CN117276730A - Method for recycling waste lithium cobaltate and lithium iron phosphate mixed materials and regenerating waste lithium cobaltate and lithium iron phosphate mixed materials into lithium iron phosphate - Google Patents
Method for recycling waste lithium cobaltate and lithium iron phosphate mixed materials and regenerating waste lithium cobaltate and lithium iron phosphate mixed materials into lithium iron phosphate Download PDFInfo
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- CN117276730A CN117276730A CN202310027810.5A CN202310027810A CN117276730A CN 117276730 A CN117276730 A CN 117276730A CN 202310027810 A CN202310027810 A CN 202310027810A CN 117276730 A CN117276730 A CN 117276730A
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- Prior art keywords
- lithium
- iron phosphate
- lithium iron
- solution
- cobaltate
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- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 title claims abstract description 101
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 65
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000002699 waste material Substances 0.000 title abstract description 44
- 230000001172 regenerating effect Effects 0.000 title abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000002244 precipitate Substances 0.000 claims abstract description 29
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 22
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims abstract description 19
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims abstract description 19
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 17
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 14
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 14
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 14
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 9
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000007864 aqueous solution Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 8
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 19
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 19
- 239000000843 powder Substances 0.000 abstract description 10
- 238000001914 filtration Methods 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000007774 positive electrode material Substances 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 description 17
- 238000002386 leaching Methods 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 239000011888 foil Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910000398 iron phosphate Inorganic materials 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- -1 therefore Chemical compound 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4242—Regeneration of electrolyte or reactants
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a method for recycling a mixed material of waste lithium cobaltate and lithium iron phosphate and regenerating the mixed material into lithium iron phosphate, which comprises the following specific steps: firstly, carrying out pretreatment such as discharging, disassembling and separating on waste lithium cobalt oxide batteries and lithium iron phosphate batteries to obtain lithium cobalt oxide and lithium iron phosphate powder, and fully mixing the lithium cobalt oxide and the lithium iron phosphate powder to obtain a mixed material which is mixed with Fe-containing material 3+ Mixing and stirring the solution, filtering to obtain ferric phosphate precipitate and Fe-containing solution 2+ Mixing solution of Co and Li, adding alkaline matter to regulate pH, filtering to separate to obtain cobalt hydroxide precipitate and lithium ion solution, adding carbonate to form lithium carbonate precipitate, and final filteringAnd calcining the ferric phosphate at high temperature to regenerate lithium iron phosphate. According to the treatment method provided by the invention, not only is the environmental pollution caused by waste lithium cobaltate and lithium iron phosphate effectively prevented, but also the waste materials in the waste lithium cobaltate and lithium iron phosphate can be completely recovered and efficiently regenerated into lithium iron phosphate positive electrode materials for use.
Description
Technical Field
The invention relates to the field of waste lithium ion battery recovery, in particular to a method for recovering waste lithium cobaltate and lithium iron phosphate mixed materials and regenerating the mixed materials into lithium iron phosphate.
Background
For many years, the production and application of electric vehicles have been significantly increased under the push of urgent demands for improving the environment and saving energy. Meanwhile, a large number of scrapped lithium ion batteries are rapidly accumulated, and if the scrapped batteries are not properly treated, heavy metals and other toxic and harmful substances contained in the scrapped batteries can cause serious environmental pollution. The waste battery is a battery which is discarded after long-time use, has a larger drop in the existing capacity than the initial capacity or has a larger damage to the battery structure, and cannot meet the normal use. Taking an electric automobile as an example, the service life of the power battery is about 3-5 years. When the capacity of the power battery is reduced to less than 80% of the initial capacity, the power battery can be considered as incapable of meeting the daily use, and a new battery needs to be replaced.
The lithium resources contained in the lithium ion battery are national strategic metals, and are also the shortage resources in China, so that the recovery significance of lithium in the positive electrode material is great. In addition, the recycling of the lithium ion battery not only can reduce environmental pollution, but also has certain economic benefit and great propulsion effect on the sustainable development of the battery industry.
