CN111799524A - Method for preparing five-element high-entropy lithium battery material precursor from retired lithium battery positive plate - Google Patents
Method for preparing five-element high-entropy lithium battery material precursor from retired lithium battery positive plate Download PDFInfo
- Publication number
- CN111799524A CN111799524A CN202010667810.8A CN202010667810A CN111799524A CN 111799524 A CN111799524 A CN 111799524A CN 202010667810 A CN202010667810 A CN 202010667810A CN 111799524 A CN111799524 A CN 111799524A
- Authority
- CN
- China
- Prior art keywords
- solution
- lithium battery
- quinary
- reaction
- positive plate
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002243 precursor Substances 0.000 title claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 65
- 238000006243 chemical reaction Methods 0.000 claims abstract description 61
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 32
- 238000001914 filtration Methods 0.000 claims abstract description 25
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims abstract description 4
- 238000000975 co-precipitation Methods 0.000 claims abstract description 3
- 239000003085 diluting agent Substances 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 50
- 239000003350 kerosene Substances 0.000 claims description 43
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 40
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 21
- 229910001431 copper ion Inorganic materials 0.000 claims description 21
- 229910052782 aluminium Inorganic materials 0.000 claims description 20
- 239000012066 reaction slurry Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 12
- 239000002002 slurry Substances 0.000 abstract description 3
- 239000011572 manganese Substances 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- 238000007792 addition Methods 0.000 description 13
- 150000002500 ions Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 230000001276 controlling effect Effects 0.000 description 9
- 238000011084 recovery Methods 0.000 description 7
- 239000011888 foil Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910001386 lithium phosphate Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- 239000006148 magnetic separator Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/30—Alkali metal phosphates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/003—Preparation involving a liquid-liquid extraction, an adsorption or an ion-exchange
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
- C22B1/00—Preliminary treatment of ores or scrap
- C22B1/02—Roasting 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- 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 belongs to the field of lithium battery recycling, and particularly relates to a method for preparing a five-element high-entropy lithium battery material precursor from a retired lithium battery positive plate, which comprises the steps of carrying out mixed roasting on the retired ternary and lithium iron phosphate battery positive plates to obtain a positive plate with organic matters removed; acid leaching the obtained positive plate, and filtering the reaction solution to obtain a quinary first solution; removing Cu from the quinary first solution, extracting metal ions in the quinary first solution by using an extracting agent, and performing back extraction to obtain a back-extracted quinary second solution; adjusting the proportion of metal ions in the quinary second solution, carrying out coprecipitation reaction, washing slurry, filtering, drying and roasting to obtain a precursor of the quinary high-entropy lithium battery material; according to the method, the retired ternary and lithium iron phosphate positive plates are recycled in a unified manner, so that the recycling process and the recycling cost are greatly simplified, and the prepared five-element high-entropy lithium battery material solves the problems of poor high-temperature stability and rapid capacity attenuation of the traditional lithium battery material.
Description
Technical Field
The invention belongs to the field of recycling of lithium batteries, and particularly relates to a method for preparing a five-element high-entropy lithium battery material precursor from a retired lithium battery positive plate.
Background
In recent years, as new energy automobiles are increasingly valued and developed, the replacement of traditional automobiles has become a necessary trend. The new energy automobile creates green travel and brings corresponding problems, the service life of the lithium ion power battery as the heart of the new energy automobile is only 5 years on average, and the accumulated scrappage of the power battery of the electric automobile in China reaches the scale of 12-17 ten thousand tons by 2020. Due to the complex structure of the lithium ion power battery, the high cost of recovery and the imperfect process, the recovery and utilization are always in a state of low enthusiasm.
