CN111799524B - Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate - Google Patents
Method for preparing pentabasic high-entropy lithium battery material precursor by retired lithium battery positive plate Download PDFInfo
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- CN111799524B CN111799524B CN202010667810.8A CN202010667810A CN111799524B CN 111799524 B CN111799524 B CN 111799524B CN 202010667810 A CN202010667810 A CN 202010667810A CN 111799524 B CN111799524 B CN 111799524B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 47
- 239000000463 material Substances 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002243 precursor Substances 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 67
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 30
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 24
- 238000000605 extraction Methods 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000002386 leaching Methods 0.000 claims abstract description 5
- 238000000975 co-precipitation Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000005406 washing Methods 0.000 claims abstract description 3
- 239000003085 diluting agent Substances 0.000 claims description 55
- 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 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 22
- 229910001431 copper ion Inorganic materials 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 17
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910052748 manganese Inorganic materials 0.000 claims description 12
- 239000012066 reaction slurry Substances 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 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 5
- 239000010949 copper Substances 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 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
- 238000007865 diluting Methods 0.000 claims 2
- 238000004064 recycling Methods 0.000 abstract description 13
- 239000002002 slurry Substances 0.000 abstract 1
- 239000011572 manganese Substances 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 10
- 239000012074 organic phase Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-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
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- -1 copper aluminum iron Chemical compound 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
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005955 Ferric phosphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 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
- 239000011889 copper foil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011978 dissolution method Methods 0.000 description 1
- 229940032958 ferric phosphate Drugs 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 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
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229920006255 plastic film Polymers 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 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
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 recycling of lithium batteries, and particularly relates to a method for preparing a pentabasic high-entropy lithium battery material precursor from a retired lithium battery positive plate, which comprises the steps of mixing and roasting 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 five-membered first solution; removing Cu from the pentad first solution, extracting metal ions in the pentad first solution by using an extracting agent, and carrying out back extraction to obtain a back-extracted pentad second solution; adjusting the proportion of each metal ion in the pentary second solution, performing coprecipitation reaction, washing slurry, filtering, drying and roasting to obtain a pentary high-entropy lithium battery material precursor; according to the method, retired ternary and lithium iron phosphate positive plates are uniformly recycled, so that the recycling process and recycling cost are greatly simplified, and the prepared five-membered 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 pentabasic high-entropy lithium battery material precursor from a retired lithium battery positive plate.
Background
In recent years, as new energy automobiles continue to be paid attention to and developed, replacement of conventional automobiles has become a necessary trend. The new energy automobile creates green trip and brings corresponding difficult problems, the service life of the lithium ion power battery serving as the heart of the new energy automobile is only 5 years on average, and the accumulated scrapping amount of the power battery of the electric automobile in China reaches the scale of 12 ten thousand to 17 ten thousand tons by 2020. And because of the complex structure of the lithium ion power battery, the recovery cost is high, the process is imperfect, and the recovery and the utilization are always in a low-state.
At present, an acid dissolution method is one of the main methods for recovering valuable metal materials in lithium iron phosphate, as patent 201710657055.3 discloses a recovery method of waste lithium iron phosphate anode materials, wherein the lithium iron powder from which organic matters are removed is leached by sulfuric acid, the PH of the solution is regulated to obtain ferric phosphate, and sodium carbonate is added to generate lithium carbonate after the PH of the solution is continuously regulated; the retired ternary material is mainly utilized by preparing ternary positive electrode materials through recycling and regeneration, as in patent CN107419096B, ternary waste is leached by inorganic acid, copper aluminum iron is removed, and then alkaline condition coprecipitation is carried out to obtain ternary material precursors, and the ternary material precursors and lithium carbonate are ball-milled and then calcined to prepare the regenerated ternary positive electrode materials. Although the existing retired ternary and lithium iron separate recovery process is mature, the two material recovery processes are quite different and cannot be uniformly recovered, so that 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 disassembly and separation, such as CN105811040B, and waste lithium batteries are separated by water type induced draft breakers, magnetic separators, horizontal winnowing machines, water type friction machines, first vortex separators, second vortex separators and other devices, so that the separation purity of materials such as plastics, diaphragms, stainless steel, aluminum plastic films, aluminum, plastics, copper foils, aluminum foils, graphite and the like can reach 94-99%. The method for recycling the aluminum foil has the advantages that on one hand, the recycling efficiency is not ideal, and on the other hand, the aluminum remained in the anode powder brings certain difficulty to the subsequent impurity removal and recycling.