Since the commercialization time of lithium cobaltate and lithium iron phosphate is long, there are a large number of retired waste lithium cobaltate and lithium iron phosphate batteries on the market. The current common recovery method for these two batteries is acid leaching, i.e. leaching valuable metals with inorganic and organic acids. The acid leaching method is to completely destroy the integral structure of the material, so that all metal ions in the material are transferred into an aqueous solution, and selective separation cannot be achieved. The acid leaching process also has the following problems: the process flow is complex, the operation steps are complex, the economic benefit is low, a large amount of water resources are consumed, and the influence of the subsequently generated wastewater on the environment is large.
Disclosure of Invention
The present inventors have made intensive studies to solve the above problems, and have proposed a salt leaching method for recovering high-value metals from two materials simultaneously, using a leaching reagent containing only Fe 3+ The solution does not need to use pickle liquor or add additional reagents such as oxidant or reducing agent, and the energy consumption, labor cost and water consumption are lower than those of the traditional acid leaching method, the process flow is simple, the complex operation is avoided, and the method is a green and efficient recovery method.
The invention provides a method for recycling a mixed material of lithium cobaltate and lithium iron phosphate, which comprises the following steps,
step 1: immersing lithium cobalt oxide and lithium iron phosphate in an acidic aqueous solution, wherein the pH value of the acidic aqueous solution is 0.5-2.5, and the acidic aqueous solution contains Fe 3+ ，Fe 3+ The concentration of the Fe of the lithium iron phosphate is 100-1000 mg/L 2+ By Fe 3+ Displacing to form ferric phosphate precipitate, and displacing the obtained Fe in the solution 2+ Decomposing lithium cobaltate to enable Co and Li to enter a solution, and performing first solid-liquid separation; step 2: adjusting the pH value of the solution after the first solid-liquid separation to be alkaline to generate cobalt hydroxide precipitate, and performing the second solid-liquid separation; step 3: adding carbonate into the solution after the second solid-liquid separation to generate lithium carbonate precipitate, and performing the third solid-liquid separation; the mass ratio of the lithium cobaltate to the lithium iron phosphate is 1:1-1:6.
Preferably, the lithium carbonate precipitate and the ferric phosphate precipitate are mixed and roasted to obtain the regenerated lithium iron phosphate.
Preferably, fe in the acidic aqueous solution 3+ From one or more of ferric sulphate, ferric nitrate and ferric chloride.
Preferably, the reaction temperature in the step 1 is 20-90 ℃.
Preferably, stirring is performed in the step 1, wherein the stirring time is 20-120 min, and the stirring speed is 100-300 r/min.
Preferably, in the step 2, the pH of the solution after the first solid-liquid separation is adjusted to be alkaline, which is adjusted by one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, in the step 3, carbonate is added to the solution after the second solid-liquid separation, wherein the carbonate comprises one or more of sodium carbonate, calcium carbonate and potassium carbonate.
Preferably, in the step 1, the lithium cobaltate and the lithium iron phosphate are calcined first, wherein the temperature of the calcination is 400-500 ℃ and the time is 3-6 h.
Iron in the lithium iron phosphate is in a divalent state and has certain reducibility, and strong acid and an oxidant are simultaneously added in the traditional acid leaching process to oxidize the iron into a trivalent state so as to leach the lithium iron phosphate. In this patent, to solve this problem, fe is contained 3+ The solution is a leaching agent, so that the use and consumption of the reagent in the leaching process are simplified, and the specific principle is as follows: fe (Fe) 3+ The solution after hydrolysis is acidic, fe 3+ The higher the concentration of (c), the more acidic, which provides a good acidic environment for precipitation of iron phosphate. Unhydrolyzed Fe 3+ Can be combined with Fe in lithium iron phosphate 2+ A displacement reaction occurs and precipitates as iron phosphate under acidic conditions while L i goes into solution as ions. Fe displaced from the solution 2+ The lithium cobalt oxide is reduced, the Co and L i can be decomposed and enter into the solution, and the leaching process of the lithium cobalt oxide and the lithium iron phosphate is completed in one step.
