CN113151680A - Method for recycling waste lithium batteries - Google Patents
Method for recycling waste lithium batteries Download PDFInfo
- Publication number
- CN113151680A CN113151680A CN202110171619.9A CN202110171619A CN113151680A CN 113151680 A CN113151680 A CN 113151680A CN 202110171619 A CN202110171619 A CN 202110171619A CN 113151680 A CN113151680 A CN 113151680A
- Authority
- CN
- China
- Prior art keywords
- solution
- lithium
- acid
- battery material
- waste
- 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
Images
Classifications
-
- 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
-
- 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
-
- 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
Abstract
The invention relates to the technical field of waste lithium battery recovery, in particular to a method for recycling waste lithium batteries, which comprises the following steps: A) reacting waste lithium battery materials with acid liquor, and filtering to obtain leachate and solid slag; B) carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain impurity-removed solution; C) performing bipolar membrane electrodialysis on the impurity-removed solution to obtain a lithium hydroxide solution, an acid solution and a salt solution; blending the salt solution according to the element proportion, and reacting the blended salt solution, alkali liquor and a first auxiliary agent to obtain a precursor of the battery material; evaporating and crystallizing the lithium hydroxide solution to obtain a lithium hydroxide solid; D) and mixing the lithium hydroxide solid with the 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 recovered, high lithium recovery rate is obtained, high-valued comprehensive recovery and reutilization of all valuable metal ions are realized, and the overall acid consumption is reduced.
Description
Technical Field
The invention relates to the technical field of waste lithium battery recovery, in particular to a method for recycling waste lithium batteries.
Background
The recovery of waste lithium batteries is an important problem to be solved urgently. If the waste lithium battery is improperly disposed, potential safety hazards such as electric shock, explosion, corrosion and the like exist, and even spontaneous combustion or explosion can be caused under the conditions of special temperature, humidity and poor contact, for example, safety accidents such as recent electric automobile power battery ignition and the like 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 urban mine, and is an important solution for solving the problems of large demand, difficult exploitation and great dependence on import of the valuable metals such as nickel, cobalt, lithium and the like in China; in addition, if heavy metals, electrolyte and the like contained in the waste lithium batteries cannot be effectively recovered, the natural environment such as soil, rivers and the like can be damaged. Therefore, the development of green recovery of the waste lithium batteries has important economic value and social value and plays an important role in reducing environmental pollution and promoting sustainable development of the industry.
At present, the domestic waste lithium battery recovery process mainly adopts wet recovery. The method comprises the steps of adding sulfuric acid solution to waste lithium battery materials for leaching to obtain valuable metal solution containing lithium, nickel, cobalt and the like, then obtaining salt solutions of different metals through a multi-stage extraction process, evaporating and crystallizing the metal salt solutions of nickel, cobalt and the like to obtain corresponding metal salt products, finally adding sodium carbonate to the lithium solution to perform a lithium precipitation reaction to obtain a lithium carbonate product, and then respectively selling the lithium carbonate and the metal salt product to a precursor manufacturer and a positive electrode material manufacturer for production.
The drawbacks of the above recycling process include:
the existing waste lithium battery recovery process is to separately recover metals such as lithium, nickel and cobalt to obtain different products, and then the products are sold to a precursor manufacturer and a positive electrode material manufacturer respectively, so that the resource circulation process is long;
the recovery of lithium is usually carried out at the end of the whole process flow, the recovery rate of lithium is low, and the produced product is usually lithium carbonate;
the existing waste lithium battery recovery process is firstly acid leaching treatment, and the subsequent process needs to neutralize the acid, so that the overall consumption of sulfuric acid is large;
according to the change of the market demand for high specific capacity materials, the market share of the high nickel anode material is gradually increased at present, lithium hydroxide is needed for the production of the high nickel anode material, most lithium salt products recovered from the waste lithium batteries are lithium carbonate at present, and the lithium hydroxide products cannot be directly provided.
CN 111867980A discloses a method for preparing nickel-cobalt-manganese hydroxide, which comprises reacting metal sulfate containing nickel, cobalt, lithium and the like with a chelating agent to obtain metal hydroxide solid and liquid containing lithium sulfate, then obtaining lithium hydroxide from the liquid containing lithium sulfate by a two-chamber monopolar or bipolar membrane electrolysis process, wherein the electrodialysis raw material is a single lithium sulfate solution, and the production of nickel-cobalt-manganese hydroxide needs to consume various chemical reagents and has large dosage, high production cost and long process flow.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for recycling waste lithium batteries, so as to realize effective 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 waste lithium battery materials with acid liquor, and filtering to obtain leachate;
B) carrying out chemical impurity removal and resin adsorption on the leachate to obtain impurity-removed liquid;
C) performing bipolar membrane electrodialysis on the impurity removal solution to obtain a lithium hydroxide solution, an acid solution and a salt solution;
blending the salt solution according to the element proportion, and reacting the blended salt solution, alkali liquor and a first auxiliary agent to obtain a precursor of the battery material;
evaporating and crystallizing the lithium hydroxide solution to obtain a 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 solution comprises sulfuric acid and phosphoric acid, and the concentration of the acid solution 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 material of the reaction further comprises a second auxiliary agent;
the second auxiliary agent comprises one or more of hydrogen peroxide and sodium thiosulfate;
the acid solution is sulfuric acid, and the concentration of the acid solution is 0.1-4 mol/L.
