CN113151680B - Method for recycling waste lithium batteries - Google Patents
Method for recycling waste lithium batteries Download PDFInfo
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- CN113151680B CN113151680B CN202110171619.9A CN202110171619A CN113151680B CN 113151680 B CN113151680 B CN 113151680B CN 202110171619 A CN202110171619 A CN 202110171619A CN 113151680 B CN113151680 B CN 113151680B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Abstract
The invention relates to the technical field of waste lithium batteries, in particular to a method for recycling waste lithium batteries, which comprises the following steps: a) Reacting the waste lithium battery material with acid liquor, and filtering to obtain leaching liquid and solid slag; b) Carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain an impurity-removing solution; c) Performing bipolar membrane electrodialysis on the impurity removal solution to obtain a lithium hydroxide solution, an acid solution and a salt solution; preparing the salt solution according to the element proportion, and reacting the prepared salt solution, alkali liquor and a first auxiliary agent to obtain a battery material precursor; evaporating and crystallizing the lithium hydroxide solution to obtain lithium hydroxide solid; d) And mixing the lithium hydroxide solid with a battery material precursor, and sintering to obtain the lithium battery anode material. According to the technical scheme, lithium and other metals can be separated and recycled, so that high lithium recovery rate is obtained, high-valued comprehensive recycling of all valuable metal ions is realized, and the overall acid consumption is reduced.
Description
Technical Field
The invention relates to the technical field of waste lithium batteries, in particular to a method for recycling waste lithium batteries.
Background
The recovery of waste lithium batteries becomes an important problem to be solved urgently. If the waste lithium batteries are improperly disposed, potential safety hazards such as electric shock, explosion, corrosion and the like exist, and under the conditions of special temperature, humidity and poor contact, spontaneous combustion or explosion can be even caused, for example, safety accidents such as fire of recent electric automobile power batteries frequently occur; the waste lithium battery is rich in a large amount of valuable metals such as lithium, nickel, cobalt and the like, is a famous and practical urban mine, and is an important solution for solving the problems that the valuable metals such as nickel, cobalt, lithium and the like in China are large in demand, difficult to mine and depend on importation to a great extent; in addition, if heavy metals, electrolyte and the like contained in the waste lithium batteries cannot be effectively recovered, the natural environments such as soil, rivers and the like can be damaged. Therefore, the development of green recovery of the waste lithium batteries has important economic and social values, and plays a vital role in reducing environmental pollution and promoting sustainable development of industries.
At present, the domestic waste lithium battery recovery process mainly adopts wet recovery. The method comprises the steps of adding sulfuric acid solution into waste lithium battery materials to leach to obtain valuable metal solutions containing lithium, nickel, cobalt and the like, then obtaining salt solutions of different metals through a multistage extraction process, obtaining corresponding metal salt products through evaporation and crystallization of the metal salt solutions containing nickel, cobalt and the like, finally adding sodium carbonate into the lithium solution to perform lithium precipitation reaction to obtain lithium carbonate products, and selling the lithium carbonate products and the metal salt products to a precursor manufacturer and a positive electrode material manufacturer for production.
The defects of the recovery process include:
the existing waste lithium battery recycling process is to separate and recycle metals such as lithium, nickel and cobalt to obtain different products, and then sell the different products to a precursor manufacturer and a positive electrode material manufacturer respectively, so that the resource recycling process is long;
lithium recovery is typically carried out at the end of the overall process flow, with low lithium recovery and the product produced is typically lithium carbonate;
at present, the waste lithium battery recovery process is acid leaching treatment firstly, and the subsequent process needs to neutralize acid, so that the consumption of sulfuric acid is large as a whole;
according to the change of the market demand for high specific capacity materials, the market share of the current high-nickel positive electrode materials is gradually increased, lithium hydroxide is needed in the production of the high-nickel positive electrode materials, most of lithium salt products recovered from the current waste lithium batteries are only lithium carbonate, and lithium hydroxide products cannot be directly provided.
CN 111867980a discloses a method for preparing solid metal hydroxide and liquid containing lithium sulfate by reacting metal sulfate containing nickel, cobalt, lithium and the like with chelating agent, then preparing lithium hydroxide from the liquid containing lithium sulfate by adopting two-chamber monopolar or bipolar membrane electrolysis process, wherein electrodialysis raw material is single lithium sulfate solution, various chemical and chemical reagents are required to be consumed for producing nickel cobalt manganese hydroxide, the consumption is large, the production cost is high, and the process flow is long.
Disclosure of Invention
In view of the above, the technical problem to be solved by the invention is to provide a method for recycling waste lithium batteries, which realizes the effective and comprehensive utilization of waste lithium battery materials.
The invention also provides a method for recycling the waste lithium battery, which comprises the following steps:
a) Reacting the waste lithium battery material with acid liquor, and filtering to obtain leaching liquid;
b) Carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain impurity removal liquid;
c) Performing bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution;
preparing the salt solution according to the element proportion, and reacting the prepared salt solution, alkali liquor and a first auxiliary agent to obtain a battery material precursor;
evaporating and crystallizing the lithium hydroxide solution to obtain lithium hydroxide solid;
d) And mixing the lithium hydroxide solid with a battery material precursor, and sintering to obtain the lithium battery anode material.