And then, separating Co in the form of hydroxide from L i by adjusting the pH value of the leaching solution, recovering L i in the form of lithium carbonate by adding sodium carbonate, and finally, preparing the recovered lithium carbonate and ferric phosphate into lithium iron phosphate again to complete all recovery processes.
The method for recycling the mixed material of the waste lithium cobaltate and the lithium iron phosphate and regenerating the mixed material into the lithium iron phosphate comprises the following steps: firstly, carrying out pretreatment such as discharging, disassembling and separating on waste lithium cobaltate and lithium iron phosphate batteries to obtain lithium cobaltate and lithium iron phosphate powder, and mixing the powder, the mixture and Fe-containing powder 3+ Mixing and stirring the solution to obtain a solid-liquid mixture, and carrying out suction filtration and separation to obtain ferric phosphate precipitate and Fe-containing solution 2 Adding alkaline substances into the mixed solution of Co and L i to adjust the pH, reacting for a period of time, filtering to obtain cobalt hydroxide precipitate and L i-containing solution, and adding carbonate into L i solution to obtain the final productAnd precipitating lithium carbonate, and calcining the precipitated lithium carbonate and ferric phosphate to regenerate lithium iron phosphate. According to the method for recycling the mixed materials of the waste lithium cobaltate and the lithium iron phosphate, provided by the invention, the recycling process of the waste lithium ion battery can be effectively simplified, and the recycled materials can be fully utilized, so that the recycled materials are regenerated into new lithium iron phosphate anode materials.
The invention aims to provide the following technical scheme:
(1) A method for recycling waste lithium cobaltate and lithium iron phosphate mixed materials and regenerating the waste lithium cobaltate and lithium iron phosphate mixed materials into lithium iron phosphate is adopted, and ferric sulfate solution and the waste lithium cobaltate and lithium iron phosphate mixed materials are treated together and regenerated;
wherein, the mass ratio of the waste lithium cobaltate to the lithium iron phosphate is 1:1-1:6, and is preferably 1:2;
wherein the concentration of the ferric sulfate solution is 100-1000 mg/L, preferably 200mg/L;
(2) The method according to the above (1), which further comprises adding waste lithium cobalt oxide and lithium iron phosphate to the Fe-containing material 3+ Stirring the solution;
wherein the stirring reaction time is 20-120 min, preferably 60min;
wherein the reaction temperature is 20-90 ℃, preferably 90 ℃;
wherein the stirring speed is 100-300 r/min, preferably 300r/min.
(3) The method according to the above (1), wherein Fe in the acidic aqueous solution 3+ From one or more of ferric sulphate, ferric nitrate and ferric chloride.
(4) The method according to the above (1), further comprising adding an alkaline substance to the sulfate solution for cobalt precipitation, wherein the alkaline substance is any alkaline substance such as sodium hydroxide, potassium hydroxide, ammonia water, and the like, preferably sodium hydroxide.
(5) The method according to the above (1), wherein the lithium ion solution obtained after adding the alkaline substance is subjected to precipitation by adding carbonate, which includes any carbonate such as sodium carbonate, calcium carbonate, potassium carbonate, etc., preferably sodium carbonate.
The beneficial effects are that:
(1) According to the method, the waste lithium cobaltate and lithium iron phosphate are mixed, and other additives such as an oxidant, a reducing agent or inorganic organic acid are not needed, so that the cost can be effectively saved;
(2) The mixed material treated by the method can be regenerated into a new lithium iron phosphate anode material, and cobalt element is recovered in the form of hydroxide, so that the environmental pollution is reduced, and the resources are saved;
(3) The method improves the process flow, saves the resource consumption, has lower energy consumption, labor cost and water consumption than the traditional acid leaching method, has simple process flow and no complex operation, and is a green and efficient recovery method.