An acid dissolution method is one of the main methods for recovering valuable metal materials in lithium iron phosphate at present, and for example, patent 201710657055.3 discloses a method for recovering a waste lithium iron phosphate positive electrode material, which comprises the steps of leaching lithium iron powder from which organic matters are removed with sulfuric acid, adjusting the pH of the solution to obtain iron phosphate, continuously adjusting the pH of the solution, and adding sodium carbonate to generate lithium carbonate; the retired ternary material is mainly recycled and regenerated to prepare a ternary positive electrode material, for example, in patent CN107419096B, the ternary waste is leached by inorganic acid, after copper, aluminum and iron are removed, coprecipitated under alkaline conditions to obtain a ternary material precursor, and the ternary material precursor is ball-milled with lithium carbonate and then calcined to prepare the regenerated ternary positive electrode material. Although the existing technology for recovering the retired ternary lithium iron and lithium iron independently is mature, the technology for recovering the two materials is very different, so that unified recovery cannot be realized, the process flow and equipment are complex, and the recovery cost is high.
At present, in the recycling process of retired lithium batteries, aluminum foils are separated after being disassembled and sorted, for example, CN105811040B, waste lithium batteries are sorted out by a water-type air suction crusher, a magnetic separator, a horizontal winnowing machine, a water-type friction machine, a first vortex sorting machine, a second vortex sorting machine and other equipment, and the sorting purity can reach 94% -99%. The method for recycling the aluminum foil is not ideal in recycling efficiency on one hand, and on the other hand, the aluminum remained in the anode powder brings certain difficulty for subsequent impurity removal and recycling.
At present, the anode material of the power battery is mainly lithium iron phosphate (LFP), ternary (NCA/NCM) material and lithium manganate. Although the performance advantages of each material are obvious, the respective defects are not ignored, wherein the gram volume density of the lithium iron phosphate is low, and the energy density is low; the lithium manganate has poor cycle performance and short service life; at present, the ternary material is widely applied due to the ultrahigh capacity and rate capability, but the preparation cost is high, and the poor safety performance is always the problem to be further solved.
Therefore, research and development of a technical scheme for uniformly and efficiently recycling retired ternary and iron phosphate lithium battery materials and breakthrough of the defects of the traditional lithium battery materials in structural performance become important targets and directions for the development of the current lithium battery materials.
At present, there is no method for uniformly recycling all valuable metals in the out-of-service ternary lithium battery and lithium iron phosphate battery positive plates, and there is no method for solving the problems of poor high-temperature stability and rapid capacity attenuation of lithium battery materials through the mixed high-entropy effect of multiple principal elements.
Disclosure of Invention
In order to solve the problems that the unified recovery of metals in the anode plate of the existing retired ternary lithium ion battery and lithium iron phosphate battery is difficult, the high-temperature stability of the traditional lithium battery material is poor, and the capacity attenuation is fast, the invention utilizes the prepared quinary high-entropy material to solve the problem of complex recovery process, so as to achieve the purpose of improving the safety of the ternary material and the energy density of the lithium iron phosphate. The method greatly simplifies the recovery process of valuable metals of the retired lithium battery, and the prepared high-entropy lithium battery material has stable high-temperature performance and slow capacity attenuation.
The invention provides a method for preparing a five-element high-entropy lithium battery material precursor by using a retired lithium battery positive electrode material, which is characterized by comprising the following steps of:
(1) mixing and roasting the retired ternary lithium iron phosphate battery positive plate to obtain a positive plate with organic matters removed;
(2) acid leaching the positive plate obtained in the step (1), and filtering the reaction solution to obtain a first solution of five elements of Fe, Al, Ni, Co and Mn;
(3) removing Cu from the quinary first solution in the step (2), and extracting Fe in the quinary first solution by using an extracting agent3+,Al3+,Ni2+,Co2+,Mn2+Metal ions are stripped to obtain a stripping five-element second solution;
(4) and adjusting the proportion of each metal ion in the quinary second solution, carrying out coprecipitation reaction on the metal ions, the sodium hydroxide solution and the citric acid solution, filtering, washing and drying the reaction slurry, and roasting to obtain the precursor of the quinary high-entropy lithium battery material.