Preferably, in the step a), the waste lithium battery material is a waste lithium iron phosphate battery material;
the acid liquor comprises sulfuric acid and phosphoric acid, and the concentration of the acid liquor is 0.1-4 mol/L.
Preferably, in the step a), the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, and the raw materials for the reaction further comprise a second auxiliary agent;
the second auxiliary agent comprises one or more of hydrogen peroxide and sodium thiosulfate;
the acid liquor is sulfuric acid, and the concentration of the acid liquor is 0.1-4 mol/L.
Preferably, in the step A), the temperature of the reaction is 15-50 ℃ and the time is 30-180 min.
Preferably, when the waste lithium battery material is a waste lithium iron phosphate material, in step B):
the chemical impurity removal includes:
mixing the leaching solution, iron powder and a pH regulator, and then reacting;
the pH value of the mixed solution after mixing is 2.8-5.0; in the mixing of the leaching solution and the iron powder, the excess coefficient of the iron powder is 10% -100%; the pH regulator comprises ammonium carbonate and/or urea; the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min;
the resin adopted by the resin adsorption is phosphoramidate chelate resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃.
Preferably, when the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, in step B):
the chemical impurity removal includes:
mixing the leaching solution, iron powder and a pH regulator, and then reacting;
the pH value of the mixed solution after mixing is 3.5-5.5; in the mixing of the leaching solution and the iron powder, the excess coefficient of the iron powder is 10% -100%; the pH regulator comprises one or more of lithium carbonate, ammonium carbonate and lithium hydroxide; the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min;
the resin adopted by the resin adsorption is phosphoramidate chelate resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃.
Preferably, in step C), the bipolar membrane electrodialysis device comprises a bipolar membrane, an anion exchange membrane and a monovalent cation exchange membrane, which form a salt compartment, an acid compartment and an alkali compartment; the anion exchange membrane and monovalent cation exchange membrane group pairs; the impurity removing solution is subjected to bipolar membrane electrodialysis in a three-chamber bipolar membrane electrodialysis device, and finally lithium hydroxide solution is output from an alkali chamber, salt solution is output from a salt chamber, and acid solution is output from an acid chamber;
the conductive liquid entering the acid chamber is sulfuric acid solution; the mass concentration of the sulfuric acid solution is 0.01% -5%;
the conductive liquid entering the alkali chamber is lithium hydroxide solution; the mass concentration of the lithium hydroxide solution is 0.01% -5%;
the current of the bipolar membrane electrodialysis is less than 4.5A;
the acid solution output from the acid chamber is reused in the step A).
Preferably, the waste lithium battery material is a waste lithium iron phosphate battery material, and in the step C), the mole ratio of P to Fe in the prepared salt solution is 0.95-3.0: 1.
preferably, in the step C), the alkali solution includes one or more of ammonia water, sodium carbonate solution and sodium bicarbonate solution, the first auxiliary agent is hydrogen peroxide solution, the reaction temperature of the prepared salt solution, alkali solution and first auxiliary agent is 35-90 ℃, and the reaction pH value is 1.7-2.9, so as to obtain the ferric phosphate precursor.
Preferably, the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, and in the step C), the mole ratio of Ni, co and Mn in the prepared salt solution is 5:2: 3. 6:2:2 or 8:1:1.
preferably, in the step C), the alkali solution includes one or more of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution, the first auxiliary agent is ammonia water solution, the reaction temperature of the prepared salt solution, alkali solution and first auxiliary agent is 45-80 ℃, and the reaction pH value is 10-13, so as to obtain the ternary nickel-cobalt-manganese precursor.
Preferably, in the step D), after mixing the lithium hydroxide solid and the battery material precursor, ball milling is further included;
the ball milling time is 2-6 hours;
the sintering temperature is 600-900 ℃ and the sintering time is 4-12 h.
The invention provides a method for recycling waste lithium batteries, which comprises the following steps: a) Reacting the waste lithium battery material with acid liquor, and filtering to obtain leaching liquid; b) Carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain impurity removal liquid; c) Performing bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution; preparing the salt solution according to the element proportion, and reacting the prepared salt solution, alkali liquor and a first auxiliary agent to obtain a battery material precursor; evaporating and crystallizing the lithium hydroxide solution to obtain lithium hydroxide solid; d) And mixing the lithium hydroxide solid with a battery material precursor, and sintering to obtain the lithium battery anode material. According to the technical scheme provided by the invention, lithium and other valuable metal ions can be separated to directly obtain a pure lithium hydroxide solution and other valuable metal ion solutions without lithium, the recovery rate of lithium is high, and lithium hydroxide can be produced in one step; the high-valued comprehensive recycling of all valuable metal ions is realized, and the byproduct acid liquor of electrodialysis can be directly recycled to a leaching working section, so that the overall acid consumption is reduced; meanwhile, the recovered metal salt solution is used for synthesizing a precursor, and then the recovered lithium hydroxide and the precursor material are mixed and sintered to obtain a newly synthesized positive electrode material, so that a final product is the newly synthesized positive electrode material, the resource circulation flow is greatly shortened, and the social resource waste is avoided.