Currently, the positive electrode materials of the power battery are mainly lithium iron phosphate (LFP), ternary (NCA/NCM) materials and lithium manganate. Although the performance advantages of each material are obvious, the respective disadvantages are not ignored, wherein the lithium iron phosphate has lower capacity density and lower energy density; lithium manganate has poor cycle performance and short service life; at present, although the ternary material is widely applied due to the ultrahigh capacity and rate capability, the preparation cost is high, and the poor safety performance is always a problem to be further solved.
Therefore, research and development of a technical scheme for uniformly and efficiently recycling retired ternary and lithium iron phosphate battery materials and breaking through the defects of the traditional lithium battery materials in terms of structural performance have become an important target and direction of the development of the current lithium battery materials.
At present, a method for uniformly recycling all valuable metals in retired ternary and lithium iron phosphate battery positive plates does not exist, and a method for solving the problems of poor high-temperature stability and rapid capacity decay of lithium battery materials through the mixed high-entropy effect of multiple principal elements does not exist.
Disclosure of Invention
In order to solve the problems of difficult uniform recovery of metals in the existing retired ternary and lithium iron phosphate battery positive plates, poor high-temperature stability and faster capacity decay of the traditional lithium battery material, the invention utilizes the preparation of the five-membered high-entropy material to solve the problem of complicated recovery process, so as to achieve the aim of improving the safety of the ternary material and the energy density of the lithium iron phosphate. The ternary and lithium iron phosphate pole pieces roasted at low temperature are uniformly dissolved, the high-valence metal elements are extracted and back extracted to obtain sulfate solution by adopting an extraction method, and finally the pentary high-entropy lithium battery material precursor is prepared.
The invention provides a method for preparing a pentatomic high-entropy lithium battery material precursor by utilizing a retired lithium battery anode material, which is characterized by comprising the following steps:
(1) Mixing and roasting the retired ternary and 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Removing Cu from the five-membered first solution in the step (2), and extracting Fe in the solution by using an extractant 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions are back extracted to obtain a back extracted five-membered second solution;
(4) And adjusting the proportion of each metal ion in the pentad second solution, performing coprecipitation reaction with a sodium hydroxide solution and a citric acid solution, filtering, washing, drying and roasting the reaction slurry to obtain the pentad high-entropy lithium battery material precursor.
Preferably, in step (1):
the roasting temperature is 300-600 ℃, and the constant temperature time is 2-6h.
Preferably, in step (2):
the acid is one or more of sulfuric acid, hydrochloric acid and phosphoric acid.
The concentration of the acid is 70-200g/L, and the solid-liquid ratio is 50-200g/L.
The acid leaching temperature is 50-90 ℃ and the reaction time is 2-5h.
Preferably, in step (3):
in the step (2), cu is removed by adopting an extraction method, the extracting agent is LIX984N, and the molar dosage of the extracting agent is 2.0-4.0 times of the molar dosage of copper ions in the solution; preferably, the extractant is diluted with a diluent, which is a common extractant diluent; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of extractant to diluent is from 1:20 to 1:50, preferably from 1:30 to 1:40;
after Cu is removed, extracting agent is one or a combination of more of P507, P204 and Cyanex272, and the total molar amount is 3.5-5.0 times of the total molar amount of the five-membered metal ions; preferably, the extractant is diluted with a diluent, which is a common extractant diluent; preferably, the diluent is selected from sulfonated kerosene; preferably, the volume ratio of extractant to diluent is from 1:2 to 1:8, preferably from 1:4 to 1:6.
The back extraction agent is one or a combination of 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 species after the solution adjustment 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.
The molar quantity of the citric acid added in the step (4) is five-membered salt (Fe 3+ +Al 3+ +Ni 2+ +Co 2+ +Mn 2+ ) 0.1 to 0.30 times the total molar amount.
The reaction temperature of the solution is 50-90 ℃, and the reaction is continued for 2-4h after the solution is added.
The roasting temperature is 450-800 ℃, and the roasting constant temperature time is 2-4h.