Drawings
Fig. 1 shows a flow chart for recovering a mixture of lithium cobaltate and lithium iron phosphate and regenerating the mixture into lithium iron phosphate.
FIG. 2 shows a morphology of the preparation of lithium iron phosphate from 100ml of 200mg/L ferric sulfate solution according to example 1 of the present invention.
Detailed Description
The features and advantages of the present invention will become more apparent and clear from the following detailed description of the invention.
The lithium ion battery has a plurality of advantages of high working voltage, high energy density, long cycle life, low self-discharge rate and the like, and has been widely used. The number of spent lithium ion batteries has shown explosive growth in various fields. In general, if the waste lithium ion battery is not recycled in a professional way, serious harm is caused to the environment and human health. Meanwhile, lithium and cobalt belong to scarce resources, and the contradiction between raw material supply and demand is increasingly prominent in China, so that the efficient recovery of valuable metals in the lithium ion battery has important environmental protection value and economic value.
For waste lithium ion batteries, the current main recycling process is a hydrometallurgical technology, and the method mainly comprises the following operation steps: firstly discharging, disassembling and crushing the waste lithium ion battery to obtain a positive plate composed of an active material and an aluminum foil, then calcining the positive plate or separating active substances from the aluminum foil by using a polar solvent, and finally leaching the active substances by inorganic acid or organic acid and then separating by virtue of extraction, precipitation or other methods.
Therefore, the existing hydrometallurgical process can achieve higher recovery rate, but has the defects of complex process flow, high recovery cost, difficult waste liquid treatment and the like.
Therefore, the method effectively solves the defects existing in the current recovery process, and the efficient recovery and utilization of the elements in the waste lithium cobalt oxide and the lithium iron phosphate are the problems to be solved.
In order to solve the problems, the invention provides a method for recycling the mixture of waste lithium cobalt oxide and lithium iron phosphate and regenerating the mixture into lithium iron phosphate by containing Fe 3+ The solution reacts with lithium cobaltate and lithium iron phosphate to generate ferric phosphate sediment and contains Li, co and Fe 2+ Li is recovered as carbonate, and then calcined with iron phosphate to regenerate lithium iron phosphate, and cobalt is recovered as hydroxide. The method provided by the invention is simple to operate, has short steps, can effectively treat the waste lithium cobalt oxide and the lithium iron phosphate, can recycle the waste lithium cobalt oxide and the lithium iron phosphate, and tightly combines environmental protection and economic benefits.
The invention provides a method for recycling waste lithium cobaltate and lithium iron phosphate and regenerating the waste lithium cobaltate and the lithium iron phosphate into lithium iron phosphate, which comprises the steps of mixing the waste lithium cobaltate and the lithium iron phosphate with Fe 3+ The solution is stirred together and then reacts, and the solution is regenerated;
wherein the Fe-containing alloy comprises 3+ The concentration of the solution is 100-1000 mg/L, preferably 200mg/L.
Wherein the reaction time is 20-120 min, preferably 60min;
containing Fe 3+ Fe contained in the solution 3+ Can react with lithium iron phosphate to generate ferric phosphate sediment and contains Li and Fe 2+ Is a mixed solution of (a) and (b). Due to Fe 2 The lithium cobalt oxide has a certain reducibility, and can be reduced to generate a mixed solution of Co and Li, so that the purpose of recycling Fe, li and Co in the mixed material in one step is achieved.
Wherein the stirring speed is 100-300 r/min, preferably 300r/min;
in the present invention, the oxidizing Fe in the leachate 3+ Fe in lithium iron phosphate 2+ Generating displacement reaction to generate ferric phosphate sediment and Fe 2+ Mixed solutions of L i; then reducing Fe 2+ Can decompose lithium cobalt oxide, and finally separate Co and L i by adjusting the pH value of the leaching solution, so as to recycle lithium cobalt oxide and lithium iron phosphate in one step. In this experiment, other metal ions such as Na, K, ca, mg and the like are difficult to react due to insufficient redox, large ionic radius, small hydrolysis degree and the like, so the method has certain specificity for selecting leaching liquid.