Drawings
FIG. 1 is a schematic diagram of bipolar membrane electrodialysis of a removing solution obtained by using a waste lithium iron phosphate material as a waste lithium battery material;
FIG. 2 is a schematic diagram of bipolar membrane electrodialysis of a solution obtained by using a waste nickel-cobalt-manganese ternary battery material as a waste lithium battery material;
fig. 3 is a process flow diagram of recycling waste lithium batteries according to an embodiment of the present invention;
FIG. 4 is an XRD pattern of a ternary nickel cobalt manganese precursor according to example 1 of the present invention;
FIG. 5 is an XRD pattern of the positive electrode material of the lithium battery in example 1 of the present invention;
FIG. 6 is an XRD pattern of an iron phosphate precursor according to example 3 of the present invention;
fig. 7 is an XRD pattern of the positive electrode material of the lithium battery in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a method for recycling waste lithium batteries, which comprises the following steps:
a) Reacting the waste lithium battery material with acid liquor, and filtering to obtain leaching liquid;
b) Carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain impurity removal liquid;
c) Performing bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution;
preparing the salt solution according to the element proportion, and reacting the prepared salt solution, alkali liquor and a first auxiliary agent to obtain a battery material precursor;
evaporating and crystallizing the lithium hydroxide solution to obtain lithium hydroxide solid;
d) And mixing the lithium hydroxide solid with a battery material precursor, and sintering to obtain the lithium battery anode material.
The method comprises the steps of reacting waste lithium battery materials with acid liquor, and filtering to obtain leaching liquid and solid slag.
In certain embodiments of the invention, the spent lithium battery material is spent lithium iron phosphate battery material or spent nickel cobalt manganese ternary battery material.
In certain embodiments of the invention, the spent lithium battery material is spent lithium iron phosphate battery material.
Specifically, the method comprises the following steps:
and (3) reacting the lithium iron phosphate battery material with acid liquor, and filtering to obtain leaching liquid and solid slag.
In certain embodiments of the present invention, the acid solution comprises sulfuric acid and phosphoric acid, and the acid solution has a concentration of 0.1 to 4mol/L. In certain embodiments, the acid solution is at a concentration of 1mol/L or 3mol/L.
In certain embodiments of the present invention, the mass ratio of the lithium iron phosphate battery material to the acid solution is 1:1 to 5. In certain embodiments, the mass ratio of the lithium iron phosphate battery material to the acid solution is 1:3 or 1:2.
in certain embodiments of the invention, the reaction is carried out at a temperature of 15 to 50℃for a period of 30 to 180 minutes. In certain embodiments, the temperature of the reaction is 30 ℃ or 50 ℃. In certain embodiments, the time of the reaction is 90 minutes or 120 minutes.
The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
In some embodiments of the present invention, the waste lithium battery material is a waste nickel cobalt manganese ternary battery material, and the raw materials for the reaction further include a second auxiliary agent.
Specifically, the method comprises the following steps:
and (3) reacting the nickel-cobalt-manganese ternary battery material, the acid liquor and the second auxiliary agent, and filtering to obtain leaching liquid and solid slag.
In certain embodiments of the present invention, the acid solution is sulfuric acid, and the concentration of the acid solution is 0.1 to 4mol/L. In certain embodiments, the acid solution is at a concentration of 1mol/L or 2mol/L.
In certain embodiments of the present invention, the mass ratio of the nickel-cobalt-manganese ternary battery material to the acid solution is 1:1 to 3. In certain embodiments, the mass ratio of the nickel-cobalt-manganese ternary battery material to the acid solution is 1:1 or 1:2.
in some embodiments of the present invention, the second auxiliary agent includes one or more of hydrogen peroxide and sodium thiosulfate.
In certain embodiments of the present invention, the mass ratio of the nickel-cobalt-manganese ternary battery material to the second auxiliary agent is 1:0.1 to 2. In certain embodiments, the mass ratio of the nickel-cobalt-manganese ternary battery material to the second auxiliary agent is 1:0.5 or 1:1.
in certain embodiments of the invention, the reaction is carried out at a temperature of 15 to 50℃for a period of 30 to 120 minutes. In certain embodiments, the temperature of the reaction is 20 ℃ or 40 ℃. In certain embodiments, the reaction time is 60 minutes or 80 minutes.
The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
After the leaching solution is obtained, the leaching solution is subjected to chemical impurity removal and resin adsorption to obtain impurity removal liquid and impurity removal slag.
When the waste lithium battery material is a waste lithium iron phosphate material:
in certain embodiments of the invention, the chemical decontamination comprises:
and mixing the leaching solution, the iron powder and the pH regulator, and then carrying out reaction.
In certain embodiments of the invention, the pH of the mixed liquor after mixing is from 2.8 to 5.0. In certain embodiments, the pH of the mixed liquor after mixing is 3.0.
In certain embodiments of the invention, the iron powder has an excess factor of 10% to 100% in the mixing of the leachate and the iron powder. In certain embodiments, the iron powder has a coefficient of excess of 30% or 60% in the blending of the leachate and the iron powder.
In certain embodiments of the invention, the pH adjuster comprises ammonium carbonate and/or urea.
In certain embodiments of the invention, the reaction is carried out at a temperature of 25 to 60℃for a period of 30 to 180 minutes. In certain embodiments, the temperature of the reaction is 40 ℃ or 50 ℃. In certain embodiments, the time of the reaction is 90 minutes or 120 minutes.
In some embodiments of the present invention, after the chemical impurity removal, the method further comprises: and (5) filtering. The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
In certain embodiments of the present invention, the resin employed for the resin adsorption is a phosphoramidate chelate resin, which may be commercially available in general.