Preferably, in the step A), the reaction temperature is 15-50 ℃ and the reaction time is 30-180 min.
Preferably, when the waste lithium battery material is a waste lithium iron phosphate material, in the step B):
the chemical impurity removal comprises the following steps:
mixing the leachate, iron powder and a pH regulator, and reacting;
the pH value of the mixed liquid 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 to 100 percent; 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 for resin adsorption is amino phosphoric acid type chelating 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 the step B):
the chemical impurity removal comprises the following steps:
mixing the leachate, iron powder and a pH regulator, and reacting;
the pH value of the mixed liquid 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 to 100 percent; 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 for resin adsorption is amino phosphoric acid type chelating resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃.
Preferably, in step C), the device for bipolar membrane electrodialysis comprises a bipolar membrane, an anion exchange membrane and a monovalent cation exchange membrane, and forms a salt compartment, an acid compartment and an alkali compartment; the anion exchange membrane and monovalent cation exchange membrane pair; performing bipolar membrane electrodialysis on the impurity-removed solution in a three-chamber bipolar membrane electrodialysis device, finally outputting a lithium hydroxide solution from an alkali chamber, outputting a salt solution from a salt chamber, and outputting an acid solution from an acid chamber;
the conducting solution 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 by 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 molar ratio of P to Fe in the prepared salt solution is 0.95-3.0: 1.
preferably, in the step C), the alkali liquor comprises one or more of ammonia water, a sodium carbonate solution and a sodium bicarbonate solution, the first auxiliary agent is a hydrogen peroxide solution, the temperature of the reaction of the prepared salt solution, the alkali liquor and the first auxiliary agent is 35-90 ℃, and the pH value of the reaction is 1.7-2.9, so as to obtain the iron phosphate precursor.
Preferably, 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.
preferably, in the step C), the alkali liquor comprises one or more of a sodium hydroxide solution, a sodium carbonate solution and a sodium bicarbonate solution, the first auxiliary agent is an ammonia water solution, the reaction temperature of the prepared salt solution, the alkali liquor and the first auxiliary agent is 45-80 ℃, and the reaction pH value is 10-13, so that the ternary nickel-cobalt-manganese precursor is obtained.
Preferably, in the step D), after the lithium hydroxide solid and the battery material precursor are mixed, ball milling is further performed;
the ball milling time is 2-6 h;
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 waste lithium battery materials with acid liquor, and filtering to obtain leachate; B) carrying out chemical impurity removal and resin adsorption on the leachate to obtain impurity-removed liquid; C) performing bipolar membrane electrodialysis on the impurity removal solution to obtain a lithium hydroxide solution, an acid solution and a salt solution; blending the salt solution according to the element proportion, and reacting the blended salt solution, alkali liquor and a first auxiliary agent to obtain a precursor of the battery material; evaporating and crystallizing the lithium hydroxide solution to obtain a 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 technical scheme provided by the invention can separate lithium from other valuable metal ions to directly obtain pure lithium hydroxide solution and other valuable metal ion solutions without lithium, the recovery rate of lithium is high, and lithium hydroxide can be obtained by one-step production; the high-valued comprehensive recovery and reutilization of all valuable metal ions are realized, and the acid liquor as a byproduct of electrodialysis can be directly recycled to a leaching working section, so that the overall acid consumption is reduced; meanwhile, the recycled metal salt solution is used for synthesizing a precursor, and then the recycled lithium hydroxide and the precursor material are mixed and sintered to obtain a newly synthesized anode material, so that the finally produced product is the newly synthesized anode material, the resource circulation flow is greatly shortened, and the social resource waste is avoided.
Drawings
FIG. 1 is a schematic diagram of the principle of bipolar membrane electrodialysis by using impurity removing liquid obtained by using waste lithium iron phosphate materials as waste lithium battery materials;
FIG. 2 is a schematic diagram of the principle of performing bipolar membrane electrodialysis on impurity removal liquid obtained by using waste nickel-cobalt-manganese ternary battery materials as waste lithium battery materials according to the invention;
fig. 3 is a process flow chart of recycling waste lithium batteries according to an embodiment of the present invention;
FIG. 4 is an XRD diagram of the ternary Ni-Co-Mn precursor in example 1 of the present invention;
FIG. 5 is an XRD pattern of the positive electrode material for a lithium battery in example 1 of the present invention;
fig. 6 is an XRD pattern of the iron phosphate precursor in example 3 of the present invention;
fig. 7 is an XRD pattern of the lithium battery positive electrode material in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for recycling waste lithium batteries, which comprises the following steps:
A) reacting waste lithium battery materials with acid liquor, and filtering to obtain leachate;
B) carrying out chemical impurity removal and resin adsorption on the leachate to obtain impurity-removed liquid;
C) performing bipolar membrane electrodialysis on the impurity removal solution to obtain a lithium hydroxide solution, an acid solution and a salt solution;
blending the salt solution according to the element proportion, and reacting the blended salt solution, alkali liquor and a first auxiliary agent to obtain a precursor of the battery material;
evaporating and crystallizing the lithium hydroxide solution to obtain a 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 leachate and solid slag.
In some embodiments of the present invention, the waste lithium battery material is a waste lithium iron phosphate battery material or a waste nickel-cobalt-manganese ternary battery material.
