granularity for the zinc powder being added in step (4) is 100-150 mesh, and the molal quantity that zinc powder is added is nickel cobalt copper-manganese mole in the second filtrate
Several 1.1-1.2 times, the pH for maintaining that zinc powder process is added is 3.5-4, and the extraction of P204 extractants is 8- except iron, zinc, copper, manganese process
10 stage countercurrents extract, and the volume flow ratio of P204 extractants and third filtrate is 1:3-5, the organic phase after extraction pass through 5-6 grades
Countercurrent washing, cleaning solution return are extracted after being mixed with third filtrate, and cleaning solution is molten using the sulfuric acid of 0.15-0.25mol/L
The volume flow ratio of liquid, organic phase and cleaning solution after extraction is 1:The extraction of 0.1-0.15, P507 extractant contains nickel cobalt magnesium lithium
Raffinate when, using 8-10 stage countercurrents extract, P507 extractants and the volume flow ratio of the raffinate containing nickel cobalt magnesium lithium are
1:1-2, the organic phase after extraction are washed by 2-3 stage countercurrents, after cleaning solution return is mixed with the raffinate containing nickel cobalt magnesium lithium
It is extracted, cleaning solution uses the sulfuric acid solution of 0.1-0.15mol/L, the volume flow ratio of organic phase and cleaning solution after extraction
It is 1:0.2-0.25.
6. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
It is filtered again after flocculant is added after completion of the reaction in step (5), the amount that flocculant is added is that 30-40g is added in solution per ton
Flocculant, flocculant PAM.
7. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
Step (6) complexing agent is ammonium hydroxide, citric acid, tartaric acid, sulfosalicylic acid or EDTA, and the concentration of complexing agent after complexing agent is added
For 0.1-0.2mol/L, the molal quantity of the ammonium hydrogen carbonate of addition is 1.2-1.3 times of lithium molal quantity in the 4th filtrate.
8. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：It is described
Pass through magnetic separation in step (4), obtains cobalt nickel by powder and copper-manganese powder, cobalt nickel by powder is passed through ozone after peracid dissolves, obtains hydroxyl
Base cobalt oxide and nickel solution, hydroxy cobalt oxide are that 850-900 DEG C of calcining obtains battery-grade cobaltosic oxide in 2-4 hours in temperature,
Nickel solution obtains nickel sulfate hexahydrate crystal by condensing crystallizing, and copper-manganese powder is added the sulfuric acid solution of 0.1-0.2mol/L, it is molten to obtain manganese
Liquid and copper powder, manganese solution obtain manganese sulfate crystal by condensing crystallizing.
9. the method that a kind of waste lithium cell according to claim 5 prepares battery-level lithium carbonate, it is characterised in that：It is described
P204 extractants after washing are stripped by 5-6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid zinc by condensing crystallizing,
It is 50-51 to be concentrated into Baume degrees, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate, after washing
P507 extractants are stripped by 5-6 stage countercurrents, and obtained strip liquor obtains technical grade sulfuric acid magnesium by condensing crystallizing, is concentrated into wave
U.S. degree is 52-53, and it is 10-15 DEG C to be then cooled to temperature, and mother liquor return is mixed with the second filtrate.
10. the method that a kind of waste lithium cell according to claim 1 prepares battery-level lithium carbonate, it is characterised in that：Institute
The 4th filter residue return to step (2) is stated to be dissolved.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810280312.0A CN108408745B (en) | 2018-04-02 | 2018-04-02 | Method for preparing battery-grade lithium carbonate from waste lithium batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810280312.0A CN108408745B (en) | 2018-04-02 | 2018-04-02 | Method for preparing battery-grade lithium carbonate from waste lithium batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108408745A true CN108408745A (en) | 2018-08-17 |
| CN108408745B CN108408745B (en) | 2020-07-14 |
Family
ID=63132684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810280312.0A Active CN108408745B (en) | 2018-04-02 | 2018-04-02 | Method for preparing battery-grade lithium carbonate from waste lithium batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108408745B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468472A (en) * | 2018-12-18 | 2019-03-15 | 江苏理工学院 | A method of separating cobalt from the material containing cobalt and nickel |
| CN109536728A (en) * | 2019-01-25 | 2019-03-29 | 广东省稀有金属研究所 | A method of recycling nickel cobalt from battery electrode material leachate |