Preferably, in step (1):
the roasting temperature is 300-600 ℃, and the constant temperature time is 2-6 h.
Preferably, in step (2):
the acid is one or more of sulfuric acid, hydrochloric acid and phosphoric acid.
The concentration of the used acid is 70-200g/L, and the solid-to-liquid ratio is 50-200 g/L.
The acid leaching temperature is 50-90 ℃, and the reaction time is 2-5 h.
Preferably, in step (3):
in the step (2), an extraction method is adopted for removing Cu, the extractant is LIX984N, and the molar dosage of the extractant is 2.0-4.0 times of the molar quantity of the copper ions in the solution; preferably, the extracting agent is diluted by a diluent, and the diluent can be common extracting agent diluents; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of the extracting agent to the diluting agent is 1:20-1:50, preferably 1:30-1: 40;
after Cu is removed, one or a plurality of combinations of P507, P204 and Cyanex272 are used as an extracting agent, and the total molar amount is 3.5 to 5.0 times of the total molar amount of the five-membered metal ions; preferably, the extracting agent is diluted by a diluent, and the diluent can be common extracting agent diluents; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of the extractant to the diluent is from 1:2 to 1:8, preferably from 1:4 to 1: 6.
The back extraction agent is one or more of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 40-100g/L, and the oil-liquid ratio O/L is 5:1-10: 1.
Preferably, in step (4):
the metal ion ratio of the regulated species of the solution is 0.98-1.0:0.98-1.0:0.98-1.0:0.98-1.0: 0.98-1.0.
The pH of the solution reaction is 10.5-11.5.
Adding the citric acid in the step (4) to obtain pentabasic salt (Fe)3++Al3++Ni2++Co2++Mn2+) 0.1-0.30 times of total molar weight.
The reaction temperature of the solution is 50-90 ℃, and the solution is continuously reacted for 2-4h after being added.
The roasting temperature is 450-800 ℃, and the roasting constant temperature time is 2-4 h.
By adopting the technical scheme, the invention has the advantages that:
(1) the method uniformly recycles the valuable metals in the anode materials of the retired ternary lithium and iron phosphate lithium batteries, wherein nickel, cobalt, manganese, iron and aluminum are recycled in a manner of a five-element high-entropy lithium battery material precursor, lithium ions in raffinate can be recycled by lithium phosphate or lithium carbonate, the recycling process is realized, and the recycling equipment is greatly simplified.
(2) The invention directly utilizes the aluminum foils in the two retired lithium battery materials, reduces the separation process of the aluminum foils and the anode powder in the mechanical disassembly process of the retired batteries, and improves the utilization rate of the aluminum foils and the anode material.
(3) The five-element high-entropy lithium battery material prepared by the invention breaks through the design concept of the traditional lithium battery material which mainly comprises one or two or three metal elements. And the high entropy effect generated by the mixing of the multiple main elements can effectively improve the thermal stability and the cycle performance of the lithium battery material.
Drawings
The invention is further described below with reference to the accompanying drawings.
Fig. 1 is an electron microscope image of a five-element high-entropy lithium battery material precursor in example 1.
Fig. 2 is an XRD pattern of the pentabasic high-entropy lithium battery material precursor in example 1.
Detailed Description
The present invention will be further described with reference to the following examples. The described embodiments and their results are only intended to illustrate the invention and should not be taken as limiting the invention described in detail in the claims.
Example 1
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 300 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, the solid-liquid mass ratio of 120g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 80 ℃ for 3h, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 2.2 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by P2043+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 3.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, the organic phase is back-extracted by 80g/L sulfuric acid solution with the oil-liquid ratio of O/L to 8:1 to obtain a second quinaryA solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:1.0:1.0:1.0: 1.0; adding citric acid in a molar amount which is 0.2 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 11.0, controlling the temperature of the reaction system to be 60 ℃, continuing to react for 2 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 700 ℃ for 3 hours in an air atmosphere to obtain the precursor of the pentabasic high-entropy lithium battery material.