In the present invention, the Fe-containing material 3+ The liquid-solid ratio of the solution to the lithium cobaltate and the lithium iron phosphate is not required to be fixed, and the solid-liquid ratio is 1:10-1:100. The smaller the liquid-solid ratio is, the better from the viewpoint of the liquid-solid ratio for particle dissolution, but the step involving subsequent precipitation may cause difficulty in recovery thereof. The inventor finds that when the liquid-solid ratio is 80:1-100:1, the reaction efficiency is higher, and the reaction requirement can be met.
In the present invention, there is no particular limitation on the reaction temperature, and the reaction may be carried out at room temperature; the reaction may also be carried out after heating. The reaction temperature is 20 to 90 ℃, preferably 90 ℃.
Detailed Description
The invention is further described below by means of specific examples. These examples are merely exemplary and are not intended to limit the scope of the present invention in any way.
Example 1
Firstly, soaking waste lithium cobaltate and lithium iron phosphate batteries in saturated sodium chloride solution for 1h, taking out the batteries after full discharge, cleaning and drying. And disassembling the battery to obtain a battery shell and an inner core, and further disassembling and separating the inner core to obtain the positive pole piece. And (3) placing the positive electrode plate into a tubular furnace filled with argon, roasting for 1h at 500 ℃, and separating the positive electrode plate from an aluminum foil to obtain lithium cobaltate and lithium iron phosphate powder respectively.
1.154g of waste lithium cobaltate and 1.403g of lithium iron phosphate are weighed, 100ml of 200mg/L ferric sulfate solution is added, and the mixture is mixed and stirred at the stirring rate of 300r/min. After 60mi of reaction, solid-liquid separation was performed to obtain 1.341g of iron phosphate precipitate and a sulfate solution. The solution after ferric phosphate precipitation also contains lithium and cobalt elements, the precipitation pH of cobalt hydroxide (6.5 < pH < 9.0) is smaller than that of lithium hydroxide (pH > 10.0), therefore, sodium hydroxide is added into sulfate solution by adding sodium hydroxide to adjust the pH value of the solution to 9.0-10.0, solid-liquid separation is carried out after standing for 30min, 1.071g of lithium ion solution and cobalt hydroxide precipitate are obtained, and the recovery rate of cobalt is 97.86%. Sodium carbonate was added to the lithium ion solution to obtain 0.753g of lithium carbonate precipitate, and the recovery rate of lithium was 98.54%. Finally, the lithium carbonate and the iron phosphate were calcined at 750℃for 6 hours to obtain 1.355g of lithium iron phosphate. As in fig. 2.
To further investigate the optimum process for the use of ferric sulphate, the amount was varied in this example and the leachate element i cp test results (mass ratio) were carried out and the results are given in the following table.
The purity of the sediment obtained by the application is tested by ICP, the purity is more than 99%, the primary particle size of lithium iron phosphate is about 0.1-1 mu m, and the secondary particle size is about 2-5 mu m; the surface is smooth and has no impurity, the particle shape is irregular, but the distribution is even and has no obvious agglomeration phenomenon; lithium carbonate: most of the particles are in block distribution, and the small part of the particles are in agglomeration shape, and the particle size distribution is uneven, and the size is 1-5 mu m; the surface of the particles is smooth, and no impurity particles exist. Can meet the reproduction requirement.