The invention adopts the technical proposal and has the advantages that:
(1) According to the invention, valuable metals in retired ternary and lithium iron phosphate battery anode materials are uniformly recycled, wherein nickel, cobalt, manganese, iron and aluminum are recycled in a mode of five-membered high-entropy lithium battery material precursors, lithium ions in raffinate can be recycled in a mode of lithium phosphate or lithium carbonate, the recycling process is greatly simplified, and recycling equipment is greatly simplified.
(2) According to the invention, the aluminum foils in the two retired lithium battery materials are directly utilized, so that the separation process of the aluminum foils and the positive electrode powder in the mechanical disassembly process of the retired battery is reduced, and the utilization rate of the aluminum foils and the positive electrode material is improved.
(3) The five-membered high-entropy lithium battery material prepared by the invention breaks through the design concept of the traditional lithium battery material mainly comprising one or two or three metal elements. And the high entropy effect generated by mixing multiple principal 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 pentad high entropy lithium battery material precursor in example 1.
Fig. 2 is an XRD pattern of a pentad high entropy lithium battery material precursor in example 1.
Detailed Description
The invention is further described below with reference to examples. The described embodiments and the results thereof are only intended to illustrate the invention and should not limit the invention as detailed in the claims.
Example 1
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 300 ℃ for 3 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 120g/L, putting 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 from raffinate by P204 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 3.5 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using 80g/L sulfuric acid solution with the oil liquid ratio of O/L=8:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:1.0:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is adjusted to 11.0 by adding sodium hydroxide solution, the temperature of the reaction system is 60 ℃, the reaction is continued for 2 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 700 ℃ for 3 hours in the air atmosphere.
Example 2
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 400 ℃ for 2 hours to obtain 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 and solid-liquid mass ratio of 200g/L, putting into a water bath kettle for heating reaction at 50 ℃ for 5 hours, and filtering the solution after the reaction to obtain a five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 with P507 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 4.0 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using a sulfuric acid solution with the concentration of 40g/L and O/L=5:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =0.98:0.98:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.1 time of the total molar quantity of the pentabasic salt, the PH of the solution is regulated to 10.5 by adding sodium hydroxide solution, the temperature of the reaction system is 50 ℃, the reaction is continued for 4 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 450 ℃ for 4 hours in the air atmosphere.
Example 3
(1) 100g of retired ternary and lithium iron phosphate positive plates are respectively taken to carry out roasting reaction for 3 hours at 500 ℃ to obtain 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 and solid-liquid mass ratio of 70g/L, putting into a water bath kettle for heating reaction at 60 ℃ for 4 hours, and filtering the solution after the reaction to obtain a five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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; the raffinate was extracted with Cyanex272 for Fe 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 4.3 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then 50g/L sulfuric acid solution is used for back extraction of the organic phase with O/L=6:1 to obtain five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =0.98:0.98:0.98:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is adjusted to 11.5 by adding sodium hydroxide solution, the temperature of the reaction system is 70 ℃, the reaction is continued for 3 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 500 ℃ for 3 hours in the air atmosphere.
Example 4
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 600 ℃ for 2 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 150g/L, putting into a water bath kettle for heating reaction at 90 ℃ for 2 hours, and filtering the solution after the reaction to obtain a five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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; the raffinate is used for extracting Fe in the raffinate by using the volume ratio of P204 to P507 of 1:1 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant dosage is 4.5 times of the metal ion molar quantity to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using 100g/L sulfuric acid solution, wherein O/L=10:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:0.98:0.98:1.0:1.0; the molar quantity of the citric acid added is 0.3 times of the total molar quantity of the pentabasic salt, the PH of the solution is regulated to 10.5 by adding sodium hydroxide solution, the temperature of the reaction system is 90 ℃, the reaction is continued for 2 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 800 ℃ for 2 hours in the air atmosphere.
Example 5
(1) 100g of retired ternary and lithium iron phosphate positive plates are respectively taken to carry out roasting reaction for 3 hours at 500 ℃ to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 180g/L and solid-liquid mass ratio of 180g/L, putting into a water bath kettle for heating reaction at 85 ℃ for 3.5h, and filtering the solution after the reaction to obtain a five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 1:20; the raffinate was subjected to extraction of Fe with P204 and Cyanex272 in a volume ratio of 1:1 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 4.7 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:8; then, carrying out back extraction on the organic phase by using 80g/L sulfuric acid solution with O/L=8:1 to obtain five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:0.98:0.98:1.0:0.98; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is adjusted to 11.0 by adding sodium hydroxide solution, the temperature of the reaction system is 80 ℃, the reaction is continued for 3 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 600 ℃ for 3 hours in the air atmosphere.