Example 2
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 2 hours at 400 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 70g/L, wherein the solid-liquid mass ratio is 200g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 50 ℃ for 5h, and filtering the solution after the reaction to obtain a first solution of five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 2.6 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by P5073+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 4.0 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, back-extracting the organic phase by using 40g/L sulfuric acid solution, wherein O/L is 5:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 0.98:0.98:1.0:1.0: 1.0; adding citric acid in a molar amount of 0.1 times of the total molar amount of pentanary salt, adding sodium hydroxide solution to adjust the pH of the solution to 10.5, controlling the temperature of the reaction system to be 50 ℃, continuing to react for 4h after the addition is finished, and reactingAnd filtering, washing and drying the slurry, and then keeping the temperature of the slurry at 450 ℃ in the air atmosphere for 4 hours to obtain the five-element high-entropy lithium battery material precursor.
Example 3
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 500 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 100g/L, wherein the solid-liquid mass ratio is 70g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 60 ℃ for 4 hours, and filtering the solution after the reaction to obtain a first solution of five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 3.0 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by Cyanex2723+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 4.3 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by a sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then back-extracting the organic phase by using 50g/L sulfuric acid solution, wherein O/L is 6:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 0.98:0.98:0.98:1.0: 1.0; adding citric acid in a molar amount which is 0.2 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 11.5, controlling the temperature of a reaction system to be 70 ℃, continuing to react for 3 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 500 ℃ for 3 hours in an air atmosphere to obtain the precursor of the pentabasic high-entropy lithium battery material.
Example 4
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 2 hours at 600 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, the solid-liquid mass ratio of 150g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 90 ℃ for 2 hours, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 3.5 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in the raffinate by using the volume ratio of P204 to P507 of 1:13+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 4.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by a sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then back-extracting the organic phase by using 100g/L sulfuric acid solution, wherein O/L is 10:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:0.98:0.98:1.0: 1.0; adding citric acid with the molar weight being 0.3 times of the total molar weight of pentanary salt, adding a sodium hydroxide solution to adjust the pH of the solution to 10.5, controlling the temperature of the reaction system to be 90 ℃, continuing to react for 2 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 800 ℃ for 2 hours in an air atmosphere to obtain the precursor of the pentanary high-entropy lithium battery material.
Example 5
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 500 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 180g/L, wherein the solid-liquid mass ratio is 180g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 85 ℃ for 3.5 hours, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extractant to remove copper ions in the quinary first solution, wherein the dosage of the extractant is copper in the solutionThe ion concentration is 3.5 times, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 20; extracting Fe in the raffinate by using P204 and Cyanex272 in a volume ratio of 1:13+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 4.7 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 8; then, back-extracting the organic phase by using 80g/L sulfuric acid solution, wherein O/L is 8:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:0.98:0.98:1.0: 0.98; adding citric acid in a molar amount which is 0.2 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 11.0, controlling the temperature of the reaction system to be 80 ℃, continuing to react for 3 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 600 ℃ in the air atmosphere for 3 hours to obtain the precursor of the pentabasic high-entropy lithium battery material.
Example 6
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 5 hours at 400 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, wherein the solid-liquid mass ratio is 160g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 75 ℃ for 2.5h, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 4.0 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 30; extracting Fe in the raffinate by using P204, Cyanex272 and P507 in a volume ratio of 1:1:13+,Al3+,Ni2 +,Co2+,Mn2+Metal ions, the dosage of the extracting agent is 5.0 times of the molar weight of the metal ions to be extracted, and the extracting agent is sulfonated coalDiluting with an oil diluent, wherein the volume ratio of the sulfonated kerosene to the diluent is 1: 2; then, back-extracting the organic phase by using a 60g/L sulfuric acid solution, wherein O/L is 6:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:0.98:0.98:0.98: 0.98; adding citric acid in a molar amount which is 0.25 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 10.7, controlling the temperature of a reaction system to be 75 ℃, continuing to react for 3 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 550 ℃ in air for 3.5 hours to obtain the precursor of the pentabasic high-entropy lithium battery material.
