CN110527837B - Efficient leaching method of battery positive electrode material - Google Patents
Efficient leaching method of battery positive electrode material Download PDFInfo
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- CN110527837B CN110527837B CN201910892860.3A CN201910892860A CN110527837B CN 110527837 B CN110527837 B CN 110527837B CN 201910892860 A CN201910892860 A CN 201910892860A CN 110527837 B CN110527837 B CN 110527837B
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- 238000002386 leaching Methods 0.000 title claims abstract description 52
- 238000000034 method Methods 0.000 title claims abstract description 19
- 239000007774 positive electrode material Substances 0.000 title claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000706 filtrate Substances 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000002253 acid Substances 0.000 claims abstract description 32
- 239000010405 anode material Substances 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 238000004321 preservation Methods 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 abstract description 6
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 5
- 238000006386 neutralization reaction Methods 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 238000007796 conventional method Methods 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- 239000010926 waste battery Substances 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a high-efficiency leaching method of a battery anode material, belongs to the field of waste battery recovery, and solves the problems of low leaching rate, low utilization rate of sulfuric acid and large consumption of a neutralizing agent in the conventional method. The technical scheme of the invention is as follows: uniformly mixing the battery anode material with water according to the liquid-solid ratio of 5.5-7.5mL:1g to obtain a mixed solution, adding concentrated sulfuric acid, heating to 80-95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, and filtering and separating to obtain primary filter residue and primary filtrate; mixing the primary filtrate with a battery anode material, heating to 80-95 ℃, keeping the temperature for reaction for 1-2h, and filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted; and returning the secondary filter residue to the first step for continuous leaching. The invention improves the leaching rate by two-step solid-liquid cycle leaching; the acid concentration of the leached liquid is reduced, and the utilization rate of sulfuric acid is improved; the dosage of alkaline reagent required by neutralization reaction is reduced, and the cost is reduced.
Description
Technical Field
The invention belongs to the field of waste battery recovery, and particularly relates to a high-efficiency leaching method of a battery anode material.
Background
Regarding the leaching of the battery anode material, the prior art adopts a sulfuric acid hydrogen peroxide system one-step leaching method, the leaching rate reaches 98 percent, the leaching rate needs to be further improved, the consumption of hydrogen peroxide is high, the concentration of the subsequent liquid acid is high, the consumption of alkaline reagents for neutralization reaction in the subsequent process is large, and the cost is high. The sulfuric acid or the citric acid and the hydrogen peroxide are mixed and leached by ultrasound, the same problems exist, and the requirements on ultrasound equipment and production environment are higher. In addition, microwave is also used for improving the leaching effect, but the effect is still not ideal, the obtained leached liquid acid has higher concentration, the utilization rate of sulfuric acid is lower, the neutralization amount of subsequent reaction is large, and unnecessary reagent waste is caused.
Disclosure of Invention
The invention aims to provide a high-efficiency leaching method of a battery anode material, and aims to solve the problems of low leaching rate, low utilization rate of sulfuric acid and large consumption of a neutralizing agent in the conventional method.
The technical scheme of the invention is as follows: a high-efficiency leaching method of a battery positive electrode material comprises the following steps:
firstly, uniformly mixing a battery anode material with water according to the liquid-solid ratio of 5.5-7.5mL:1g to obtain a mixed solution, adding concentrated sulfuric acid, heating to 80-95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, and filtering and separating to obtain primary filter residue and primary filtrate;
step two, mixing the primary filtrate obtained in the step one with a battery anode material, heating to 80-95 ℃, carrying out heat preservation reaction for 1-2h, and filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
As a further improvement of the invention, in the step one, the volume fraction of the sulfuric acid is 98%, the adding amount of the sulfuric acid is 250-350g/L mixed solution, and the adding volume of the hydrogen peroxide is 0.4-0.7 times of the mass of the battery anode material.
As a further improvement of the invention, in the second step, the adding amount of the battery anode material is 1.6-2 times of the mass of the acid left in the primary filtrate.
As a further improvement of the invention, the method is characterized in that: the battery positive electrode material comprises nickel cobalt lithium manganate, lithium cobaltate or lithium manganate.
Compared with the prior art, the invention has the following advantages:
1. the traditional one-step leaching is improved into two-step leaching, the primary filtrate obtained in the step one is used for the reaction in the step two, the primary filter residue is the final residual carbon residue, the secondary filter residue obtained in the step two is returned to the step one to participate in the leaching continuously, and the secondary filtrate is the leachate of the finally obtained elements, so that the leachate is used as the two-step solid-liquid circulation leaching, and the leaching rate is improved;
2. the invention reduces the dosage of hydrogen peroxide in the leaching reaction by two-step leaching; the acid concentration of the leached liquid is reduced, and the utilization rate of sulfuric acid is improved; the dosage of alkaline reagents required by subsequent neutralization reaction is reduced, and the cost is reduced;
3. the invention has simple operation and solves the existing problems.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention in any way.