In some embodiments of the present invention, the waste lithium battery material is a waste lithium iron phosphate battery material.
Specifically, the method comprises the following steps:
reacting the lithium iron phosphate battery material with acid liquor, and filtering to obtain leachate and solid slag.
In some embodiments of the present invention, the acid solution comprises sulfuric acid and phosphoric acid, and the concentration of the acid solution is 0.1-4 mol/L. In certain embodiments, the acid solution has a concentration of 1mol/L or 3 mol/L.
In some 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 some embodiments, the mass ratio of the lithium iron phosphate battery material to the acid solution is 1: 3 or 1: 2.
in some embodiments of the present invention, the reaction temperature is 15-50 ℃ and the reaction time is 30-180 min. In certain embodiments, the temperature of the reaction is 30 ℃ or 50 ℃. In certain embodiments, the time of the reaction is 90min or 120 min.
The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
In some embodiments of the present invention, the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, and the raw material of the reaction further includes a second auxiliary agent.
Specifically, the method comprises the following steps:
reacting the nickel-cobalt-manganese ternary battery material, the acid liquor and the second auxiliary agent, and filtering to obtain a leaching solution and solid slag.
In some embodiments of the invention, the acid solution is sulfuric acid, and the concentration of the acid solution is 0.1-4 mol/L. In certain embodiments, the acid solution has a concentration of 1mol/L or 2 mol/L.
In some embodiments of the invention, the mass ratio of the nickel-cobalt-manganese ternary battery material to the acid solution is 1: 1 to 3. In some embodiments, the mass ratio of the nickel-cobalt-manganese ternary battery material to the acid solution is 1: 1 or 1: 2.
in certain embodiments of the present invention, the second auxiliary agent comprises one or more of hydrogen peroxide and sodium thiosulfate.
In some embodiments of the invention, the mass ratio of the nickel-cobalt-manganese ternary battery material to the second auxiliary agent is 1: 0.1 to 2. In some 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 some embodiments of the present invention, the reaction temperature is 15-50 ℃ and the reaction time is 30-120 min. In certain embodiments, the temperature of the reaction is 20 ℃ or 40 ℃. In certain embodiments, the time of the reaction is 60min or 80 min.
The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
And after obtaining the leaching solution, carrying out chemical impurity removal and resin adsorption on the leaching solution to obtain impurity removal solution 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 leachate, iron powder and a pH regulator, and reacting.
In some embodiments of the invention, the pH of the mixed solution after mixing is 2.8-5.0. In certain embodiments, the pH of the mixed liquor after mixing is 3.0.
In some embodiments of the invention, the leaching solution is mixed with iron powder, and the excess factor of the iron powder is 10% to 100%. In some embodiments, the leaching solution is mixed with iron powder, and the iron powder has an excess factor of 30% or 60%.
In certain embodiments of the invention, the pH adjusting agent comprises ammonium carbonate and/or urea.
In some embodiments of the present invention, the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min. In certain embodiments, the temperature of the reaction is 40 ℃ or 50 ℃. In certain embodiments, the time of the reaction is 90min or 120 min.
In some embodiments of the present invention, after the chemically removing, the method further comprises: and (5) filtering. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
In some embodiments of the present invention, the resin used for the resin adsorption is an aminophosphonic acid type chelating resin, which may be generally commercially available.
In some embodiments of the invention, the resin adsorption rate is 2-6 BV. In certain embodiments, the rate of resin adsorption is 2BV or 4 BV.
In some embodiments of the invention, the resin adsorption temperature 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 leachate, iron powder and a pH regulator, and reacting.
In some embodiments of the invention, the pH of the mixed solution after mixing is 3.5 to 5.5. In certain embodiments, the pH of the mixed liquor after mixing is 4.0.
In some embodiments of the invention, the leaching solution is mixed with iron powder, and the excess factor of the iron powder is 10% to 100%. In some embodiments, the leaching solution is mixed with iron powder, and the iron powder has an excess factor of 20%.
In certain embodiments of the present invention, the pH adjusting agent comprises one or more of lithium carbonate, ammonium carbonate, and lithium hydroxide.
In some embodiments of the present invention, the reaction temperature is 25-60 ℃ and the reaction time is 30-180 min. In certain embodiments, the temperature of the reaction is 35 ℃ or 40 ℃. In certain embodiments, the time of the reaction is 60min or 120 min.
In some embodiments of the present invention, after the chemically removing, the method further comprises: and (5) filtering. The method of filtration is not particularly limited in the present invention, and a filtration method known to those skilled in the art may be used.
In some embodiments of the present invention, the resin used for the resin adsorption is an aminophosphonic acid type chelating resin, which may be generally commercially available.
In some embodiments of the invention, the resin adsorption rate is 2-6 BV. In certain embodiments, the rate of resin adsorption is 3BV or 6 BV.
In some embodiments of the invention, the resin adsorption temperature is 15-50 ℃. In certain embodiments, the temperature of the resin adsorption is 30 ℃ or 40 ℃.
And after the impurity removal liquid is obtained, performing bipolar membrane electrodialysis on the impurity removal liquid to obtain a lithium hydroxide solution, an acid solution and a salt solution.
