CN117737438A - Fe of waste lithium-containing positive electrode active material 7 S 8 Auxiliary alkaline leaching lithium and recovery and regeneration method - Google Patents
Fe of waste lithium-containing positive electrode active material 7 S 8 Auxiliary alkaline leaching lithium and recovery and regeneration method Download PDFInfo
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- CN117737438A CN117737438A CN202410025356.4A CN202410025356A CN117737438A CN 117737438 A CN117737438 A CN 117737438A CN 202410025356 A CN202410025356 A CN 202410025356A CN 117737438 A CN117737438 A CN 117737438A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 127
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 127
- 238000002386 leaching Methods 0.000 title claims abstract description 68
- 239000002699 waste material Substances 0.000 title claims abstract description 50
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 45
- 238000011084 recovery Methods 0.000 title claims abstract description 16
- 238000011069 regeneration method Methods 0.000 title abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 47
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 44
- 229910052723 transition metal Inorganic materials 0.000 claims description 16
- 150000003624 transition metals Chemical class 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims description 14
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 13
- 229910001416 lithium ion Inorganic materials 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002243 precursor Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002893 slag Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011149 active material Substances 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 239000006258 conductive agent Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 239000010926 waste battery Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 9
- 230000002441 reversible effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical class [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 208000028659 discharge Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention belongs to the field of waste battery treatment, and in particular relates to Fe of a waste lithium-containing positive electrode active material 7 S 8 Auxiliary alkaline leaching lithium method, wherein to-be-treated material containing waste lithium-containing positive electrode active material is treated in Fe 7 S 8 And (3) carrying out alkaline leaching lithium treatment with the assistance of a source to obtain a lithium-rich leaching solution. The invention also comprises a recovery and regeneration method of the waste materials. The method of the invention can be under normal pressureThe efficient extraction of lithium can be realized, and in addition, the regeneration performance of the obtained material can be improved.
Description
Technical Field
The invention belongs to the field of battery waste recovery, and particularly relates to the field of waste lithium battery material recovery.
Background
Lithium secondary batteries, such as the common lithium ion batteries, are widely used in secondary energy storage fields of consumer electronics, electric vehicles and power grid systems due to their high energy density, high power density, long life and compact size. Currently, the global market value of lithium ion batteries has reached $400 billion. With the increasing demand of electric vehicles, the demand of lithium ion batteries is also greatly increasing, and 100 tens of thousands of lithium ion batteries are expected to be reached in 2030. Because of the wide application of lithium ion batteries in electronic equipment, electric automobiles and energy storage, the recovery speed of metals in waste lithium ion batteries is very high. From the aspects of resource utilization and environmental protection, the recycling mode meets the requirement of sustainable development.
For waste materials, the idea of the prior art mainly consists in leaching a section of all elements (such as common acid leaching), and the process is simple and convenient to operate, but the effect of the section of all leaching of metals is still to be improved, and the strategic resource lithium is easy to be lost in the treatment process. For this reason, the prior art has also developed some processes for recovering other elements after pre-extraction of lithium. For example, chinese patent publication No. CN114956130a discloses a subcritical lithium pre-extraction method for a waste lithium battery positive electrode material, wherein a mixed solution containing waste lithium battery positive electrode powder, water and polyhydroxy alcohol is heated, so that water in the mixed solution is in a subcritical state, and is maintained in the subcritical state, and subjected to lithium pre-extraction treatment, and after the treatment is completed, solid-liquid separation is performed, so as to obtain a lithium extraction liquid; the polyhydroxy alcohol is one or more of ethylene glycol or propylene glycol; in the water and the polyhydroxy alcohol, the volume fraction of the polyhydroxy alcohol is 30-95%; the temperature of the subcritical stage is 180-220 ℃. For another example, chinese patent