Comparative example 1
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 300 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, the solid-liquid mass ratio of 120g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 80 ℃ for 3h, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 2.2 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by P2043+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 3.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, back-extracting the organic phase by using 80g/L sulfuric acid solution with the oil-liquid ratio of O/L to 8:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 0.1:1.0:1.0:1.0: 1.0; with addition of citric acidThe molar weight is 0.2 times of the total molar weight of the pentabasic salt, a sodium hydroxide solution is added to adjust the pH of the solution to 11.0, the temperature of a reaction system is 60 ℃, the reaction continues for 2 hours after the addition is completed, and the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 700 ℃ in the air atmosphere for 3 hours to obtain the precursor of the pentabasic high-entropy lithium battery material.
Comparative example 2
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 300 ℃ to obtain the positive plates with organic matters removed;
(2) removing aluminum foil from the positive plate obtained in the step (1), putting the positive plate into a solution with the sulfuric acid concentration of 150g/L, wherein the solid-liquid mass ratio is 120g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 80 ℃ for 3 hours, and filtering the solution after the reaction to obtain a first quaternary solution of Fe, Ni, Co and Mn;
(3) extracting the quaternary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the quaternary first solution, wherein the using amount of the extracting agent is 2.2 times of the concentration of the copper ions in the quaternary first solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by P2043+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 3.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, back-extracting the organic phase by using 80g/L sulfuric acid solution, wherein O/L is 8:1 to obtain a quaternary second solution;
(4) adjusting the concentrations of the four ions in step (3) so that c (Fe)3+):c(Ni2+):c(Co2+):c(Mn2+) 1.0:1.0:1.0: 1.0; adding citric acid with the molar weight being 0.2 times of the total molar weight of the quaternary salt, adding a sodium hydroxide solution to adjust the pH of the solution to 11.0, controlling the temperature of the reaction system to be 60 ℃, continuing to react for 2 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 700 ℃ for 3 hours in an air atmosphere to obtain the precursor of the quaternary lithium battery material.
Comparative example 3
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 300 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, the solid-liquid mass ratio of 120g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 80 ℃ for 3h, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) extracting the quinary first solution obtained in the step (2) by using a LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 2.2 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluting agent, and the volume ratio of the sulfonated kerosene to the diluting agent is 1: 50; extracting Fe in raffinate by P2043+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 3.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, back-extracting the organic phase by using 80g/L sulfuric acid solution with the oil-liquid ratio of O/L to 8:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:1.0:1.0:1.0: 1.0; adding citric acid in a molar amount which is 0.2 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 10.0, controlling the temperature of the reaction system to be 60 ℃, continuing to react for 2 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 700 ℃ for 3 hours in an air atmosphere to obtain the precursor of the pentabasic high-entropy lithium battery material.
Comparative example 4
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction for 3h at 300 ℃ to obtain the positive plates with organic matters removed;
(2) putting the positive plate obtained in the step (1) into a solution with the sulfuric acid concentration of 150g/L, the solid-liquid mass ratio of 120g/L, putting the positive plate into a water bath kettle for heating reaction at the reaction temperature of 80 ℃ for 3h, and filtering the solution after the reaction to obtain a first solution containing five elements of Fe, Al, Ni, Co and Mn;
(3) the first quinary element obtained in the step (2)Extracting the solution by using an LIX984N extracting agent to remove copper ions in the solution, wherein the using amount of the extracting agent is 2.2 times of the concentration of the copper ions in the solution, the extracting agent is diluted by using a sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 50; extracting Fe in raffinate by P2043+,Al3+,Ni2+,Co2+,Mn2+The metal ions, the dosage of the extracting agent is 3.5 times of the molar weight of the metal ions to be extracted, the extracting agent is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1: 4; then, back-extracting the organic phase by using 80g/L sulfuric acid solution with the oil-liquid ratio of O/L to 8:1 to obtain a quinary second solution;
(4) adjusting the concentration of the five ions in the step (3) to make c (Fe)3+):c(Al3+):c(Ni2+):c(Co2+):c(Mn2 +) 1.0:1.0:1.0:1.0: 1.0; adding citric acid in a molar amount which is 0.2 times of the total molar amount of the pentabasic salt, adding a sodium hydroxide solution to adjust the pH of the solution to 10.0, controlling the temperature of the reaction system to be 60 ℃, continuing to react for 2 hours after the addition is finished, filtering, washing and drying the reaction slurry, and keeping the temperature of the reaction slurry at 300 ℃ for 3 hours in an air atmosphere to obtain the precursor of the pentabasic high-entropy lithium battery material.