Example 6
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 400 ℃ for 5 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 160g/L, putting 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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; the raffinate was subjected to extraction of Fe with P204, cyanex272 and P507 in a volume ratio of 1:1:1 3+ ，Al 3+ ，Ni 2 + ，Co 2+ ，Mn 2+ The metal ions, the extractant is 5.0 times of the molar quantity of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:2; then, carrying out back extraction on the organic phase by using a sulfuric acid solution with the concentration of 60g/L and O/L=6:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:0.98:0.98:0.98:0.98; the molar quantity of the citric acid added is 0.25 times of the total molar quantity of the five-membered salt, the PH of the solution is regulated to 10.7 by adding sodium hydroxide solution, the temperature of the reaction system is 75 ℃, the reaction is continued for 3 hours after the addition is completed, and the reaction slurry is filtered, washed and dried and then is subjected to air atmosphere at 550 DEG CAnd keeping the temperature for 3.5 hours to obtain the pentatomic high-entropy lithium battery material precursor.
Comparative example 1
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 300 ℃ for 3 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 120g/L, putting 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 from raffinate by P204 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 3.5 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using 80g/L sulfuric acid solution with the oil liquid ratio of O/L=8:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =0.1:1.0:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is adjusted to 11.0 by adding sodium hydroxide solution, the temperature of the reaction system is 60 ℃, the reaction is continued for 2 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 700 ℃ for 3 hours in the air atmosphere.
Comparative example 2
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 300 ℃ for 3 hours to obtain 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 sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 120g/L, putting the solution into a water bath kettle for heating reaction, wherein the reaction temperature is 80 ℃, the reaction time is 3 hours, and filtering the solution after the reaction to obtain a quaternary first solution of Fe, ni, co and Mn;
(3) Extracting the quaternary first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 from raffinate by P204 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 3.5 times of the molar weight of the metal ions to be extracted, the extractant 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 using 80g/L sulfuric acid solution, and O/L=8:1, so as to obtain quaternary second solution;
(4) Adjusting the concentrations of the four ions in step (3) so that c (Fe 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2+ ) =1.0:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the quaternary salt, the PH of the solution is adjusted to 11.0 by adding sodium hydroxide solution, the temperature of the reaction system is 60 ℃, the reaction is continued for 2 hours after the addition is completed, and the quaternary lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 700 ℃ for 3 hours in the air atmosphere.
Comparative example 3
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 300 ℃ for 3 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 120g/L, putting 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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; p for raffinate204 to extract Fe therein 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 3.5 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using 80g/L sulfuric acid solution with the oil liquid ratio of O/L=8:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:1.0:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is regulated to 10.0 by adding sodium hydroxide solution, the temperature of the reaction system is 60 ℃, the reaction is continued for 2 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 700 ℃ for 3 hours in the air atmosphere.
Comparative example 4
(1) Respectively taking 100g of retired ternary and lithium iron phosphate positive plates, and carrying out roasting reaction at 300 ℃ for 3 hours to obtain positive plates with organic matters removed;
(2) Putting the positive plate obtained in the step (1) into a solution with sulfuric acid concentration of 150g/L and solid-liquid mass ratio of 120g/L, putting 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Extracting the five-membered first solution obtained in the step (2) by using an LIX984N extracting agent to remove copper ions, 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 from raffinate by P204 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions, the extractant is 3.5 times of the molar weight of the metal ions to be extracted, the extractant is diluted by sulfonated kerosene diluent, and the volume ratio of the sulfonated kerosene to the diluent is 1:4; then, carrying out back extraction on the organic phase by using 80g/L sulfuric acid solution with the oil liquid ratio of O/L=8:1 to obtain a five-membered second solution;
(4) Adjusting the concentrations of the five ions in step (3) so that c (Fe 3+ ):c(Al 3+ ):c(Ni 2+ ):c(Co 2+ ):c(Mn 2 + ) =1.0:1.0:1.0:1.0:1.0; the molar quantity of the citric acid added is 0.2 times of the total molar quantity of the pentabasic salt, the PH of the solution is regulated to 10.0 by adding sodium hydroxide solution, the temperature of the reaction system is 60 ℃, the reaction is continued for 2 hours after the addition is completed, and the pentabasic high-entropy lithium battery material precursor is obtained after the reaction slurry is filtered, washed and dried and then is kept at the constant temperature of 300 ℃ for 3 hours in the air atmosphere.