| CN110205491A (en) * | 2019-06-25 | 2019-09-06 | 中南大学 | A kind of metal lithium simple substance and the preparation method and application thereof |
| CN110724818A (en) * | 2019-09-29 | 2020-01-24 | 湖南雅城新材料有限公司 | Full-wet recovery process of waste lithium battery |
| CN111519031A (en) * | 2020-04-29 | 2020-08-11 | 江苏北矿金属循环利用科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder |
| CN112366304A (en) * | 2020-11-16 | 2021-02-12 | 湖南上临新材料科技有限公司 | Nanocrystalline iron-silicon alloy-based cathode material for lithium ion battery and preparation method thereof |
| CN112499694A (en) * | 2020-12-02 | 2021-03-16 | 贵州鹏程新材料有限公司 | Method for extracting battery-grade cobalt chloride from waste battery materials |
| WO2022228233A1 (en) * | 2021-04-25 | 2022-11-03 | 湖南金源新材料股份有限公司 | Method for extracting and preparing battery-grade lithium carbonate from p507 raffinate, and extraction device |
| CN116040692A (en) * | 2022-12-30 | 2023-05-02 | 中铁资源集团有限公司 | Method for improving grade of cobalt oxide for crude hydrogen production |
Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0517832A (en) * | 1991-07-10 | 1993-01-26 | Daito Kagaku Kk | Method for recovering lithium from waste lithium battery |
| US5888463A (en) * | 1998-01-02 | 1999-03-30 | Toxco | Li reclamation process |
| CN101628869A (en) * | 2009-08-18 | 2010-01-20 | 沈阳张明化工有限公司 | Method for preparing cobalt octoate by using LiCoO, anode material of waste lithium battery |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN102088124A (en) * | 2010-12-24 | 2011-06-08 | 佛山市邦普循环科技有限公司 | High-purity polymetallic-element solid mixed salt and preparation method and application thereof |
| CN102952954A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Processing method of trivalent cobalt nickel oxide waste material and waste cobalt nickel alloy |
| CN106505225A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | The method that lithium prepares battery-level lithium carbonate is reclaimed in a kind of old and useless battery from lithium |
| CN107267759A (en) * | 2017-06-12 | 2017-10-20 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive recovering process of anode material for lithium-ion batteries |
| CN107437626A (en) * | 2017-07-31 | 2017-12-05 | 蒋央芳 | Method for preparing carbon-coated manganese phosphate from waste zinc-manganese battery |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN107815550A (en) * | 2017-12-08 | 2018-03-20 | 蒋央芳 | Method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries |
-
2018
- 2018-04-02 CN CN201810280312.0A patent/CN108408745B/en active Active
Patent Citations (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0517832A (en) * | 1991-07-10 | 1993-01-26 | Daito Kagaku Kk | Method for recovering lithium from waste lithium battery |
| US5888463A (en) * | 1998-01-02 | 1999-03-30 | Toxco | Li reclamation process |
| CN101628869A (en) * | 2009-08-18 | 2010-01-20 | 沈阳张明化工有限公司 | Method for preparing cobalt octoate by using LiCoO, anode material of waste lithium battery |
| CN101871048A (en) * | 2010-06-25 | 2010-10-27 | 浙江华友钴业股份有限公司 | Method for recovering cobalt, nickel and manganese from waste lithium cells |
| CN102088124A (en) * | 2010-12-24 | 2011-06-08 | 佛山市邦普循环科技有限公司 | High-purity polymetallic-element solid mixed salt and preparation method and application thereof |
| CN102952954A (en) * | 2011-08-26 | 2013-03-06 | 深圳市格林美高新技术股份有限公司 | Processing method of trivalent cobalt nickel oxide waste material and waste cobalt nickel alloy |
| CN106505225A (en) * | 2016-12-12 | 2017-03-15 | 江西赣锋锂业股份有限公司 | The method that lithium prepares battery-level lithium carbonate is reclaimed in a kind of old and useless battery from lithium |
| CN107267759A (en) * | 2017-06-12 | 2017-10-20 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive recovering process of anode material for lithium-ion batteries |
| CN107437626A (en) * | 2017-07-31 | 2017-12-05 | 蒋央芳 | Method for preparing carbon-coated manganese phosphate from waste zinc-manganese battery |
| CN107653378A (en) * | 2017-08-25 | 2018-02-02 | 金川集团股份有限公司 | The recovery method of valuable metal in a kind of waste and old nickel cobalt manganese lithium ion battery |
| CN107815550A (en) * | 2017-12-08 | 2018-03-20 | 蒋央芳 | Method for producing battery-grade manganese sulfate and zinc sulfate from waste zinc-manganese batteries |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109468472A (en) * | 2018-12-18 | 2019-03-15 | 江苏理工学院 | A method of separating cobalt from the material containing cobalt and nickel |
| CN109536728A (en) * | 2019-01-25 | 2019-03-29 | 广东省稀有金属研究所 | A method of recycling nickel cobalt from battery electrode material leachate |
| CN110205491A (en) * | 2019-06-25 | 2019-09-06 | 中南大学 | A kind of metal lithium simple substance and the preparation method and application thereof |
| CN110724818A (en) * | 2019-09-29 | 2020-01-24 | 湖南雅城新材料有限公司 | Full-wet recovery process of waste lithium battery |
| CN110724818B (en) * | 2019-09-29 | 2021-05-18 | 湖南雅城新材料有限公司 | Full-wet recovery process of waste lithium battery |