document with publication number CN113862476a discloses a method for pre-extracting lithium from waste lithium ion batteries, comprising: step 1: pretreating a waste lithium ion battery to obtain electrode active material powder; step 2: alkaline solution is utilized to carry out alkaline washing treatment on the electrode active material powder, copper and aluminum are removed by filtration, and drying treatment is carried out on the electrode active material powder after the alkaline washing treatment; step 3: putting the dried electrode active material powder and transition metal salt solution into a high-pressure reaction kettle according to a certain solid-to-liquid ratio for hydrothermal reaction; step 4: taking out the solution after the hydrothermal reaction, and filtering to obtain a lithium-rich leaching solution and a transition metal oxide leaching residue; step 5: purifying and removing impurities from the lithium-rich leaching solution, and adding carbonate or bicarbonate to precipitate lithium to obtain lithium carbonate. For another example, chinese patent publication No. CN117004823a discloses a method for preferentially extracting lithium and manganese from waste LNCM material, which is characterized in that a raw material solution containing waste LNCM material and alkali is filled and sealed in a pressure-resistant container chamber, heated to a temperature T, then introduced with an oxygen-containing atmosphere to be boosted to P, and subjected to leaching treatment under heat and pressure preservation; then decompressing and cooling, and carrying out solid-liquid separation to obtain leaching liquid enriched with lithium and manganese and leaching slag enriched with nickel and cobalt; the pressure P of the leaching treatment stage is 1.1-5 times of the system pressure of the pressurizing initial stage, and the T is 200-350 ℃.
In summary, although the prior art provides more processes for pre-extracting lithium, most of the processes need to be performed under higher temperature conditions, and the effect of pre-extracting lithium at normal pressure needs to be improved, and the loss of other transition metals in the cathode material is easily caused.
Disclosure of Invention
Aiming at the problems faced by the recycling of the positive electrode of the existing waste lithium ion battery, the invention aims to provide Fe of a waste lithium-containing positive electrode active material 7 S 8 The auxiliary alkaline leaching lithium method aims at improving the pre-leaching lithium effect under normal pressure and reducing the accompanying loss of transition metal elements.
The second object of the invention is to provide a method for recycling waste lithium-containing positive electrode active materials.
The third object of the invention is to provide a method for regenerating waste lithium-containing positive electrode active materials.
Fe of waste lithium-containing positive electrode active material 7 S 8 Auxiliary alkaline leaching lithium method, wherein to-be-treated material containing waste lithium-containing positive electrode active material is treated in Fe 7 S 8 Of the sourceAnd carrying out alkaline leaching lithium treatment with the assistance of the alkaline leaching lithium to obtain a lithium-rich leaching solution.
Aiming at the problems that lithium is difficult to deeply remove from the crystal lattice of the waste lithium-containing positive electrode active material, the selectivity of the removal is not ideal, and the like, the invention creatively researches and shows that Fe is creatively adopted 7 S 8 The auxiliary alkaline leaching lithium treatment can obtain excellent pre-extraction lithium effect under normal pressure and relatively low temperature, and can avoid the loss of other elements and show excellent pre-extraction lithium selectivity.
In the invention, the waste lithium-containing positive electrode active material can be stripped from the waste lithium ion battery based on a known process.
In the invention, the technical scheme has good universality and can be suitable for preferentially extracting lithium from any active material. For example, as an alternative method, the lithium-containing positive electrode active material may be at least one of lithium-containing phosphate, oxidizing salt containing at least one element of iron, nickel, cobalt, manganese; further, the lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium cobaltate, lithium nickelate, lithium manganate and nickel cobalt manganese ternary material can be selected.
In the invention, the raw material type requirements of the material to be treated are relatively loose, for example, the material to be treated is allowed to contain at least one of a binder, a conductive agent, a negative electrode active material, a diaphragm, a current collector and an electrolyte;
in the present invention, the content of the waste lithium-containing positive electrode active material in the material to be treated is not particularly required, and the content of the waste lithium-containing positive electrode active material is preferably 50wt.% or more, more preferably 80 wt.% or more, still more preferably 80 to 95wt.% in view of the economical efficiency of the process.