The discharge capacity test is carried out on the five-membered high-entropy lithium battery material prepared from the retired lithium battery positive plate, and the performance analysis is shown in table 1; the test was conducted using a BT2000 battery test system (manufactured by japan) with a voltage range of 2.5 to 5.0V, a test temperature of 25 ℃ and a rate performance charge-discharge current of 0.2C, respectively.
Table 1: performance analysis of five-membered high-entropy lithium battery material prepared from retired lithium battery positive plate
The foregoing is merely illustrative of the specific embodiments of this application and it will be appreciated by those skilled in the art that variations and modifications may be made without departing from the principles of this application and yet remain within the scope of this application.
Claims (10)
1. A method for preparing a pentatomic high-entropy lithium battery material precursor from a retired lithium battery positive plate comprises the following steps:
(1) Mixing and roasting the retired ternary and 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 five-element first solution of Fe, al, ni, co and Mn;
(3) Removing Cu from the five-membered first solution in the step (2), and extracting Fe in the solution by using an extractant 3+ ，Al 3+ ，Ni 2+ ，Co 2+ ，Mn 2+ The metal ions are back extracted to obtain a back extracted five-membered second solution;
(4) Regulating the proportion of each metal ion in the pentad second solution, performing coprecipitation reaction with a sodium hydroxide solution and a citric acid solution, filtering, washing, drying and roasting the reaction slurry to obtain a pentad high-entropy lithium battery material precursor;
the roasting temperature in the step (1) is 300-600 ℃, and the constant temperature time is 2-6h;
in the step (3), cu is removed by adopting an extraction method, the extracting agent is LIX984N, and the molar dosage of the extracting agent is 2.0-4.0 times of the molar dosage of copper ions in the solution; diluting the extractant with a diluent; the volume ratio of the extractant to the diluent is 1:20-1:50;
the Cu is removed in the step (3), and the total molar amount of the extractant is one or a combination of more of P507, P204 and Cyanex272, which is 3.5-5.0 times of the total molar amount of the five-membered metal ions; diluting the extractant with a diluent; the volume ratio of the extractant to the diluent is 1:2-1:8;
the back extractant in the step (3) is one or a combination of more of sulfuric acid, hydrochloric acid and nitric acid;
the reaction temperature of the solution in the step (4) is 50-90 ℃, and the solution is continuously reacted for 2-4 hours after the solution is added;
the roasting temperature in the step (4) is 450-800 ℃, and the roasting constant temperature time is 2-4h.
2. The method according to claim 1, wherein the volume ratio of the Cu-removing extractant and the diluent in step (3) is 1:30 to 1:40.
3. The method of claim 1, wherein the volume ratio of extractant to diluent used in step (3) after Cu removal is 1:4 to 1:6.
4. A process according to claim 1 or 2 or 3, wherein the diluent is a sulphonated kerosene.
5. The method according to claim 1, wherein the acid used in step (2) is one or more of sulfuric acid, hydrochloric acid, phosphoric acid; in the step (2), the acid concentration is 70-200g/L, and the solid-liquid ratio is 50-200g/L.
6. The method according to claim 1, characterized in that: the acid leaching temperature in the step (2) is 50-90 ℃ and the reaction time is 2-5h.
7. The process of claim 1 wherein the acid concentration of the stripping agent in step (3) is 40-100g/L and the oil to O/L ratio is 5:1-10:1.
8. The method of claim 1, wherein the ratio of the five metal ions after the solution adjustment in step (4) is 0.98-1.0:0.98-1.0:0.98-1.0:0.98-1.0:0.98-1.0.
9. The method according to claim 1, wherein the solution in step (4) has a reaction pH of 10.5 to 11.5.
10. The method according to claim 1, wherein the citric acid is added in the step (4) in a molar amount of Fe 3+ 、Al 3+ 、Ni 2+ 、Co 2+ And Mn of 2+ 0.1 to 0.3 times the total molar amount.
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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 |
|---|
| High entropy oxides for reversible energy storage;Abhishek Sarkar et al.;《nature communications》;第9卷;第1-9页 * |
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