In certain embodiments of the present invention, the bipolar membrane electrodialysis device is a three-compartment bipolar membrane electrodialysis device. Specifically, the device comprises a bipolar membrane, an anion exchange membrane and a monovalent cation exchange membrane, and a salt chamber, an acid chamber and an alkali chamber are formed; the anion exchange membrane and the monovalent cation exchange membrane are paired. And the impurity removal solution enters a salt chamber in a three-chamber bipolar membrane electrodialysis device for bipolar membrane electrodialysis, finally, a lithium hydroxide solution is output from an alkali chamber, a salt solution is output from the salt chamber, and an acid solution is output from an acid chamber.
In certain embodiments of the present 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 the principle of performing bipolar membrane electrodialysis on an 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 the principle of performing bipolar membrane electrodialysis on an 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 material of the bipolar membrane, the anion exchange membrane and the monovalent cation exchange membrane is not particularly limited in the present invention, and those known to those skilled in the art can be used.
In certain embodiments of the invention, the conducting 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 conducting liquid entering the base 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 present invention, the bipolar membrane electrodialysis has a current of less than 4.5A. In certain embodiments, the bipolar membrane electrodialysis has a current of 4.0A, 3.5A, 3.8A, or 3.0A.
In certain embodiments of the present invention, the acid solution output from the acid chamber is recycled to step a).
The preparation method comprises the steps of blending the salt solution according to the element proportion, and reacting the blended salt solution, the alkali liquor and the first auxiliary agent to obtain the precursor of the battery material.
In some embodiments of the present invention, when the waste lithium battery material is a waste lithium iron phosphate battery material:
in the prepared salt solution, the molar ratio of P to Fe is 0.95-3.0: 1; in certain embodiments, the molar ratio of P to Fe in the formulated salt solution is 1: 1 or 3: 1;
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: 1-3; in certain embodiments, the mass ratio of the formulated salt solution to the first auxiliary agent is 10: 1 or 11: 2;
the temperature of the reaction of the prepared salt solution, the alkali liquor and the 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 reaction time is 1h or 2 h;
after the reaction, filtering, washing and drying are also carried out; the method of filtering, washing and drying is not particularly limited in the present invention, and a method of filtering, washing and drying well known to those skilled in the art may be used;
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 molar ratio of Ni to Co to Mn is 5-9: 0.5-2: 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 auxiliary agent is 10: 1 or 11: 0.9;
the temperature of the reaction of the prepared salt solution, the alkali liquor and the 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 reaction time is 80h or 60 h;
after the reaction, filtering, washing and drying are also carried out; the method of filtering, washing and drying is not particularly limited in the present invention, and a method of filtering, washing and drying well known to those skilled in the art may be used;
the obtained precursor of the battery material is a ternary nickel-cobalt-manganese precursor.
In the invention, lithium hydroxide solution output from an alkali chamber of the three-chamber bipolar membrane electrodialysis device is evaporated and crystallized to obtain lithium hydroxide solid. The method of evaporative crystallization is not particularly limited in the present invention, and any method of evaporative crystallization known to those skilled in the art may be used.
In certain embodiments of the present invention, the evaporative crystallization is followed by drying. The drying method and parameters are not particularly limited in the present invention, and those known to those skilled in the art can be used.
And after obtaining a battery material precursor and a lithium hydroxide solid, mixing the lithium hydroxide solid with the battery material precursor, and sintering to obtain the lithium battery anode material.
In certain embodiments of the invention, the lithium hydroxide solid is mixed with the battery material precursor with an excess factor of the lithium hydroxide solid ranging from 2% to 10%. In certain embodiments, the lithium hydroxide solids are mixed with the battery material precursor with an excess factor of 5%, 8%, 3%, or 10% for the lithium hydroxide solids.
In certain embodiments of the present invention, after mixing the lithium hydroxide solid and the battery material precursor, ball milling is also included.
In some embodiments of the invention, the ball milling time is 2-6 h. In certain embodiments, the ball milling time is 3h, 5h, 6h, or 4 h.
In some embodiments of the invention, the sintering temperature is 600-900 ℃ and the sintering time is 4-12 h. In certain embodiments, the temperature of the sintering is 700 ℃, 900 ℃, 600 ℃, or 800 ℃. In certain embodiments, the sintering time is 10h, 6h, 8h, or 12 h.
In some embodiments of the present invention, when the waste lithium battery material is a waste lithium iron phosphate material, the sintering is performed in an argon atmosphere or a nitrogen atmosphere.
In some embodiments of the present invention, when the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, the sintering is performed in an oxygen atmosphere.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
Fig. 3 is a process flow chart of recycling waste lithium batteries according to an embodiment of the present invention.
The technical scheme provided by the invention can separate lithium from other valuable metal ions to directly obtain pure lithium hydroxide solution and other valuable metal ion solutions without lithium, the recovery rate of lithium is high, and lithium hydroxide can be obtained by one-step production; the high-valued comprehensive recovery and reutilization of all valuable metal ions are realized, and the acid liquor as a byproduct of electrodialysis can be directly recycled to a leaching working section, so that the overall acid consumption is reduced; meanwhile, the recycled metal salt solution is used for synthesizing a precursor, and then the recycled lithium hydroxide and the precursor material are mixed and sintered to obtain a newly synthesized anode material, so that the finally produced product is the newly synthesized anode 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 will describe the method for recycling waste lithium batteries in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention.
The starting materials used in the following examples are all generally commercially available.