Example 1, the high-efficiency leaching method of the nickel cobalt lithium manganate battery positive electrode material comprises the following steps:
firstly, uniformly mixing a nickel-cobalt lithium manganate battery anode material with water according to a liquid-solid ratio of 5.5ml to 1g to obtain a mixed solution, adding concentrated sulfuric acid (volume fraction is 98%) into the mixed solution with the addition of 350g/L, heating to 95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, adding hydrogen peroxide with the volume of 0.7 times (ml to g) of the mass of the anode material, filtering and separating to obtain primary filter residue and primary filter liquor, and detecting to obtain the primary filter liquor with the acid concentration of 120g/L, the residual slag rate of 4% and the total metal content of 5%;
step two, mixing the primary filtrate obtained in the step one with a nickel cobalt lithium manganate battery positive electrode material, wherein the addition amount of the nickel cobalt lithium manganate battery positive electrode material is 2 times of the mass of the residual sulfuric acid in the primary filtrate, heating to 95 ℃, carrying out heat preservation reaction for 2 hours, filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted, and detecting after reaction, wherein the acid concentration of the secondary filtrate is 0 g/L;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
In this example, the metal leaching rate was 99.2%. The concentration of acid in the finally obtained sulfate solution (secondary filtrate) reaches 0g/L, the utilization rate of sulfuric acid reaches 100%, the consumption of hydrogen peroxide is saved by 13%, the acid amount to be neutralized in the subsequent process is reduced by 120g/L, and the consumption of alkali liquor is saved.
Embodiment 2, the high-efficiency leaching method of the nickel cobalt lithium manganate battery positive electrode material comprises the following steps:
firstly, uniformly mixing a nickel-cobalt lithium manganate battery anode material with water according to the liquid-solid ratio of 7.5ml:1g to obtain a mixed solution, adding concentrated sulfuric acid (volume fraction is 98%) into the mixed solution with the addition amount of 250g/L, heating to 80 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, adding the hydrogen peroxide with the volume of 0.4 times (ml: g) of the mass of the anode material, filtering and separating to obtain primary filter residue and primary filter liquor, and detecting to obtain the primary filter liquor with the acid concentration of 60 g/L;
step two, mixing the primary filtrate obtained in the step one with a nickel cobalt lithium manganate battery positive electrode material, wherein the addition amount of the nickel cobalt lithium manganate battery positive electrode material is 1.6 times of the mass of the residual sulfuric acid in the primary filtrate, heating to 80 ℃, carrying out heat preservation reaction for 1 hour, filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted, and detecting after reaction, wherein the acid concentration of the secondary filtrate is 5 g/L;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
In this example, the metal leaching rate was 98%. The addition amount of hydrogen peroxide is less, the consumption of 50 percent is saved, the metal leaching rate is reduced, the acid concentration in the finally obtained sulfate solution (secondary filtrate) reaches 5g/L, the utilization rate of sulfuric acid reaches 98 percent, the acid amount to be neutralized in the subsequent process is reduced by 55g/L, and the consumption of alkali liquor is reduced.
Example 3, a high efficiency leaching method of a nickel cobalt manganese acid lithium battery positive electrode material comprises the following steps:
firstly, uniformly mixing a nickel-cobalt lithium manganate battery anode material with water according to a liquid-solid ratio of 6ml:1g to obtain a mixed solution, adding concentrated sulfuric acid (volume fraction is 98%) into the mixed solution with the addition amount of 300g/L, heating to 90 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, adding hydrogen peroxide with the volume of 0.5 times (ml: g) of the mass of the anode material, filtering and separating to obtain primary filter residue and primary filter liquor, and detecting to obtain the primary filter liquor with the acid concentration of 80 g/L;
step two, mixing the primary filtrate obtained in the step one with a nickel cobalt lithium manganate battery positive electrode material, wherein the addition amount of the nickel cobalt lithium manganate battery positive electrode material is 1.8 times of the mass of the residual sulfuric acid in the primary filtrate, heating to 90 ℃, carrying out heat preservation reaction for 1.5h, filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted, and detecting after reaction, wherein the acid concentration of the secondary filtrate is 2 g/L;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
In this example, the metal leaching rate was 99%. The hydrogen peroxide is saved by 37 percent, the acid concentration of the primary filtrate is 80g/L, the acid concentration of the secondary filtrate reaches 2g/L through neutralization, the utilization rate of the sulfuric acid reaches 99.3 percent, and the amount of the neutralized acid is reduced by 78 g/L.
As can be seen from examples 1-3, for nickel cobalt lithium manganate, the best leaching effect can be achieved by reacting according to the material proportion and the reaction time of example 1, no excess acid is left in the secondary filtrate after the reaction, and sulfuric acid is completely utilized; the leaching effect of the embodiment 3 is better, and after the reaction, a trace amount of unreacted sulfuric acid is remained in the secondary filtrate.