| CN111519031A (en) * | 2020-04-29 | 2020-08-11 | 江苏北矿金属循环利用科技有限公司 | Method for recycling nickel, cobalt, manganese and lithium from waste power lithium ion battery black powder |
| CN112366304A (en) * | 2020-11-16 | 2021-02-12 | 湖南上临新材料科技有限公司 | Nanocrystalline iron-silicon alloy-based cathode material for lithium ion battery and preparation method thereof |
| CN112499694A (en) * | 2020-12-02 | 2021-03-16 | 贵州鹏程新材料有限公司 | Method for extracting battery-grade cobalt chloride from waste battery materials |
| WO2022228233A1 (en) * | 2021-04-25 | 2022-11-03 | 湖南金源新材料股份有限公司 | Method for extracting and preparing battery-grade lithium carbonate from p507 raffinate, and extraction device |
| CN116040692A (en) * | 2022-12-30 | 2023-05-02 | 中铁资源集团有限公司 | Method for improving grade of cobalt oxide for crude hydrogen production |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108408745B (en) | 2020-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108408745A (en) | A kind of method that waste lithium cell prepares battery-level lithium carbonate | |
| CN102234721B (en) | Treatment method of nickel-cobalt material | |
| CN104099474B (en) | A kind of electroplating sludge recycles technique | |
| KR102008582B1 (en) | A Method for Preparing Nickel-Cobalt-Manganese Complex Sulfate Solution by Recycling A Waste Cathode Material of Lithium Secondary Battery Using Solvent Extraction Process to Control Impurities | |
| CN102021331B (en) | Processing method for comprehensively recovering high manganese asbolite | |
| CN105200235B (en) | The method that valuable metal prepares tough cathode and LITHIUM BATTERY nickel sulfate is reclaimed from electroplating sludge | |
| CN103468979B (en) | The method of scandium is reclaimed from smelting laterite-nickel ores iron aluminium slag | |
| CN109868373A (en) | A method of substep leaching nickel, cobalt from nickel, cobalt, manganese mixture | |
| JPH06116660A (en) | Method for frecovering valuable metal from oxidized ore | |
| CN112159897B (en) | Method for purifying nickel-cobalt-manganese leaching solution | |
| CN103468972B (en) | The treatment process of red soil nickel ore synthetical recovery scandium and nickel cobalt | |
| CN105648214B (en) | It is a kind of to control the method that current potential vulcanization separates valuable metal in solution | |
| CN103074490B (en) | Purification method in electrolytic metal manganese production process by multi-mine method | |
| CN111910075A (en) | Method for leaching nickel and cobalt from rough nickel and cobalt hydroxide in two stages | |
| CN113265532B (en) | Method for leaching nickel-ammonia solution from nickel-iron alloy by wet method and application | |
| CN103468980B (en) | A kind of red soil nickel ore extracts the method for scandium | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| US20230344030A1 (en) | Method for removing elemental copper from ternary battery waste and application thereof | |
| CN108502915A (en) | A method of nano zine oxide is prepared with high zinc dedusting ash | |
| CN105274352B (en) | A kind of method that copper cobalt manganese is separated in the manganese cobalt calcium zinc mixture from copper carbonate | |
| CN109797294A (en) | The method of nickel, cobalt is recycled in a kind of magnesium water | |
| CN108754158A (en) | A kind of method of copper-contained sludge production cupric sulfate purified | |
| CN107502743A (en) | A kind of processing method of cathode copper waste liquid | |
| CN114604837A (en) | Preparation method of iron phosphate and preparation method of lithium iron phosphate | |
| EP2883969B1 (en) | Method for effluent treatment in smelting of nickel oxide ore |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220614 Address after: Building 148000, South Building, Guangdong Province, Guangdong science and Technology Park Patentee after: Yuanbang JIAYE (Shenzhen) Industrial Co.,Ltd. Address before: No.42 Xiashan village, Baita Town, Xianju County, Taizhou City, Zhejiang Province Patentee before: Fang Jiacheng |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220920 Address after: No. 2708-5, 27th Floor, International Trade Center, Building 1, Furao Center, No. 200, Changjiang Road, Yantai District, China (Shandong) Pilot Free Trade Zone, Yantai City, Shandong Province, 264001 Patentee after: China Lithium New Energy Technology (Yantai) Co.,Ltd. Address before: Building 148000, South Building, Guangdong Province, Guangdong science and Technology Park Patentee before: Yuanbang JIAYE (Shenzhen) Industrial Co.,Ltd. |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for preparing battery grade lithium carbonate from waste lithium batteries Effective date of registration: 20230331 Granted publication date: 20200714 Pledgee: Yantai Rural Commercial Bank Co.,Ltd. Zhifu District Branch Pledgor: China Lithium New Energy Technology (Yantai) Co.,Ltd. Registration number: Y2023980037201 |