The five-element high-entropy lithium battery material prepared from the retired lithium battery positive plate is subjected to discharge capacity test, and the performance analysis is shown in table 1; the test is carried out by using a BT2000 battery test system (manufactured by Japan), the voltage range is 2.5-5.0V, the test temperature is respectively 25 ℃, 55 ℃, and the multiplying power performance charge-discharge current is 0.2C.
Table 1: performance analysis of five-element high-entropy lithium battery material prepared from retired lithium battery positive plate
The above description is only for the specific implementation of the claimed patent, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the principle of the claimed patent, and these modifications and additions should also fall within the protection scope of the present application.
Claims (10)
1. A method for preparing a five-element high-entropy lithium battery material precursor from an out-of-service lithium battery positive plate comprises the following steps:
(1) mixing and roasting the retired ternary lithium iron phosphate battery positive plate to obtain a positive plate with organic matters removed;
(2) acid leaching the positive plate obtained in the step (1), and filtering the reaction solution to obtain a first solution of five elements of Fe, Al, Ni, Co and Mn;
(3) removing Cu from the quinary first solution in the step (2), and extracting Fe in the quinary first solution by using an extracting agent3+,Al3+,Ni2+,Co2+,Mn2+Metal ions are stripped to obtain a stripping five-element second solution;
(4) and adjusting the proportion of each metal ion in the quinary second solution, carrying out coprecipitation reaction on the metal ions, the sodium hydroxide solution and the citric acid solution, filtering, washing and drying the reaction slurry, and roasting to obtain the precursor of the quinary high-entropy lithium battery material.
2. The method as claimed in claim 1, wherein the calcination temperature in step (1) is 300-600 ℃ and the constant temperature time is 2-6 h.
3. The method according to claim 1, wherein the acid used in step (2) is one or more of sulfuric acid, hydrochloric acid, phosphoric acid; preferably, the acid concentration in the step (2) is 70-200g/L, and the solid-to-liquid ratio is 50-200 g/L.
4. The method of claim 1, wherein the acid leaching temperature in the step (2) is 50-90 ℃ and the reaction time is 2-5 h.
5. The method of claim 1, wherein:
step (3) has one or more of the following characteristics:
in the step (3), an extraction method is adopted for removing Cu, the extractant is LIX984N, and the molar dosage of the extractant is 2.0-4.0 times of the molar dosage of the copper ions in the solution; preferably, the extracting agent is diluted by a diluent, and the diluent can be common extracting agent diluents; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of the extracting agent to the diluting agent is 1:20-1:50, preferably 1:30-1: 40;
in the step (3), after removing Cu, one or a combination of more of an extracting agent P507, P204 and Cyanex272 is used, and the total molar amount is 3.5-5.0 times of the total molar amount of the five-membered metal ions; preferably, the extracting agent is diluted by a diluent, and the diluent can be common extracting agent diluents; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of the extractant to the diluent is from 1:2 to 1:8, preferably from 1:4 to 1: 6.
6. The method according to claim 1, wherein the stripping agent in the step (3) is one or more of sulfuric acid, hydrochloric acid and nitric acid, the acid concentration is 40-100g/L, and the oil-to-oil ratio O/L is 5:1-10: 1.