The research of the invention shows that the Fe 7 S 8 Fe in source 7 S 8 The active ingredients are key to assist in improving the normal pressure alkaline leaching effect.
Fe according to the invention 7 S 8 In the source, fe 7 S 8 The content of the active ingredient is 85wt.% or more, and more preferably 95wt.% or more.
In the present invention, fe 7 S 8 Source through FeS 2 Calcining the source at 500-900 deg.c for 10-60 min. The research of the invention shows that by adopting the mode and combining the temperature and time, fe with high phase purity can be obtained unexpectedly 7 S 8 The product is favorable for improving the auxiliary normal pressure alkaline effect.
In the invention, the atmosphere in the calcination process is a protective atmosphere;
in the present invention, the temperature of the calcination process may be 550 to 750 ℃.
In the present invention, the time for the thermal insulation calcination is 15 to 50 minutes, more preferably 30 to 45 minutes.
In the invention, the waste lithium-containing positive electrode active material and Fe in the material to be treated 7 S 8 Fe in source 7 S 8 The weight ratio of (2) is 1:1-10, and can be 1:2 to 5.
In the invention, the alkaline solute in the alkaline solution in the alkaline leaching lithium process comprises at least one of sodium hydroxide, potassium hydroxide and ammonia water;
the concentration of the alkaline solute in the alkaline solution can be adjusted conventionally as required, and can be 1-3M in consideration of the treatment process and the operation convenience.
In the invention, the alkaline leaching lithium process is carried out under normal pressure;
in the invention, the temperature of the alkaline leaching lithium stage is 40-80 ℃, and further 45-65 ℃;
in the invention, the liquid-solid ratio in the alkaline leaching lithium stage can be adjusted conventionally according to the requirement, and the process simplicity is considered, and the liquid-solid ratio can be further 10-50 mL/g, and further 20-40 mL/g;
in the invention, the time of the alkaline leaching lithium stage is more than 0.5h, more preferably 1 to 4h, still more preferably 1.5 to 2.5h.
The invention also provides an element recovery method of the waste lithium-containing positive electrode active material, and the method is used for carrying out alkaline leaching lithium treatment to obtain a lithium-rich leaching solution and leaching residues enriched with transition metals in the lithium-containing positive electrode active material; and carrying out acid leaching treatment on the leaching slag to obtain the transition metal leaching solution.
The process of the present invention may be based on known processes to recover lithium from a lithium rich extract and to recover transition metals from a transition metal leach solution.
For example, according to the alternative scheme of the invention, lithium precipitation treatment can be carried out on the lithium-rich leaching solution to obtain a lithium source;
in the present invention, the acid leaching process may be conventional in order to ensure efficient leaching of the metal elements in the active material therein.
In the present invention, a desired precursor material may be obtained from the leachate based on a known process, for example, an alternative scheme of adjusting the pH of the transition metal leachate to 4 to 5, performing a impurity removal treatment, and then performing a coprecipitation treatment after adjusting the element ratio to obtain a transition metal precursor.
The invention also provides a regeneration method of the waste lithium-containing positive electrode active material, and the method is adopted to obtain a lithium source and a transition metal precursor, and then the lithium source and the transition metal precursor are mixed and roasted to prepare the regenerated active material.
Advantageous effects
The innovative research of the invention shows that the invention adopts Fe 7 S 8 The auxiliary alkaline leaching lithium treatment can obtain excellent pre-extraction lithium effect under the conditions of normal pressure and relatively low temperature, and can avoid the loss of other elements and show excellent pre-extraction lithium selectivity.
Drawings
FIG. 1 is FeS of example 1 2 Fe before and after calcination 7 S 8 Product XRD;
Detailed Description
The present invention will be described in further detail with reference to the following examples, but the present invention is not limited to the following examples.