Example 4, a high efficiency leaching method of a cobalt acid lithium battery positive electrode material includes the following steps:
firstly, uniformly mixing a cobalt acid lithium battery anode material with water according to the liquid-solid ratio of 7.5mL:1g to obtain a mixed solution, adding concentrated sulfuric acid (volume fraction is 98%) into the mixed solution with the addition amount of 300g/L, heating to 95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, adding hydrogen peroxide with the volume of 0.6 times (mL: g) of the mass of the anode material, filtering and separating to obtain primary filter residue and primary filter liquor, and detecting to obtain the primary filter liquor with the acid concentration of 100 g/L;
step two, mixing the primary filtrate obtained in the step one with a lithium cobaltate battery positive electrode material, wherein the addition amount of the lithium cobaltate battery positive electrode material is 1.8 times of the mass of the residual sulfuric acid in the primary filtrate, heating to 90 ℃, carrying out heat preservation reaction for 2 hours, filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted, and detecting after reaction, wherein the acid concentration of the secondary filtrate is 3 g/L;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
In the embodiment, the lithium cobaltate has good leaching effect, and can be completely leached by adding the reagent in proportion, and the leaching rate reaches 99.5%. The consumption of hydrogen peroxide is saved by 14 percent, the acid concentration in the finally obtained secondary filtrate is 3g/L, and the utilization rate of sulfuric acid reaches 99 percent.
Example 5, a high efficiency leaching method for lithium manganate battery positive electrode material comprises the following steps:
firstly, uniformly mixing a lithium manganate battery anode material with water according to the liquid-solid ratio of 7.5mL:1g to obtain a mixed solution, adding concentrated sulfuric acid (volume fraction is 98%) into the mixed solution with the addition amount of 350g/L, heating to 95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, adding hydrogen peroxide with the volume of 0.7 times (mL: g) of the mass of the anode material, filtering and separating to obtain primary filter residue and primary filtrate, and detecting to obtain the primary filtrate with the acid concentration of 120 g/L;
step two, mixing the primary filtrate obtained in the step one with a lithium manganate battery anode material, wherein the adding amount of the lithium manganate battery anode material is 2 times of the mass of the residual sulfuric acid in the primary filtrate, heating to 95 ℃, carrying out heat preservation reaction for 2 hours, filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted, and detecting after reaction, wherein the acid concentration of the secondary filtrate is 5 g/L;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
Compared with other anode materials, the lithium manganate is difficult to leach, needs high-temperature high-acid leaching, has a little more hydrogen peroxide, is leached according to the feeding proportion, and has a metal leaching rate of 98%. The final sulfate solution (secondary filtrate) had an acid concentration of 5g/L and a sulfuric acid utilization of 98.5%.
In conclusion, the method disclosed by the invention is used for leaching metal elements in the anode material, the consumption of hydrogen peroxide is low, the acid concentration in the finally obtained secondary filtrate is extremely low, the utilization rate of sulfuric acid is more than 98%, alkali liquor which is required for neutralizing 60-120g/L acid in post-treatment is saved, the metal leaching rate can at least reach 98%, and the metal leaching rate can reach more than 99% when the reaction is carried out under the optimal condition. The invention achieves the purposes of high-efficiency leaching and high-efficiency utilization through two-step leaching.
Claims (2)
1. The efficient leaching method of the battery positive electrode material is characterized by comprising the following steps of:
firstly, uniformly mixing a battery anode material with water according to the liquid-solid ratio of 5.5-7.5mL:1g to obtain a mixed solution, adding concentrated sulfuric acid, heating to 80-95 ℃, carrying out heat preservation reaction, dropwise adding hydrogen peroxide until the reaction is complete, and filtering and separating to obtain primary filter residue and primary filtrate; wherein the volume fraction of the sulfuric acid is 98 percent, the adding amount of the sulfuric acid is 250-350g/L mixed solution, and the adding volume of the hydrogen peroxide is 0.4-0.7 time of the mass of the battery anode material;
step two, mixing the primary filtrate obtained in the step one with a battery anode material, wherein the adding amount of the battery anode material is 1.6-2 times of the mass of the residual acid in the primary filtrate, heating to 80-95 ℃, carrying out heat preservation reaction for 1-2 hours, and filtering and separating to obtain secondary filter residue and secondary filtrate which are not completely reacted;
and step three, returning the secondary filter residue obtained in the step two to the step one for continuous leaching.
2. The method for efficiently leaching a battery positive electrode material according to claim 1, wherein: the battery positive electrode material comprises nickel cobalt lithium manganate, lithium cobaltate or lithium manganate.
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| CN113913606A (en) * | 2021-12-10 | 2022-01-11 | 矿冶科技集团有限公司 | Two-stage countercurrent leaching method for anode material of waste power battery |
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