Grinding the obtained lithium iron phosphate, and mixing the ground lithium iron phosphate with carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare the electrode. Adding proper amount of N-methyl-2-pyrrolidone, and stirring uniformly. And then coating the slurry on an aluminum foil, drying for 10 hours at 80 ℃, and assembling the aluminum foil into a button cell for electrochemical performance test. At a voltage of 1 in the range of 2.2 to 4.0VConstant current circulation is carried out at the C multiplying power, and the first discharge capacity is 132 mAh.g -1 The coulomb efficiency was 97%, and the discharge capacity after 100 cycles was 130 mA.g -1 。
Example 2
Firstly, soaking waste lithium cobaltate and lithium iron phosphate batteries in saturated sodium chloride solution for 1h, taking out the batteries after full discharge, cleaning and drying. And disassembling the battery to obtain a battery shell and an inner core, and further disassembling and separating the inner core to obtain the positive pole piece. And (3) placing the positive electrode plate into a tubular furnace filled with argon, roasting for 1h at 500 ℃, and separating the positive electrode plate from an aluminum foil to obtain lithium cobaltate and lithium iron phosphate powder respectively.
1.154g of waste lithium cobaltate and 1.403g of lithium iron phosphate are put into 100mL of pure water, and 2mol/L of H is used 2 SO 4 The pH of the solution was controlled at 2.0 while adding 3mL of 30% by mass H 2 O 2 The solution is placed in a water bath kettle with the temperature of 80 ℃ and stirred for reaction for 3 hours. After the completion of the reaction, the solution was separated by filtration to obtain 1.274g of a solution and iron phosphate precipitate. And adding sodium hydroxide into the solution to adjust the pH to 10.0, standing for 30min, and then carrying out solid-liquid separation to obtain 1.049g of lithium ion solution and cobalt hydroxide precipitate, wherein the recovery rate of cobalt is 95.7%. Saturated sodium carbonate solution was added to the lithium ion solution to obtain 0.738g of lithium carbonate precipitate, and the recovery rate of lithium was 96.63%. Finally, the lithium carbonate and the ferric phosphate were calcined at 750℃for 6 hours to obtain 1.306g of lithium iron phosphate.
Grinding the obtained lithium iron phosphate, and mixing the ground lithium iron phosphate with carbon black and polyvinylidene fluoride according to the mass ratio of 8:1:1 to prepare the electrode. Adding proper amount of N-methyl-2-pyrrolidone, and stirring uniformly. And then coating the slurry on an aluminum foil, drying for 10 hours at 80 ℃, and assembling the aluminum foil into a button cell for electrochemical performance test. Constant current circulation is carried out at a 1C multiplying power within a voltage range of 2.2-4.0V, and the first discharge capacity is 135 mAh.g -1 The coulomb efficiency was 96%, and the discharge capacity after 100 cycles was 128 mA.g -1 。
Example 3
Firstly, soaking waste lithium cobaltate and lithium iron phosphate batteries in saturated sodium chloride solution for 1h, taking out the batteries after full discharge, cleaning and drying. And disassembling the battery to obtain a battery shell and an inner core, and further disassembling and separating the inner core to obtain the positive pole piece. And (3) placing the positive electrode plate into a tubular furnace filled with argon, roasting for 1h at 500 ℃, and separating the positive electrode plate from an aluminum foil to obtain lithium cobaltate and lithium iron phosphate powder respectively.
1.154g of waste lithium cobaltate and 1.403g of lithium iron phosphate are put into 100mL of H with the concentration of 5mol/L 2 SO 4 3mL of H with mass fraction of 30% is added into the solution at the same time 2 O 2 The solution is placed in a water bath kettle with the temperature of 80 ℃ and stirred for reaction for 3 hours. After the completion of the reaction, the solution was separated by filtration to obtain a solution and 0.256g of a precipitate. Adding sodium hydroxide into the solution to adjust the pH value to 4.0, standing for 30min, and then carrying out solid-liquid separation to obtain 0.855g of iron removal solution and ferric hydroxide precipitate, wherein the iron removal rate is 99.1%. Adding sodium hydroxide into the iron removal solution to adjust the pH to 10.0, standing for 30min, and then carrying out solid-liquid separation to obtain cobalt removal solution and cobalt hydroxide precipitate of 0.961g, wherein the cobalt removal rate is 98.7%. A saturated sodium carbonate solution was added to the cobalt-removed solution to obtain 0.731g of lithium carbonate precipitate, and the recovery rate of lithium was 95.6%.