Example 1
The method for recycling the waste lithium battery comprises the following steps:
1) waste nickel-cobalt-manganese ternary lithium battery materials, 1mol/L sulfuric acid and hydrogen peroxide are mixed according to the mass ratio of 1: 1: 0.5, adding the mixture into a reaction kettle, reacting for 60min at the temperature of 20 ℃, and filtering to obtain a leaching solution and solid residues, wherein the leaching rate of lithium is 98.5%;
2) adding iron powder with an excess coefficient of 20% into the leachate obtained in the step 1), then adding lithium carbonate to adjust the pH of the solution to 4.0, reacting for 60min at 35 ℃, filtering, and then passing the filtrate at 30 ℃ through a resin adsorption column (the resin is amino phosphoric acid type chelating resin) at a flow rate of 3BV to obtain an impurity removal solution;
3) introducing the impurity-removing solution obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein a conductive solution entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is a sulfuric acid solution with the mass concentration of 0.05%, a conductive solution entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is a lithium hydroxide solution with the mass concentration of 0.05%, and finally outputting the lithium hydroxide solution from the alkali chamber, outputting a valuable metal salt solution from the salt chamber, and outputting an acid solution from the acid chamber under the action of 4.0A current;
4) recycling the acid solution output by the electrodialysis acid chamber for leaching in the step 1);
5) and (3) carrying out element blending on the salt solution output by the salt room in the step 3), wherein in the blended salt solution, the molar ratio of Ni to Co to Mn is 8: 1: 1, adding the prepared salt solution, a sodium hydroxide solution (with the mass concentration of 5%) and an ammonia water solution (with the mass concentration of 10%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the ammonia water solution is 10: 1, reacting for 80 hours at 50 ℃ and with the pH value controlled to be 11.5, filtering, washing and drying to obtain a ternary nickel-cobalt-manganese precursor;
6) evaporating and crystallizing the lithium hydroxide solution output by the alkali chamber in the step 3), and drying to obtain a 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%, then ball-milling for 3h, and sintering for 10h at 700 ℃ in an oxygen atmosphere to obtain the lithium battery cathode material.
In this embodiment, an X-ray diffractometer is used to analyze the obtained ternary nickel-cobalt-manganese precursor, so as to obtain an XRD pattern of the ternary nickel-cobalt-manganese precursor in embodiment 1 of the present invention, as shown in fig. 4. Fig. 4 is an XRD chart of the ternary nickel cobalt manganese precursor in example 1 of the present invention. As can be seen from fig. 4, the synthesized ternary precursor has the NCM811 structure.
In this example, the obtained lithium battery cathode material is further analyzed by an X-ray diffractometer, so as to obtain an XRD pattern of the lithium battery cathode material in example 1 of the present invention, as shown in fig. 5. Fig. 5 is an XRD pattern of the positive electrode material for lithium battery in example 1 of the present invention. As can be seen from fig. 5, the resulting cathode material is a 811 ternary cathode material structure.
Example 2
The method for recycling the waste lithium battery comprises the following steps:
1) waste nickel-cobalt-manganese ternary lithium battery materials, 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 80min at 40 ℃, and filtering to obtain a leaching solution and solid residues, wherein the leaching rate of lithium is 99.6%;
2) adding iron powder with an excess coefficient of 50% into the leachate 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 passing the filtrate at 40 ℃ through a resin adsorption column (the resin is aminophosphoric acid type chelating resin) at a flow rate of 6BV to obtain an impurity removal solution;
3) introducing the impurity-removing solution obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conducting solution entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is a sulfuric acid solution with the mass concentration of 1.0%, the conducting solution entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is a lithium hydroxide solution with the mass concentration of 1.0%, and finally outputting the lithium hydroxide solution from the alkali chamber, outputting a valuable metal salt solution from the salt chamber, and outputting an acid solution from the acid chamber under the action of 3.5A current;
4) recycling the acid solution output by the electrodialysis acid chamber for leaching in the step 1);
5) and (3) carrying out element blending on the salt solution output by the salt room in the step 3), wherein in the blended salt solution, the molar ratio of Ni to Co to Mn is 8: 1: 1, adding the prepared salt solution, a sodium hydroxide solution (with the mass concentration of 10%) and an ammonia water solution (with the mass concentration of 25%) into a synthesis reaction kettle, wherein the mass ratio of the prepared salt solution to the ammonia water solution is 11: 0.9, reacting for 60 hours at 60 ℃ under the condition that the pH value is controlled to be 10.5, and filtering, washing and drying to obtain a ternary nickel-cobalt-manganese precursor;
6) evaporating and crystallizing the lithium hydroxide solution output by the alkali chamber in the step 3), and drying to obtain a 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%, then ball-milling for 5h, and sintering at 900 ℃ for 6h in an oxygen atmosphere to obtain the lithium battery cathode material.