In certain embodiments of the invention, the resin adsorption rate is 2-6 BV. In certain embodiments, the resin adsorption rate is 2BV or 4BV.
In certain embodiments of the invention, the temperature of resin adsorption is 15-50 ℃. In certain embodiments, the temperature of the resin adsorption is 45 ℃ or 25 ℃.
When the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material:
in certain embodiments of the invention, the chemical decontamination comprises:
and mixing the leaching solution, the iron powder and the pH regulator, and then carrying out reaction.
In certain embodiments of the invention, the pH of the mixed liquor after mixing is from 3.5 to 5.5. In certain embodiments, the pH of the mixed liquor after mixing is 4.0.
In certain embodiments of the invention, the iron powder has an excess factor of 10% to 100% in the mixing of the leachate and the iron powder. In certain embodiments, the iron powder has a coefficient of excess of 20% in the blending of the leachate and the iron powder.
In certain embodiments of the present invention, the pH adjuster comprises one or more of lithium carbonate, ammonium carbonate, and lithium hydroxide.
In certain embodiments of the invention, the reaction is carried out at a temperature of 25 to 60℃for a period of 30 to 180 minutes. In certain embodiments, the temperature of the reaction is 35 ℃ or 40 ℃. In certain embodiments, the time of the reaction is 60 minutes or 120 minutes.
In some embodiments of the present invention, after the chemical impurity removal, the method further comprises: and (5) filtering. The method of the filtration is not particularly limited, and filtration methods well known to those skilled in the art may be employed.
In certain embodiments of the present invention, the resin employed for the resin adsorption is a phosphoramidate chelate resin, which may be commercially available in general.
In certain embodiments of the invention, the resin adsorption rate is 2-6 BV. In certain embodiments, the resin adsorption rate is 3BV or 6BV.
In certain embodiments of the invention, the temperature of resin adsorption is 15-50 ℃. In certain embodiments, the temperature of the resin adsorption is 30 ℃ or 40 ℃.
And (3) after the impurity removing liquid is obtained, carrying out bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution.
In certain embodiments of the invention, the bipolar membrane electrodialysis device is a three-compartment bipolar membrane electrodialysis device. Specifically, the bipolar membrane, the anion exchange membrane and the monovalent cation exchange membrane form a salt chamber, an acid chamber and an alkali chamber; the anion exchange membrane and monovalent cation exchange membrane group pairs. And the impurity removing liquid enters a salt chamber in the three-chamber bipolar membrane electrodialysis device to carry out bipolar membrane electrodialysis, and finally, lithium hydroxide solution is output from an alkali chamber, salt solution is output from the salt chamber, and acid solution is output from an acid chamber.
In certain embodiments of the invention, the bipolar membrane, anion exchange membrane, and monovalent cation exchange membrane are arranged as shown in fig. 1 and 2. Fig. 1 is a schematic diagram of a principle of bipolar membrane electrodialysis by using a impurity removing solution obtained by using a waste lithium iron phosphate material as a waste lithium battery material, and fig. 2 is a schematic diagram of a principle of bipolar membrane electrodialysis by using a impurity removing solution obtained by using a waste nickel cobalt manganese ternary battery material as a waste lithium battery material. Wherein the BP membrane is a bipolar membrane, the A membrane is an anion exchange membrane, the C membrane is a monovalent cation exchange membrane, the conductive liquid A is the conductive liquid entering the acid chamber, and the conductive liquid B is the conductive liquid entering the alkali chamber.
The materials of the bipolar membrane, the anion exchange membrane and the monovalent cation exchange membrane are not particularly limited, and materials of the bipolar membrane, the anion exchange membrane and the monovalent cation exchange membrane, which are well known to those skilled in the art, may be used.
In certain embodiments of the invention, the conductive liquid entering the acid chamber is a sulfuric acid solution; the mass concentration of the sulfuric acid solution is 0.01% -5%. In certain embodiments, the sulfuric acid solution has a mass concentration of 0.05%, 1.0%, or 1.1%.
In certain embodiments of the invention, the conductive liquid entering the alkaline chamber is a lithium hydroxide solution; the mass concentration of the lithium hydroxide solution is 0.01% -5%. In certain embodiments, the lithium hydroxide solution has a mass concentration of 0.05%, 1.0%, or 1.1%.
In certain embodiments of the invention, the current of bipolar membrane electrodialysis is less than 4.5A. In certain embodiments, the bipolar membrane electrodialysis current is 4.0A, 3.5A, 3.8A, or 3.0A.
In certain embodiments of the invention, the acid solution output from the acid chamber is recycled for use in step a).
According to the invention, the salt solution is prepared according to the element proportion, and the prepared salt solution, alkali liquor and first auxiliary agent react to obtain the battery material precursor.