The invention relates to a method for recycling a mixed material of waste lithium cobaltate and lithium iron phosphate and regenerating the mixed material into lithium iron phosphate, which comprises the following specific steps: firstly, carrying out pretreatment such as discharging, disassembling and separating on a waste lithium cobalt oxide battery and a lithium iron phosphate battery to obtain lithium cobalt oxide and lithium iron phosphate powder, fully mixing the lithium cobalt oxide and the lithium iron phosphate powder to obtain a mixed material, mixing and stirring the mixed material with an iron sulfate solution, filtering to obtain an iron phosphate precipitate and a sulfate solution containing lithium and iron, regulating the pH value of the solution by adding an alkaline substance, carrying out suction filtration and separation after reacting for a period of time to obtain a cobalt hydroxide precipitate and a lithium ion solution, adding carbonate into the lithium ion solution to generate a lithium carbonate precipitate, and finally calcining the lithium carbonate and the iron phosphate at a high temperature to regenerate the lithium iron phosphate. According to the treatment method provided by the invention, not only is the environmental pollution caused by waste lithium cobaltate and lithium iron phosphate effectively prevented, but also the waste materials in the waste lithium cobaltate and lithium iron phosphate can be completely recovered and efficiently regenerated into lithium iron phosphate positive electrode materials for use.
The invention has been described in detail in connection with the specific embodiments and exemplary examples thereof, but such description is not to be construed as limiting the invention. It will be understood by those skilled in the art that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, and these fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (8)
1. A method for recycling a mixed material of lithium cobaltate and lithium iron phosphate, which is characterized in that: comprises the steps of,
step 1: immersing lithium cobalt oxide and lithium iron phosphate in an acidic aqueous solution, wherein the pH value of the acidic aqueous solution is 0.5-2.5, and the acidic aqueous solution contains Fe 3+ ，Fe 3+ The concentration of the Fe of the lithium iron phosphate is 100-1000 mg/L 2+ By Fe 3+ Displacing to form ferric phosphate precipitate, and displacing the obtained Fe in the solution 2+ Decomposing lithium cobaltate to enable Co and Li to enter a solution, and performing first solid-liquid separation;
step 2: adjusting the pH value of the solution after the first solid-liquid separation to be alkaline to generate cobalt hydroxide precipitate, and performing the second solid-liquid separation;
step 3: adding carbonate into the solution after the second solid-liquid separation to generate lithium carbonate precipitate, and performing the third solid-liquid separation;
the mass ratio of the lithium cobaltate to the lithium iron phosphate is 1:1-1:6.
2. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: and mixing and roasting the lithium carbonate precipitate and the ferric phosphate precipitate to obtain the regenerated lithium iron phosphate.
3. A method of recovering a lithium cobalt oxide and lithium iron phosphate blend according to claim 1 or 2, characterized in that: fe in the acidic aqueous solution 3+ From one or more of ferric sulphate, ferric nitrate and ferric chloride.
4. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: the reaction temperature in the step 1 is 20-90 ℃.
5. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: stirring in the step 1, wherein the stirring time is 20-120 min, and the stirring speed is 100-300 r/min.
6. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: in the step 2, the pH value of the solution after the first solid-liquid separation is adjusted to be alkaline, and one or more of sodium hydroxide, potassium hydroxide and ammonia water are used for adjustment.
7. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: and 3, adding carbonate into the solution after the second solid-liquid separation, wherein the carbonate comprises one or more of sodium carbonate, calcium carbonate and potassium carbonate.
8. The method for recovering lithium cobaltate and lithium iron phosphate mixture according to claim 1, wherein: in the step 1, the lithium cobaltate and the lithium iron phosphate are calcined first, wherein the temperature of the calcination is 400-500 ℃ and the time is 3-6 h.
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