Example 3
The method for recycling the waste lithium battery comprises the following steps:
1) mixing waste lithium iron phosphate battery materials and 1mol/L sulfuric acid according to a mass ratio of 1: 3, adding the mixture into a reaction kettle, reacting for 90min at the temperature of 30 ℃, and filtering to obtain a leaching solution and solid residues, wherein the leaching rate of lithium is 99.5%;
2) adding iron powder with an excess coefficient of 30% into the leachate obtained in the step 1), then adding ammonium carbonate to adjust the pH of the solution to 3.0, reacting for 90min at 40 ℃, filtering, and then passing the filtrate at 25 ℃ through a resin adsorption column (the resin is aminophosphoric acid type chelating resin) at a flow rate of 2BV to obtain an impurity removal solution;
3) introducing the impurity-removing solution obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein a conductive solution entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is a sulfuric acid solution with the mass concentration of 0.05%, a conductive solution entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is a lithium hydroxide solution with the mass concentration of 0.05%, and finally outputting the lithium hydroxide solution from the alkali chamber, outputting a valuable metal salt solution from the salt chamber, and outputting an acid solution from the acid chamber under the action of 3.8A current;
4) recycling the acid solution output by the electrodialysis acid chamber for leaching in the step 1);
5) and (3) carrying out element blending on the salt solution output by the salt chamber in the step 3), wherein in the blended salt solution, the molar ratio of P to Fe is 1: adding the prepared salt solution, an ammonia water solution (with the mass concentration of 5%) and a 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 to be 2.0 at 50 ℃, reacting for 1 hour, and filtering, washing and drying to obtain an iron phosphate precursor;
6) evaporating and crystallizing the lithium hydroxide solution output by the alkali chamber in the step 3), and drying to obtain a lithium hydroxide solid;
7) mixing the lithium hydroxide solid obtained in the step 6) with the iron phosphate precursor obtained in the step 5) according to an excess coefficient of 3%, then ball-milling for 6h, and sintering at 600 ℃ for 8h in a nitrogen atmosphere to obtain the lithium battery anode material.
In this example, the XRD pattern of the iron phosphate precursor in example 3 of the present invention was obtained by analyzing the obtained iron phosphate precursor with an X-ray diffractometer, as shown in fig. 6. Fig. 6 is an XRD pattern of the iron phosphate precursor in example 3 of the present invention. According to an XRD (X-ray diffraction) pattern, the synthesized precursor is iron phosphate.
In this example, the obtained lithium battery cathode material is further analyzed by an X-ray diffractometer, so as to obtain an XRD pattern of the lithium battery cathode material in example 3 of the present invention, as shown in fig. 7. Fig. 7 is an XRD pattern of the lithium battery positive electrode material in example 3 of the present invention. The XRD spectrum shows that the synthesized material is a lithium iron phosphate anode material.
Example 4
The method for recycling the waste lithium battery comprises the following steps:
1) mixing waste lithium iron phosphate battery materials and 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 a leaching solution and solid residues, wherein the leaching rate of lithium is 99.9%;
2) adding iron powder with an excess coefficient of 60% into the leachate obtained in the step 1), then adding urea to adjust the pH of the solution to 4.5, reacting at 50 ℃ for 120min, filtering, and then passing the filtrate at 45 ℃ through a resin adsorption column at a flow rate of 4BV to obtain an impurity-removed solution;
3) introducing the impurity-removing solution obtained in the step 2) into a salt chamber in a three-chamber bipolar membrane electrodialysis device, wherein the conducting solution entering an acid chamber of the three-chamber bipolar membrane electrodialysis device is a sulfuric acid solution with the mass concentration of 1.1%, the conducting solution entering an alkali chamber of the three-chamber bipolar membrane electrodialysis device is a lithium hydroxide solution with the mass concentration of 1.1%, and finally outputting the lithium hydroxide solution from the alkali chamber, outputting a valuable metal salt solution from the salt chamber, and outputting an acid solution from the acid chamber under the action of 3.0A current;
4) recycling the acid solution output by the electrodialysis acid chamber for leaching in the step 1);
5) and (3) carrying out element blending on the salt solution output by the salt chamber in the step 3), wherein in the blended salt solution, the molar ratio of P to Fe is 3: adding the prepared salt solution, a sodium carbonate solution (with the mass concentration of 10%) and a 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 to be 2.7 at 80 ℃, reacting for 2 hours, and filtering, washing and drying to obtain an iron phosphate precursor;
6) evaporating and crystallizing the lithium hydroxide solution output by the alkali chamber in the step 3), and drying to obtain a lithium hydroxide solid;
7) mixing the lithium hydroxide solid obtained in the step 6) with the iron phosphate precursor obtained in the step 5) according to the excess coefficient of 10%, then ball-milling for 4h, and sintering at 800 ℃ for 12h 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 waste lithium battery materials with acid liquor, and filtering to obtain leachate;
B) carrying out chemical impurity removal and resin adsorption on the leachate to obtain impurity-removed liquid;
C) performing bipolar membrane electrodialysis on the impurity removal solution to obtain a lithium hydroxide solution, an acid solution and a salt solution;
blending the salt solution according to the element proportion, and reacting the blended salt solution, alkali liquor and a first auxiliary agent to obtain a precursor of the battery material;
evaporating and crystallizing the lithium hydroxide solution to obtain a lithium hydroxide solid;
D) and mixing the lithium hydroxide solid with a battery material precursor, and sintering to obtain the lithium battery anode material.
2. The method according to claim 1, wherein in the step A), 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.
3. The method as claimed in claim 1, wherein in the step a), the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, and the raw material for the reaction further comprises a second auxiliary agent;
the second auxiliary agent comprises one or more of hydrogen peroxide and sodium thiosulfate;
the acid solution is sulfuric acid, and the concentration of the acid solution is 0.1-4 mol/L.