In certain embodiments of the present invention, when the spent lithium battery material is spent lithium iron phosphate battery material:
in the prepared salt solution, the molar ratio of P to Fe is 0.95-3.0: 1, a step of; in certain embodiments, the molar ratio of P to Fe in the formulated salt solution is 1:1 or 3:1, a step of;
the alkali liquor comprises one or more of ammonia water, sodium carbonate solution and sodium bicarbonate solution; the mass concentration of the alkali liquor is 1-30%;
the first auxiliary agent is hydrogen peroxide solution; the mass concentration of the hydrogen peroxide solution is 1% -30%;
the mass ratio of the prepared salt solution to the first auxiliary agent is 10-12: 1 to 3; in certain embodiments, the mass ratio of the formulated salt solution to the first adjuvant is 10:1 or 11:2;
the temperature of the prepared salt solution, alkali liquor and first auxiliary agent is 35-90 ℃, the pH value of the reaction is 1.7-2.9, and the time is 0.5-5 h; in certain embodiments, the temperature of the reaction is 50 ℃ or 80 ℃; in certain embodiments, the pH of the reaction is 2.0 or 2.7; in certain embodiments, the time of the reaction is 1h or 2h;
after the reaction, filtering, washing and drying are further included; the method of the present invention is not particularly limited, and filtration, washing and drying methods well known to those skilled in the art may be employed;
the obtained battery material precursor is an iron phosphate precursor.
In some embodiments of the present invention, when the waste lithium battery material is a waste nickel cobalt manganese ternary battery material:
in the prepared salt solution, the mole ratio of Ni, co and Mn is 5-9: 0.5 to 2:0.5 to 3. In certain embodiments, the molar ratio of Ni, co, and Mn in the formulated salt solution is 5:2: 3. 6:2:2 or 8:1:1.
the alkali liquor comprises one or more of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution; the mass concentration of the alkali liquor is 5% -30%;
the first auxiliary agent is an ammonia water solution; the mass concentration of the ammonia water solution is 5% -30%;
the mass ratio of the prepared salt solution to the first auxiliary agent is 9-12: 0.8 to 1.2; in certain embodiments, the mass ratio of the formulated salt solution to the first adjuvant is 10:1 or 11:0.9;
the temperature of the mixed salt solution, alkali liquor and first auxiliary agent is 45-80 ℃, the pH value of the reaction is 10-13, and the time is 10-100 h; in certain embodiments, the temperature of the reaction is 50 ℃ or 60 ℃; in certain embodiments, the pH of the reaction is 11.5 or 10.5; in certain embodiments, the time of the reaction is 80 hours or 60 hours;
after the reaction, filtering, washing and drying are further included; the method of the present invention is not particularly limited, and filtration, washing and drying methods well known to those skilled in the art may be employed;
the obtained battery material precursor is a ternary nickel-cobalt-manganese precursor.
In the invention, lithium hydroxide solution output from an alkali chamber of a three-chamber bipolar membrane electrodialysis device is subjected to evaporation crystallization to obtain lithium hydroxide solid. The method of the present invention is not particularly limited, and the method of the present invention is known to those skilled in the art.
In certain embodiments of the invention, drying is also included after the evaporative crystallization. The method and parameters of the drying are not particularly limited, and those known to those skilled in the art may be used.
And after the battery material precursor and the lithium hydroxide solid are obtained, mixing the lithium hydroxide solid and the battery material precursor, and sintering to obtain the lithium battery anode material.
In certain embodiments of the invention, the lithium hydroxide solids and battery material precursor are mixed with a coefficient of excess of 2% to 10% of the lithium hydroxide solids. In certain embodiments, the lithium hydroxide solids and battery material precursor are mixed with a coefficient of excess of 5%, 8%, 3%, or 10% of the lithium hydroxide solids.
In certain embodiments of the invention, ball milling is also included after mixing the lithium hydroxide solids and the battery material precursor.
In certain embodiments of the invention, the ball milling time is 2 to 6 hours. In certain embodiments, the ball milling time is 3 hours, 5 hours, 6 hours, or 4 hours.
In certain embodiments of the invention, the sintering is performed at a temperature of 600 to 900 ℃ for a time of 4 to 12 hours. In certain embodiments, the sintering temperature is 700 ℃,900 ℃,600 ℃, or 800 ℃. In certain embodiments, the sintering time is 10h, 6h, 8h, or 12h.
In certain embodiments of the present invention, when the spent lithium battery material is spent lithium iron phosphate material, the sintering is performed under an argon atmosphere or a nitrogen atmosphere.
In certain embodiments of the present invention, the sintering is performed in an oxygen atmosphere when the spent lithium battery material is a spent nickel cobalt manganese ternary battery material.
The source of the raw materials used in the present invention is not particularly limited, and may be generally commercially available.
Fig. 3 is a process flow diagram of recycling waste lithium batteries according to an embodiment of the present invention.
According to the technical scheme provided by the invention, lithium and other valuable metal ions can be separated to directly obtain a pure lithium hydroxide solution and other valuable metal ion solutions without lithium, the recovery rate of lithium is high, and lithium hydroxide can be produced in one step; the high-valued comprehensive recycling of all valuable metal ions is realized, and the byproduct acid liquor of electrodialysis can be directly recycled to a leaching working section, so that the overall acid consumption is reduced; meanwhile, the recovered metal salt solution is used for synthesizing a precursor, and then the recovered lithium hydroxide and the precursor material are mixed and sintered to obtain a newly synthesized positive electrode material, so that a final product is the newly synthesized positive electrode material, the resource circulation flow is greatly shortened, and the social resource waste is avoided.
In order to further illustrate the present invention, the following examples are provided to describe a method for recycling waste lithium batteries in detail, but the method should not be construed as limiting the scope of the present invention.
The raw materials used in the following examples are all generally commercially available.