In the present invention, the material to be treated containing the waste positive electrode active material may be obtained by stripping based on a known process, for example, as an alternative, the stripping step is as follows: putting a waste lithium ion battery (such as a ternary battery, a lithium cobaltate battery and the like) into 1-3 mol/L saline water for 25-35 h of discharge treatment, drying the discharged battery at 80-90 ℃, disassembling and separating a positive plate and a negative plate, soaking the positive plate into N-methylpyrrolidone, separating a current collector in the positive plate, filtering, washing and drying to obtain waste positive plate powder (to-be-treated material);
in the invention, the material to be treated contains waste positive electrode active materials and also allows components such as conductive agents, binders and the like. In the present invention, the content of the active material in the positive electrode material of the waste lithium ion battery is not particularly required, and in view of the economical efficiency of the process, the content is preferably 50wt.% or more, and in the following cases, the active content is 85 to 90wt.% unless specifically stated.
In the following cases, the Fe 7 S 8 May be analytically pure starting materials, or may allow the presence of other iron sulfides and other components that do not interfere with the process. In the present invention, to better explain Fe 7 S 8 Auxiliary effect on alkaline leaching, the following cases are all carried out by using raw materials with the content of more than 95 weight percent, and the raw materials can be commercial products or FeS obtained by analysis 2 The material is obtained under the heat preservation of Ar and T, wherein the T is 500-900 ℃, T is 10-60 Min, and can be further 35-45 Min.
Example 1
Step (1):
stripping waste nickel-cobalt-manganese ternary battery (NCM 1:1:1 battery) to obtain positive electrode powder and Fe 7 S 8 (by FeS) 2 Is obtained by heat preservation for 40min at Ar and 550 ℃, wherein Fe 7 S 8 The content of (3) is 95wt.% or more, and the positive electrode active material and Fe in the positive electrode powder 7 S 8 The weight ratio of (2) is 1: 3) And (3) placing the mixture in a 2M sodium hydroxide aqueous solution (the liquid-solid ratio is 30ml/g, based on the anode powder), leaching for 2 hours at the normal pressure of 45 ℃, and then carrying out solid-liquid separation to obtain a lithium-rich solution and ternary oxide slag, wherein the purity of Li in the lithium-rich solution is 98%, the recovery rate is 98.9%, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm.
In a rich stateNa is added into the lithium liquid 2 CO 3 Evaporating and crystallizing to obtain Li 2 CO 3 ；
Step (2): other recovery and regeneration steps
Carrying out sulfuric acid leaching treatment on the ternary oxide slag obtained in the step 1 to obtain a leaching solution, then adjusting the pH value to 4.5, carrying out impurity removal and filtration, regulating the molar ratio of nickel, cobalt and manganese in the filtrate obtained after filtration to be 1:1:1, and then adding NaOH-NH 3 ·H 2 And regulating the pH value to 11 by O to precipitate nickel cobalt manganese, thereby obtaining a nickel cobalt manganese precursor. The obtained nickel cobalt manganese precursor and the obtained Li 2 CO 3 (the excess coefficient of Li is 1.03), and then annealing is carried out for 10 hours at 800 ℃ to obtain the regenerated positive electrode active material.
And mixing and slurrying the regenerated positive electrode active material, the conductive carbon black and the PVDF according to the weight ratio of 8:1:1, coating the slurry on a positive electrode current collector, and drying to obtain the positive electrode.
Use of 1M LiPF in glove box 6 The electrolyte (EC: DEC: emc=1:1:1) and the separator was a Celgard2400 polypropylene film. The positive electrode is a working electrode, lithium is a counter electrode, and the reversible capacity of 185mAh/g is shown by the positive electrode regenerated at the multiplying power of 1C at room temperature.
Example 2
The difference compared with example 1 is only that Fe is changed 7 S 8 The specific group of the obtaining conditions is as follows:
group A: fe (Fe) 7 S 8 By FeS 2 Preserving heat at Ar and 750 ℃ for 15min to obtain the compound;
group B: fe (Fe) 7 S 8 By FeS 2 Preserving heat at Ar and 650 ℃ for 35min to obtain the compound;
operation and testing was performed as in example 1, with the result that:
group A: the purity of Li in the lithium-rich liquid is 98.5%, the recovery rate is 99.1%, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm; the 1C rate regenerated positive electrode at room temperature showed a reversible capacity of 184 mAh/g.