4. The method according to claim 1, wherein the reaction temperature in step A) is 15-50 ℃ and the reaction time is 30-180 min.
5. The method as claimed in claim 1, wherein when the waste lithium battery material is a waste lithium iron phosphate material, in step B):
the chemical impurity removal comprises the following steps:
mixing the leachate, iron powder and a pH regulator, and reacting;
the pH value of the mixed liquid 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 to 100 percent; 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 for resin adsorption is amino phosphoric acid type chelating resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃.
6. The method as claimed in claim 1, wherein when the waste lithium battery material is a waste nickel-cobalt-manganese ternary battery material, in the step B):
the chemical impurity removal comprises the following steps:
mixing the leachate, iron powder and a pH regulator, and reacting;
the pH value of the mixed liquid 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 to 100 percent; 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 for resin adsorption is amino phosphoric acid type chelating resin, the resin adsorption speed is 2-6 BV, and the temperature is 15-50 ℃.
7. The process according to claim 1, wherein in step C), the means of bipolar membrane electrodialysis comprise a bipolar membrane, an anion exchange membrane and a monovalent cation exchange membrane, constituting a salt compartment, an acid compartment and a base compartment; the anion exchange membrane and monovalent cation exchange membrane pair; performing bipolar membrane electrodialysis on the impurity-removed solution in a three-chamber bipolar membrane electrodialysis device, finally outputting a lithium hydroxide solution from an alkali chamber, outputting a salt solution from a salt chamber, and outputting an acid solution from an acid chamber;
the conducting solution 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 by the acid chamber is reused in the step A).
8. The method according to claim 1, wherein the waste lithium battery material is a waste lithium iron phosphate battery material, and in the step C), the molar ratio of P to Fe in the prepared salt solution is 0.95-3.0: 1.
9. the method according to claim 8, wherein in the step C), the alkali liquor comprises one or more of ammonia water, a sodium carbonate solution and a sodium bicarbonate solution, the first auxiliary agent is a hydrogen peroxide solution, the temperature of the reaction of the prepared salt solution, the alkali liquor and the first auxiliary agent is 35-90 ℃, and the pH value of the reaction is 1.7-2.9, so as to obtain the iron phosphate precursor.
10. The method as claimed in claim 1, 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 the step C), the alkali solution comprises one or more of a sodium hydroxide solution, a sodium carbonate solution and a sodium bicarbonate solution, the first auxiliary agent is an ammonia solution, the temperature of the reaction of the prepared salt solution, the alkali solution and the first auxiliary agent is 45-80 ℃, and the pH value of the reaction is 10-13, so as to obtain the ternary nickel cobalt manganese precursor.
12. The method according to claim 1, wherein step D) further comprises ball milling after mixing the lithium hydroxide solid and the battery material precursor;
the ball milling time is 2-6 h;
the sintering temperature is 600-900 ℃, and the sintering time is 4-12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171619.9A CN113151680B (en) | 2021-02-08 | 2021-02-08 | Method for recycling waste lithium batteries |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110171619.9A CN113151680B (en) | 2021-02-08 | 2021-02-08 | Method for recycling waste lithium batteries |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113151680A true CN113151680A (en) | 2021-07-23 |
| CN113151680B CN113151680B (en) | 2023-06-16 |
Family
ID=76882848
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110171619.9A Active CN113151680B (en) | 2021-02-08 | 2021-02-08 | Method for recycling waste lithium batteries |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113151680B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117305604A (en) * | 2023-11-29 | 2023-12-29 | 湖南五创循环科技股份有限公司 | Method for recovering valuable metals in lithium cobalt oxide battery by cooperation of reduction gasification and continuous membrane separation technology |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE827642A (en) * | 1974-04-11 | 1975-07-31 | D.R. WEIR AND V.B. SEFTON | |
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
| US20120068107A1 (en) * | 2010-09-20 | 2012-03-22 | Korea Institute Of Science And Technology | Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery |
| JP2012234732A (en) * | 2011-05-02 | 2012-11-29 | Asahi Kasei Corp | Lithium recovery method |
| CN103627904A (en) * | 2013-11-29 | 2014-03-12 | 湖南邦普循环科技有限公司 | Method for recovering cobalt manganese from cobalt manganese catalyst wastes |
| WO2014154152A1 (en) * | 2013-03-28 | 2014-10-02 | 四川天齐锂业股份有限公司 | Method for recycling nickel-cobalt-manganese ternary anode material |
| CN108517409A (en) * | 2018-04-04 | 2018-09-11 | 长沙矿冶研究院有限责任公司 | A method of recycling valuable metal from waste and old power battery anode waste material |
| CN111206148A (en) * | 2020-03-16 | 2020-05-29 | 宁波容百新能源科技股份有限公司 | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery |
| CN111825110A (en) * | 2020-05-12 | 2020-10-27 | 宁夏百川新材料有限公司 | Recycling method of waste lithium ion battery anode material |