Example 1
The method for recycling the waste lithium batteries comprises the following steps:
1) Waste nickel-cobalt-manganese ternary lithium battery material, 1mol/L sulfuric acid and hydrogen peroxide are mixed according to the mass ratio of 1:1:0.5 is added into a reaction kettle, reacted for 60min at 20 ℃, and filtered to obtain leaching liquid and solid slag, wherein the leaching rate of lithium is 98.5%;
2) Adding iron powder with an excess coefficient of 20% into the leaching solution obtained in the step 1), adding lithium carbonate to adjust the pH of the solution to 4.0, reacting for 60min at 35 ℃, filtering, and then allowing the filtrate at 30 ℃ to pass through a resin adsorption column (the resin is amino-phosphoric acid type chelate resin) at a flow rate of 3BV to obtain impurity-removing liquid;
3) Introducing the impurity-removed liquid obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conductive liquid entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is sulfuric acid solution with the mass concentration of 0.05%, the conductive liquid entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is lithium hydroxide solution with the mass concentration of 0.05%, and finally outputting lithium hydroxide solution from the alkali chamber, valuable metal salt solution from the salt chamber and acid solution from the acid chamber under the action of 4.0A current;
4) Recycling the acid solution output by the electrodialysis acid chamber to the step 1) for leaching;
5) Elemental preparation is carried out on the salt solution output by the salt chamber in the step 3), and the mole ratio of Ni, co and Mn in the prepared salt solution is 8:1:1, adding the prepared salt solution, sodium hydroxide solution (the mass concentration is 5%) and ammonia water solution (the mass concentration is 10%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the ammonia water solution is 10:1, controlling the pH value to be 11.5 at 50 ℃ for reaction for 80 hours, and obtaining a ternary nickel-cobalt-manganese precursor after filtering, washing and drying;
6) Evaporating and crystallizing the lithium hydroxide solution output from the alkali chamber in the step 3), and drying to obtain lithium hydroxide solid;
7) Mixing the lithium hydroxide solid obtained in the step 6) with the ternary nickel-cobalt-manganese precursor obtained in the step 5) according to the excess coefficient of 5%, ball milling for 3h, and sintering at 700 ℃ for 10h in an oxygen atmosphere to obtain the lithium battery anode material.
In this example, the obtained ternary nickel cobalt manganese precursor was analyzed by using an X-ray diffractometer to obtain an XRD pattern of the ternary nickel cobalt manganese precursor in example 1 of the present invention, as shown in fig. 4. Fig. 4 is an XRD pattern of a ternary nickel cobalt manganese precursor in example 1 of the present invention. As can be seen from fig. 4, the synthesized ternary precursor is the NCM811 structure.
In this example, the obtained positive electrode material for lithium battery was also analyzed by using an X-ray diffractometer to obtain an XRD pattern of the positive electrode material for lithium battery in example 1 of the present invention, as shown in fig. 5. Fig. 5 is an XRD pattern of the positive electrode material of the lithium battery in example 1 of the present invention. As can be seen from fig. 5, the resulting cathode material has a 811 ternary cathode material structure.
Example 2
The method for recycling the waste lithium batteries comprises the following steps:
1) Waste nickel-cobalt-manganese ternary lithium battery material, 2mol/L sulfuric acid and sodium thiosulfate are mixed according to the mass ratio of 1:2:1, adding the mixture into a reaction kettle, reacting for 80 minutes at 40 ℃, and filtering to obtain leaching liquid and solid slag, wherein the leaching rate of lithium is 99.6%;
2) Adding iron powder with the excess coefficient of 50% into the leaching solution obtained in the step 1), then adding lithium hydroxide to adjust the pH of the solution to 5.0, reacting for 120min at 40 ℃, filtering, and then allowing the filtrate at 40 ℃ to pass through a resin adsorption column (the resin is amino-phosphoric acid type chelate resin) at the flow rate of 6BV to obtain impurity-removing liquid;
3) Introducing the impurity-removed liquid obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conductive liquid entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is sulfuric acid solution with the mass concentration of 1.0%, the conductive liquid entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is lithium hydroxide solution with the mass concentration of 1.0%, and finally outputting lithium hydroxide solution from the alkali chamber, outputting valuable metal salt solution from the salt chamber and outputting acid solution from the acid chamber under the action of 3.5A current;
4) Recycling the acid solution output by the electrodialysis acid chamber to the step 1) for leaching;
5) Elemental preparation is carried out on the salt solution output by the salt chamber in the step 3), and the mole ratio of Ni, co and Mn in the prepared salt solution is 8:1:1, adding the prepared salt solution, sodium hydroxide solution (the mass concentration is 10%) and ammonia water solution (the mass concentration is 25%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the ammonia water solution is 11:0.9, controlling the pH value to be 10.5 at 60 ℃ for 60 hours, and obtaining a ternary nickel-cobalt-manganese precursor after filtering, washing and drying;
6) Evaporating and crystallizing the lithium hydroxide solution output from the alkali chamber in the step 3), and drying to obtain lithium hydroxide solid;
7) Mixing the lithium hydroxide solid obtained in the step 6) with the ternary nickel-cobalt-manganese precursor obtained in the step 5) according to the excess coefficient of 8%, ball milling for 5h, and sintering at 900 ℃ for 6h in an oxygen atmosphere to obtain the lithium battery anode material.