Group B: the purity of Li in the lithium-rich liquid is 98.6%, the recovery rate is 99.2%, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm; the rate regenerated positive electrode at room temperature of 1C showed a reversible capacity of 187 mAh/g.
Example 3
The difference compared with example 1 is only that the positive electrode active material and Fe in the positive electrode powder are changed 7 S 8 The weight ratio of (3) is as follows:
group A: positive electrode active material and Fe in positive electrode powder 7 S 8 The weight ratio of (2) is 1:2;
group B: positive electrode active material and Fe in positive electrode powder 7 S 8 The weight ratio of (2) is 1:5, a step of;
operation and testing was performed as in example 1, with the result that:
group A: the purity of Li in the lithium-rich liquid is 97.3%, the recovery rate is 98.5%, and the content of nickel-cobalt-manganese ternary elements is less than 0.03ppm; the 1C rate regenerated positive electrode at room temperature showed a reversible capacity of 175 mAh/g.
Group B: the purity of Li in the lithium-rich liquid is 99.3%, the recovery rate is 99.3%, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm; the rate regenerated positive electrode at room temperature of 1C shows reversible capacity of 188 mAh/g.
Example 4
The only difference compared with example 1 is that the temperature and alkali concentration conditions of the leaching process are changed, and the experimental groups are respectively as follows:
group A: the leaching temperature is set to 60 ℃, and the leaching time is changed to 1.5h;
group B: the alkali concentration is set to be 3M, and the liquid-solid ratio in the leaching stage is 25mL/g;
operation and testing was performed as in example 1, with the result that:
group A: the purity of Li in the lithium-rich liquid is 98.3 percent, the recovery rate is 99.1 percent, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm; the rate regenerated positive electrode at room temperature of 1C shows reversible capacity of 188 mAh/g.
Group B: the purity of Li in the lithium-rich liquid is 99.1%, the recovery rate is 99.4%, and the content of nickel-cobalt-manganese ternary elements is less than 0.01ppm; the rate regenerated positive electrode at room temperature of 1C showed a reversible capacity of 187 mAh/g.
Comparative example 1
The difference compared with example 1 is that no Fe was added 7 S 8 Other operations and parameters were the same as in example 1.
Operation and testing was performed as in example 1, with the result that: the Li extraction rate was only 1.3%.
Comparative example 2
The difference compared with example 1 is only that Fe is changed 7 S 8 Source acquisition conditions, the distinguishing step 1 is:
positive electrode powder and auxiliary material (by FeS) stripped from waste nickel-cobalt-manganese ternary battery (same as example 1) 2 The Fe in the product is obtained under the conditions of Ar and 550 ℃ and the heat preservation time t is 2h 7 S 8 The intermediate product is converted in a large amount; in this case, feS therein 2 The raw material weight was the same as in example 1) placed in a 2M aqueous sodium hydroxide solution (liquid-solid ratio: 30ml/g, based on the positive electrode material) and leached out at 45 ℃ under normal pressure for 2 hours, followed by solid-liquid separation to obtain a lithium-rich solution and a ternary oxide slag, wherein the Li extraction rate in the lithium-rich solution was only 63.2%.
Comparative example 3
The difference compared to example 2 is only that the incubation time t is set to 10min. Other operations and parameters were the same as comparative example 2.
The results were: the Li extraction rate in the lithium-rich solution is only 75.3%.
Comparative example 4
The difference compared with example 1 is only that FeS is used 2 Replacing the Fe 7 S 8 That is, feS 2 The same amounts were used, except that no heat-retaining calcination treatment was performed, and the other operations and parameters were the same as in example 1.
The results were: the Li extraction rate in the lithium-rich solution was only 42.9%.
Claims (10)
1. Fe of waste lithium-containing positive electrode active material 7 S 8 A method for extracting lithium by auxiliary alkali is characterized in that a material to be treated containing waste lithium-containing positive electrode active material is prepared by adding Fe 7 S 8 Alkaline leaching lithium treatment is carried out with the assistance of a source,and obtaining the lithium-rich leaching solution.