| CN111867980A (en) * | 2017-11-22 | 2020-10-30 | 内玛斯卡锂业有限公司 | Process for preparing hydroxides and oxides of various metals and derivatives thereof |
-
2021
- 2021-02-08 CN CN202110171619.9A patent/CN113151680B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE827642A (en) * | 1974-04-11 | 1975-07-31 | D.R. WEIR AND V.B. SEFTON | |
| CN101847763A (en) * | 2010-04-09 | 2010-09-29 | 奇瑞汽车股份有限公司 | Comprehensive recovering method of waste lithium iron phosphate battery |
| US20120068107A1 (en) * | 2010-09-20 | 2012-03-22 | Korea Institute Of Science And Technology | Recovery and synthesis method for metaloxidic cathodic active material for lithium ion secondary battery |
| JP2012234732A (en) * | 2011-05-02 | 2012-11-29 | Asahi Kasei Corp | Lithium recovery method |
| WO2014154152A1 (en) * | 2013-03-28 | 2014-10-02 | 四川天齐锂业股份有限公司 | Method for recycling nickel-cobalt-manganese ternary anode material |
| CN103627904A (en) * | 2013-11-29 | 2014-03-12 | 湖南邦普循环科技有限公司 | Method for recovering cobalt manganese from cobalt manganese catalyst wastes |
| CN111867980A (en) * | 2017-11-22 | 2020-10-30 | 内玛斯卡锂业有限公司 | Process for preparing hydroxides and oxides of various metals and derivatives thereof |
| CN108517409A (en) * | 2018-04-04 | 2018-09-11 | 长沙矿冶研究院有限责任公司 | A method of recycling valuable metal from waste and old power battery anode waste material |
| CN111206148A (en) * | 2020-03-16 | 2020-05-29 | 宁波容百新能源科技股份有限公司 | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery |
| CN111825110A (en) * | 2020-05-12 | 2020-10-27 | 宁夏百川新材料有限公司 | Recycling method of waste lithium ion battery anode material |
Non-Patent Citations (3)
| Title |
|---|
| GAOJIE ET AL.: "Recovery or lithium battery", ADVANCED MATERIALS * |
| 邹超;潘君丽;刘维桥;周全法;: "湿法回收锂离子电池三元正极材料的进展", 电池 * |
| 高洁等: "废旧锂电池中有价金属的回收技术研究", 环境科学与管理 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117305604A (en) * | 2023-11-29 | 2023-12-29 | 湖南五创循环科技股份有限公司 | Method for recovering valuable metals in lithium cobalt oxide battery by cooperation of reduction gasification and continuous membrane separation technology |
| CN117305604B (en) * | 2023-11-29 | 2024-02-23 | 湖南五创循环科技股份有限公司 | Method for recovering valuable metals in lithium cobalt oxide battery by cooperation of reduction gasification and continuous membrane separation technology |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113151680B (en) | 2023-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA3083136C (en) | Processes for preparing hydroxides and oxides of various metals and derivatives thereof | |
| CN108075202B (en) | Comprehensive recovery method of lithium iron phosphate anode material | |
| KR101238898B1 (en) | Method for recovering with high purity lithium, lithium carbonate, lithium hydroxide and synthetic method of cathod material for lithium secondary battery from sea water | |
| CN113896211B (en) | Treatment method for funding waste lithium iron phosphate battery | |
| CN111675203A (en) | Method for recovering lithium from waste lithium iron phosphate batteries and method for recovering lithium and iron phosphate | |
| CN109554545A (en) | A method of lithium is selectively mentioned from LiFePO4 waste material | |
| US20220242746A1 (en) | Processes for preparing hydroxides and oxides of various metals and derivatives thereof | |
| CN113104827B (en) | Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution | |
| Liu et al. | A closed-loop process for selective lithium recovery from brines via electrochemical and precipitation | |
| CN108767353B (en) | Method for producing lithium-rich clean liquid from anode active material of waste lithium ion battery | |
| CN114655969B (en) | Method for preparing lithium carbonate and iron phosphate by recycling high-impurity lithium iron phosphate positive electrode waste material | |
| CN109179359A (en) | A method of extracting lithium and ferric phosphate from LiFePO4 waste material | |
| CN108183276A (en) | The preparation method of ferric phosphate | |
| CN103579608A (en) | Preparation method of electrolytic manganese dioxide for positive material-lithium manganate of lithium battery | |
| CN113415793A (en) | Method for preparing high-purity iron phosphate from lithium iron phosphate battery waste | |
| CN113151680B (en) | Method for recycling waste lithium batteries | |
| CN107792840B (en) | Method for preparing iron phosphate by using byproduct ferrophosphorus in industrial yellow phosphorus production | |
| CN115196609B (en) | Method for recovering iron phosphate from lithium iron phosphate lithium extraction slag and application thereof | |
| CN115072688B (en) | Method for recycling all components of waste lithium iron phosphate battery | |
| CN115799696A (en) | Method for pretreating waste electrolyte after disassembling lithium ion battery and method for fully recovering lithium, fluorine and phosphorus in waste electrolyte | |
| CN113666397A (en) | Method for economically recycling lithium from waste lithium iron phosphate material by acid process | |
| CN110950752A (en) | Preparation method of lithium formate solution | |
| CN114317985B (en) | Method for removing zirconium from nickel-cobalt-manganese solution generated by recycling waste power storage batteries | |
| CN116581415B (en) | Method for jointly recycling waste iron phosphate slag and waste lithium cobalt oxide all elements generated by selectively extracting lithium from waste lithium iron phosphate | |
| CN116534905B (en) | Method for recycling valuable metals in waste lithium cobaltate by utilizing carbon-containing crude ferric phosphate generated after selective lithium extraction of lithium iron phosphate |
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 |