Example 3
The method for recycling the waste lithium batteries comprises the following steps:
1) Waste lithium iron phosphate battery materials and 1mol/L sulfuric acid are mixed according to the mass ratio of 1:3, adding the mixture into a reaction kettle, reacting for 90min at 30 ℃, and filtering to obtain leaching liquid and solid slag, wherein the leaching rate of lithium is 99.5%;
2) Adding iron powder with the excess coefficient of 30% into the leaching solution obtained in the step 1), adding ammonium carbonate to adjust the pH of the solution to 3.0, reacting for 90min at 40 ℃, filtering, and then allowing the filtrate at 25 ℃ to pass through a resin adsorption column (the resin is amino-phosphoric acid type chelate resin) at the flow rate of 2BV to obtain impurity-removing liquid;
3) Introducing the impurity-removed liquid obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conductive liquid entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is sulfuric acid solution with the mass concentration of 0.05%, the conductive liquid entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is lithium hydroxide solution with the mass concentration of 0.05%, and finally outputting lithium hydroxide solution from the alkali chamber, outputting valuable metal salt solution from the salt chamber and outputting acid solution from the acid chamber under the action of 3.8A current;
4) Recycling the acid solution output by the electrodialysis acid chamber to the step 1) for leaching;
5) Elemental preparation is carried out on the salt solution output by the salt chamber in the step 3), and the mole ratio of P to Fe in the prepared salt solution is 1:1, adding the prepared salt solution, ammonia water solution (with the mass concentration of 5%) and hydrogen peroxide solution (with the mass concentration of 5%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the hydrogen peroxide solution is 10:1, adding the mixture into a synthesis reaction kettle, controlling the pH value to be 2.0 at 50 ℃ for reaction for 1h, and obtaining an iron phosphate precursor after filtering, washing and drying;
6) Evaporating and crystallizing the lithium hydroxide solution output from the alkali chamber in the step 3), and drying to obtain lithium hydroxide solid;
7) Mixing the lithium hydroxide solid obtained in the step 6) with the ferric phosphate precursor obtained in the step 5) according to the excess coefficient of 3%, ball-milling for 6 hours, and sintering at 600 ℃ for 8 hours in a nitrogen atmosphere to obtain the lithium battery anode material.
This example uses an X-ray diffractometer to analyze the resulting iron phosphate precursor to obtain the XRD pattern of the iron phosphate precursor in example 3 of the present invention, as shown in fig. 6. Fig. 6 is an XRD pattern of the iron phosphate precursor in example 3 of the present invention. As can be seen from the XRD pattern, the synthesized precursor is iron phosphate.
The obtained positive electrode material of the lithium battery in this example was also analyzed by an X-ray diffractometer to obtain an XRD pattern of the positive electrode material of the lithium battery in example 3 of the present invention, as shown in fig. 7. Fig. 7 is an XRD pattern of the positive electrode material of the lithium battery in example 3 of the present invention. As can be seen from the XRD pattern, the synthesized material is a lithium iron phosphate positive electrode material.
Example 4
The method for recycling the waste lithium batteries comprises the following steps:
1) The method comprises the steps of mixing waste lithium iron phosphate battery materials with 3mol/L sulfuric acid according to a mass ratio of 1:2, adding the mixture into a reaction kettle, reacting for 120min at 50 ℃, and filtering to obtain leaching liquid and solid slag, wherein the leaching rate of lithium is 99.9%;
2) Adding iron powder with an excess coefficient of 60% into the leaching solution obtained in the step 1), adding urea to adjust the pH of the solution to 4.5, reacting for 120min at 50 ℃, filtering, and then allowing the filtrate at 45 ℃ to pass through a resin adsorption column at a flow rate of 4BV to obtain impurity-removing liquid;
3) Introducing the impurity-removed liquid obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conductive liquid entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is sulfuric acid solution with the mass concentration of 1.1%, the conductive liquid entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is lithium hydroxide solution with the mass concentration of 1.1%, and finally outputting lithium hydroxide solution from the alkali chamber, outputting valuable metal salt solution from the salt chamber and outputting acid solution from the acid chamber under the action of 3.0A current;
4) Recycling the acid solution output by the electrodialysis acid chamber to the step 1) for leaching;
5) Elemental preparation is carried out on the salt solution output by the salt chamber in the step 3), and the mole ratio of P to Fe in the prepared salt solution is 3:1, adding the prepared salt solution, sodium carbonate solution (with the mass concentration of 10%) and hydrogen peroxide solution (with the mass concentration of 15%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the hydrogen peroxide solution is 11:2, adding the mixture into a synthesis reaction kettle, controlling the pH value to be 2.7 at 80 ℃ for 2 hours, and obtaining an iron phosphate precursor after filtering, washing and drying;
6) Evaporating and crystallizing the lithium hydroxide solution output from the alkali chamber in the step 3), and drying to obtain lithium hydroxide solid;
7) Mixing the lithium hydroxide solid obtained in the step 6) with the ferric phosphate precursor obtained in the step 5) according to the excess coefficient of 10%, ball-milling for 4 hours, and sintering at 800 ℃ for 12 hours in a nitrogen atmosphere to obtain the lithium battery anode material.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (12)
1. A method for recycling waste lithium batteries comprises the following steps:
a) Reacting the lithium iron phosphate battery material with acid liquor, and filtering to obtain leaching liquid and solid slag;
b) Carrying out chemical impurity removal, filtration and resin adsorption on the leaching solution to obtain impurity removal liquid;
the chemical impurity removal is as follows:
mixing the leaching solution, iron powder and a pH regulator, and then reacting;
the pH value of the mixed solution after mixing is 2.8-5.0; in the mixing of the leaching solution and the iron powder, the excess coefficient of the iron powder is 10% -100%; the pH regulator comprises ammonium carbonate and/or urea;
the resin adopted by the resin adsorption is phosphoramidate chelate resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃;
c) Performing bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution;
preparing the salt solution according to the element proportion, reacting the prepared salt solution, alkali liquor and a first auxiliary agent, and then filtering, washing and drying to obtain an iron phosphate precursor; in the prepared salt solution, the molar ratio of P to Fe is 0.95-3.0: 1, a step of; the alkali liquor comprises one or more of ammonia water, sodium carbonate solution and sodium bicarbonate solution; the first auxiliary agent is hydrogen peroxide solution;
evaporating and crystallizing the lithium hydroxide solution, and drying to obtain lithium hydroxide solid;
recycling the acid solution output by the acid chamber of the bipolar membrane electrodialysis device into the step A);
d) And mixing the lithium hydroxide solid with the ferric phosphate precursor, performing ball milling, and sintering to obtain the lithium battery anode material.