2. The Fe of the waste lithium-containing positive electrode active material according to claim 1 7 S 8 The auxiliary alkaline leaching lithium method is characterized in that the lithium-containing positive electrode active material is obtained by stripping from a waste lithium ion battery;
preferably, the lithium-containing positive electrode active material contains at least one of lithium-containing phosphate and oxidizing salt of at least one element of iron, nickel, cobalt and manganese; further preferably at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium cobaltate, lithium nickelate, lithium manganate, and nickel cobalt manganese ternary.
3. The Fe of the waste lithium-containing positive electrode active material according to claim 2 7 S 8 The auxiliary alkaline leaching lithium method is characterized in that the material to be treated also comprises at least one of a binder, a conductive agent, a negative electrode active material, a diaphragm, a current collector and an electrolyte;
preferably, in the material to be treated, the content of the waste lithium-containing positive electrode active material is more than 50 wt.%.
4. The Fe of the waste lithium-containing positive electrode active material according to claim 1 7 S 8 A method for auxiliary alkaline leaching of lithium is characterized in that Fe 7 S 8 The content of the active ingredient is 85wt.% or more, and more preferably 95wt.% or more.
5. The Fe of the waste lithium-containing positive electrode active material according to claim 4 7 S 8 A method for auxiliary alkaline leaching of lithium is characterized in that Fe 7 S 8 Source through FeS 2 Calcining the source at 500-900 ℃ for 10-60 min to obtain the product;
preferably, the atmosphere of the calcination process is a protective atmosphere;
preferably, the time for the calcination is 15 to 50 minutes, more preferably 30 to 45 minutes.
6. Fe of the waste lithium-containing positive electrode active material according to any one of claims 1 to 5 7 S 8 The auxiliary alkaline leaching lithium extraction method is characterized in that the waste lithium-containing positive electrode active material and Fe in the material to be treated 7 S 8 Fe in source 7 S 8 The weight ratio of (2) is 1:1-10, and can be 1:2 to 5.
7. Fe of the waste lithium-containing positive electrode active material according to any one of claims 1 to 5 7 S 8 The auxiliary alkaline leaching lithium method is characterized in that alkaline solutes in alkaline liquor in the alkaline leaching lithium process comprise at least one of sodium hydroxide, potassium hydroxide and ammonia water;
preferably, the concentration of alkaline solute in the lye is 1-3M.
8. The Fe of the waste lithium-containing positive electrode active material according to claim 7 7 S 8 The auxiliary alkaline leaching lithium method is characterized in that the alkaline leaching lithium process is carried out under normal pressure;
preferably, the temperature of the alkaline leaching lithium stage is 40-80 ℃, and further 45-65 ℃;
preferably, the liquid-solid ratio in the alkaline leaching lithium stage is 10-50 mL/g, and can be 20-40 mL/g;
preferably, the alkaline leaching lithium stage takes more than 0.5 hours, preferably 1 to 4 hours.
9. An element recovery method of a waste lithium-containing positive electrode active material, which is characterized in that the method of any one of claims 1 to 8 is adopted for carrying out alkaline leaching lithium treatment to obtain a lithium-rich leaching solution and leaching residues enriched with transition metals in the lithium-containing positive electrode active material;
carrying out acid leaching treatment on the leaching slag to obtain a transition metal leaching solution;
preferably, carrying out lithium precipitation treatment on the lithium-rich leaching solution to obtain a lithium source;
preferably, the pH value of the transition metal leaching solution is regulated to 4-5, impurity removal treatment is carried out, and then coprecipitation treatment is carried out after the element proportion is regulated to obtain a transition metal precursor.
10. A method for regenerating a waste lithium-containing positive electrode active material, which is characterized in that a lithium source and a transition metal precursor are obtained by adopting the method of claim 9, and then the regenerated active material is prepared by mixing and roasting.
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