7. The method according to claim 1, wherein the metal ion ratio of the species after the solution adjustment in the step (4) is 0.98-1.0:0.98-1.0:0.98-1.0:0.98-1.0: 0.98-1.0.
8. The method according to claim 1, wherein the solution reaction pH in the step (4) is 10.5 to 11.5.
9. The method according to claim 1, wherein citric acid is added in the step (4) in a molar amount of pentabasic salt (Fe)3++Al3++Ni2++Co2++Mn2+) 0.1-0.3 times of total molar weight.
10. The method of claim 1, wherein:
step (4) has one or more of the following characteristics:
in the step (4), the reaction temperature of the solution is 50-90 ℃, and the solution is continuously reacted for 2-4h after being added;
the roasting temperature in the step (4) is 450-.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010667810.8A CN111799524B (en) | 2020-07-13 | 2020-07-13 | Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202010667810.8A CN111799524B (en) | 2020-07-13 | 2020-07-13 | Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate |
Publications (2)
Publication Number | Publication Date |
---|---|
CN111799524A true CN111799524A (en) | 2020-10-20 |
CN111799524B CN111799524B (en) | 2023-12-26 |
Family
ID=72808324
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202010667810.8A Active CN111799524B (en) | 2020-07-13 | 2020-07-13 | Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN111799524B (en) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN112830789A (en) * | 2020-12-31 | 2021-05-25 | 南京理工大学 | High-entropy boride powder and preparation method thereof |
CN114381600A (en) * | 2022-01-28 | 2022-04-22 | 重庆大学 | Method for recovering copper in citric acid leachate by organic solvent extraction method |
WO2022088641A1 (en) * | 2020-10-29 | 2022-05-05 | 广东邦普循环科技有限公司 | Non-full extraction battery recovery method |
CN114725365A (en) * | 2022-04-02 | 2022-07-08 | 常州大学 | B-site intermediate entropy pyrochlore structure oxide battery negative electrode material and preparation method thereof |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
CN107267759A (en) * | 2017-06-12 | 2017-10-20 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive recovering process of anode material for lithium-ion batteries |
CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
CN108390119A (en) * | 2018-03-23 | 2018-08-10 | 上海应用技术大学 | A kind of recovery and treatment method of LiFePO4/ternary-lithium titanate battery |
CN109750163A (en) * | 2018-12-12 | 2019-05-14 | 江西赣锋循环科技有限公司 | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery |
CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
CN111285403A (en) * | 2020-02-19 | 2020-06-16 | 中国恩菲工程技术有限公司 | Purification treatment method of manganese sulfate solution |
-
2020
- 2020-07-13 CN CN202010667810.8A patent/CN111799524B/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106319228A (en) * | 2016-08-26 | 2017-01-11 | 荆门市格林美新材料有限公司 | Method for recycling nickel, cobalt and manganese synchronously from waste residues containing nickel, cobalt and manganese |
CN106997975A (en) * | 2017-06-06 | 2017-08-01 | 安徽安凯汽车股份有限公司 | A kind of method of waste lithium iron phosphate battery and lithium manganate battery regeneration |
CN107267759A (en) * | 2017-06-12 | 2017-10-20 | 合肥国轩高科动力能源有限公司 | A kind of comprehensive recovering process of anode material for lithium-ion batteries |
CN107666022A (en) * | 2017-09-25 | 2018-02-06 | 湖南工业大学 | Lithium, the recovery method of nickel cobalt manganese in a kind of discarded tertiary cathode material |
CN108390119A (en) * | 2018-03-23 | 2018-08-10 | 上海应用技术大学 | A kind of recovery and treatment method of LiFePO4/ternary-lithium titanate battery |
CN109750163A (en) * | 2018-12-12 | 2019-05-14 | 江西赣锋循环科技有限公司 | A kind of method of tertiary cathode material and iron lithium anode material synthetical recovery |
CN111118294A (en) * | 2020-01-15 | 2020-05-08 | 北京矿冶科技集团有限公司 | Method for recycling valuable metals from waste lithium ion battery materials step by step |