2. A method for recycling waste lithium batteries comprises the following steps:
a) Reacting the nickel-cobalt-manganese ternary battery material, the acid liquor and the second auxiliary agent, and filtering to obtain leaching liquid and solid slag;
b) Carrying out chemical impurity removal, filtration and resin adsorption on the leaching solution to obtain impurity removal liquid;
the chemical impurity removal is as follows:
mixing the leaching solution, iron powder and a pH regulator, and then reacting;
the pH value of the mixed solution after mixing is 3.5-5.5; in the mixing of the leaching solution and the iron powder, the excess coefficient of the iron powder is 10% -100%; the pH regulator comprises one or more of lithium carbonate, ammonium carbonate and lithium hydroxide;
the resin adopted by the resin adsorption is phosphoramidate chelate resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃;
c) Performing bipolar membrane electrodialysis on the impurity removing liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution;
preparing the salt solution according to the element proportion, reacting the prepared salt solution, alkali liquor and a first auxiliary agent, and then filtering, washing and drying to obtain a ternary nickel-cobalt-manganese precursor; in the prepared salt solution, the mole ratio of Ni, co and Mn is 5-9: 0.5 to 2:0.5 to 3; the alkali liquor comprises one or more of sodium hydroxide solution, sodium carbonate solution and sodium bicarbonate solution, and the first auxiliary agent is ammonia water solution;
evaporating and crystallizing the lithium hydroxide solution, and drying to obtain lithium hydroxide solid;
recycling the acid solution output by the acid chamber of the bipolar membrane electrodialysis device into the step A);
d) And mixing the lithium hydroxide solid with the ternary nickel cobalt manganese precursor, ball milling, and sintering to obtain the lithium battery anode material.
3. The method according to claim 1, wherein in the step a), when the waste lithium battery material is a waste lithium iron phosphate battery material, the acid solution comprises sulfuric acid and phosphoric acid, and the concentration of the acid solution is 0.1-4 mol/L.
4. The method according to claim 2, wherein in the step a), when the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, the acid solution is sulfuric acid, and the concentration of the acid solution is 0.1-4 mol/L;
the second auxiliary agent comprises one or more of hydrogen peroxide and sodium thiosulfate.
5. The process according to claim 1 or 2, wherein in step a) the reaction is carried out at a temperature of 15 to 50 ℃ for a time of 30 to 180min.
6. The method according to claim 1, wherein in step B):
the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min.
7. The method according to claim 2, characterized in that in step B):
the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min.
8. The method according to claim 1 or 2, characterized in that in step C) the bipolar membrane electrodialysis device comprises bipolar membranes, anion exchange membranes and monovalent cation exchange membranes, constituting a salt compartment, an acid compartment and a base compartment; the anion exchange membrane and monovalent cation exchange membrane group pairs; the impurity removing solution is subjected to bipolar membrane electrodialysis in a three-chamber bipolar membrane electrodialysis device, and finally lithium hydroxide solution is output from an alkali chamber, salt solution is output from a salt chamber, and acid solution is output from an acid chamber;
the conductive liquid entering the acid chamber is sulfuric acid solution; the mass concentration of the sulfuric acid solution is 0.01% -5%;
the conductive liquid entering the alkali chamber is lithium hydroxide solution; the mass concentration of the lithium hydroxide solution is 0.01% -5%;
the bipolar membrane electrodialysis current is less than 4.5A.
9. The method according to claim 1, wherein in step C), the temperature of the reaction of the prepared salt solution, alkali solution and first auxiliary agent is 35-90 ℃, and the pH of the reaction is 1.7-2.9.
10. The method according to claim 2, wherein the waste lithium battery material is a waste nickel cobalt manganese ternary battery material, and in the step C), the molar ratio of Ni, co and Mn in the prepared salt solution is 5:2: 3. 6:2:2 or 8:1:1.
11. the method according to claim 10, wherein in step C), the temperature of the reaction of the prepared salt solution, alkali solution and first auxiliary agent is 45-80 ℃ and the pH of the reaction is 10-13.
12. A method according to claim 1 or 2, wherein in step D),
the ball milling time is 2-6 hours;
the sintering temperature is 600-900 ℃ and the sintering time is 4-12 h.
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