CN111285403A (en) * | 2020-02-19 | 2020-06-16 | 中国恩菲工程技术有限公司 | Purification treatment method of manganese sulfate solution |
Non-Patent Citations (1)
Title |
---|
ABHISHEK SARKAR ET AL.: "High entropy oxides for reversible energy storage", 《NATURE COMMUNICATIONS》, vol. 9, pages 1 - 9 * |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2022088641A1 (en) * | 2020-10-29 | 2022-05-05 | 广东邦普循环科技有限公司 | Non-full extraction battery recovery method |
US11920213B2 (en) | 2020-10-29 | 2024-03-05 | Guangdong Brunp Recycling Technology Co., Ltd. | Method for recycling battery by incomplete extraction |
CN112830789A (en) * | 2020-12-31 | 2021-05-25 | 南京理工大学 | High-entropy boride powder and preparation method thereof |
CN114381600A (en) * | 2022-01-28 | 2022-04-22 | 重庆大学 | Method for recovering copper in citric acid leachate by organic solvent extraction method |
CN114725365A (en) * | 2022-04-02 | 2022-07-08 | 常州大学 | B-site intermediate entropy pyrochlore structure oxide battery negative electrode material and preparation method thereof |
CN114725365B (en) * | 2022-04-02 | 2024-03-15 | 常州大学 | B-site medium-entropy pyrochlore structure oxide battery anode material and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN111799524B (en) | 2023-12-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN111799524B (en) | Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate | |
CN111206148B (en) | Method for recycling and preparing ternary cathode material by using waste ternary lithium battery | |
CN107196007B (en) | Lithium battery recycling method | |
CN112467241B (en) | Short-process recycling method for ternary cathode material, recycled material and application | |
CN111129632B (en) | Method for recycling anode and cathode mixed materials of waste ternary lithium ion battery | |
CN110013822B (en) | Method for recycling waste lithium ion batteries and co-producing lithium adsorbent | |
CN103326088B (en) | Comprehensive recovery method of waste lithium ion battery | |
CN106929664B (en) | A method of recycling lithium from waste and old ternary lithium ion battery | |
CN110760686A (en) | Method for recovering lithium from waste lithium ion battery | |
CN107196004A (en) | A kind of method that valuable metal is reclaimed in the electrokinetic cell from applying waste lithium ionic | |
CN108400399A (en) | A kind of method that waste lithium manganese oxide battery prepares lithium manganese phosphate/carbon positive electrode | |
CN109256596B (en) | Method and system for reversely preparing aluminum-doped ternary precursor | |
CN113285135A (en) | Method for recycling multiple components of waste lithium iron phosphate battery | |
CN111261969B (en) | Method for recycling and regenerating lithium iron phosphate waste battery anode material | |
CN109439914A (en) | A method of the Selective Separation lithium from waste lithium ion cell anode material extract | |
CN111370799A (en) | Pretreatment method for failure lithium ion battery anode material | |
CN111321297B (en) | Method for recovering valuable metals from waste lithium ion batteries | |
CN112573586A (en) | Method for preparing cobalt oxide by using waste ternary nickel cobalt lithium manganate battery | |
CN112063847A (en) | Method for recycling ternary lithium battery positive electrode material | |
CN104466293B (en) | The renovation process of lithium ion cell anode material lithium cobaltate waste material | |
Qin et al. | Recovery and reuse of spent LiFePO4 batteries | |
CN108910965B (en) | Method for preparing ternary hydroxide precursor | |
CN105355997B (en) | A kind of separation method and its application of lithium battery collector and active material | |
CN108103323B (en) | A kind of recovery method of the positive electrode of nickel cobalt manganese old and useless battery | |
CN112591806A (en) | Method for recovering and regenerating anode active material of waste lithium ion battery |
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 |