CN114737060B - Recycling method of waste lithium battery anode material - Google Patents
Recycling method of waste lithium battery anode material Download PDFInfo
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- CN114737060B CN114737060B CN202210476938.5A CN202210476938A CN114737060B CN 114737060 B CN114737060 B CN 114737060B CN 202210476938 A CN202210476938 A CN 202210476938A CN 114737060 B CN114737060 B CN 114737060B
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- active material
- ball milling
- lithium battery
- leaching
- positive electrode
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 37
- 239000002699 waste material Substances 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 238000004064 recycling Methods 0.000 title claims description 9
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000011149 active material Substances 0.000 claims abstract description 55
- 230000001603 reducing effect Effects 0.000 claims abstract description 54
- 238000002386 leaching Methods 0.000 claims abstract description 52
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 47
- 238000000498 ball milling Methods 0.000 claims abstract description 36
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 28
- 229940120146 EDTMP Drugs 0.000 claims abstract description 28
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000002739 metals Chemical class 0.000 claims abstract description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000011084 recovery Methods 0.000 claims abstract description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 238000012216 screening Methods 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims abstract description 7
- 239000007774 positive electrode material Substances 0.000 claims description 24
- 238000001914 filtration Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 16
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 7
- 239000011230 binding agent Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 230000006872 improvement Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 32
- 238000006722 reduction reaction Methods 0.000 description 19
- 229910017052 cobalt Inorganic materials 0.000 description 17
- 239000010941 cobalt Substances 0.000 description 17
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- PFYQFCKUASLJLL-UHFFFAOYSA-N [Co].[Ni].[Li] Chemical compound [Co].[Ni].[Li] PFYQFCKUASLJLL-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009854 hydrometallurgy Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 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 3
- 239000002245 particle Substances 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- AIJRZQRTCRIQFY-UHFFFAOYSA-N dilithium cobalt(2+) dioxido(dioxo)manganese nickel(2+) Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2].[Ni+2].[Li+].[Mn](=O)(=O)([O-])[O-].[Mn](=O)(=O)([O-])[O-] AIJRZQRTCRIQFY-UHFFFAOYSA-N 0.000 description 2
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- OUYCCCASQSFEME-QMMMGPOBSA-N L-tyrosine Chemical compound OC(=O)[C@@H](N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-QMMMGPOBSA-N 0.000 description 1
- 241001089723 Metaphycus omega Species 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000009853 pyrometallurgy Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- OUYCCCASQSFEME-UHFFFAOYSA-N tyrosine Natural products OC(=O)C(N)CC1=CC=C(O)C=C1 OUYCCCASQSFEME-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B21/00—Obtaining aluminium
- C22B21/0015—Obtaining aluminium by wet processes
- C22B21/0023—Obtaining aluminium by wet processes from waste materials
-
- 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
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/0423—Halogenated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
- C22B47/00—Obtaining manganese
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of lithium battery recovery, and provides a recovery method of a waste lithium battery anode material. The recovery method comprises the steps of S1) discharging, crushing, screening, S2) separating active materials, S3) ball milling reduction and S4) acid leaching recovery. The ball milling reduction is to prepare a reducing solution by adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, and then heating and ball milling the active material and the reducing solution in a ball mill, so as to reduce the high-valence metal in the active material. The acid leaching recovery is to filter the ball-milled material, wash filter residues with deionized water, and then leach the filter residues in hydrochloric acid solution. The recovery method can improve the leaching rate of metals, especially the leaching rate of high-valence metals, and has the advantages of larger improvement range, high ball milling reduction and leaching efficiency and short time consumption.
Description
Technical Field
The invention belongs to the technical field of lithium battery recovery, and provides a recovery method of a waste lithium battery anode material.
Background
In recent years, the sales of lithium batteries have been increased in an explosive manner, but the service life of common lithium batteries is only 4-6 years, and retired abandoned lithium batteries face the difficult problem of how to treat. On the one hand, the lithium battery contains a large amount of metal elements (such as lithium, nickel, cobalt, manganese and the like), which are precious resources, and the lithium battery is directly abandoned to cause huge economic loss. On the other hand, the metal element and the organic electrolyte have huge potential safety hazards, which not only cause environmental pollution, but also threaten the health of human beings. Therefore, recovery and reuse of lithium batteries have become an important research topic.
The recovery method of metals in the waste lithium batteries mainly comprises pyrometallurgy, hydrometallurgy, biological metallurgy and the like. Hydrometallurgy is to transfer valuable metals in an electrode active material into a solution by chemical reaction (such as reduction, oxidation, hydrolysis, neutralization and the like) by using certain solvents or extractants to obtain a leaching solution containing recovered metals, and then recovering target metals from the leaching solution. The valuable metal transferring process is the leaching process of the metal element.
Hydrometallurgy is usually carried out by directly leaching the positive electrode active material by adopting inorganic acid or organic acid, and has higher leaching rate of lithium, but lower leaching rate of high-valence metal, such as cobalt in lithium cobaltate and nickel, cobalt and manganese in nickel cobalt lithium manganate. At present, the prior art adopts a leaching method of leaching solution containing a reducing agent and acid, wherein high-valence metal ions are reduced and then dissolved in the acid for leaching. Chinese patent application No. 202010094563.7 discloses a method for efficiently recycling waste lithium battery anode materials in a leaching mode, which adopts leaching liquid composed of sodium borohydride, stannous chloride, tyrosine, benzaldehyde, 3-methyl-1-amyl alcohol and water, and has leaching rates of more than 90% for lithium, iron, nickel, cobalt and manganese, but has the leaching rates of high-valence metals such as nickel, cobalt and manganese to be improved.
Disclosure of Invention
In order to further improve the leaching rate of various metals in the waste lithium battery anode material, the invention provides a recovery method of the waste lithium battery anode material, which can improve the leaching rate of metals, especially the leaching rate of high-valence metals, with larger improvement range and high recovery efficiency.
The specific technical scheme of the invention is as follows:
a recycling method of waste lithium battery anode materials comprises the following steps:
s1) discharging, crushing and screening: placing the waste lithium battery in a sodium chloride solution with the weight of 2-3% until the discharge is complete, taking out the battery, crushing and sieving the battery, and removing the metal shell, the negative electrode material, the electrolyte and the diaphragm to obtain a positive electrode material;
s2) separation of active material: placing the positive electrode material into N-methyl pyrrolidone, heating and soaking to dissolve the binder, peeling the active material from the current collector, and ultrasonically cleaning to obtain the active material;
s3) ball milling reduction: adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9-10, preparing a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material;
s4) acid leaching recovery: filtering the ball-milled material, washing filter residues with deionized water for 3-5 times, adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 10-20min, and filtering to obtain a leaching solution containing recovered metals.
Preferably, the temperature of the heating and soaking in the step S2) is 110-120 ℃ and the time is 40-60min.
Preferably, the ultrasonic frequency of the ultrasonic cleaning in the step S2) is 80-100kHz, and the time is 5-10min.
Preferably, the mass ratio of the positive electrode material to the N-methyl pyrrolidone in the S2) is 1:4-8.
Preferably, in S3), the concentration of hydrazine hydrate in the reducing solution is 0.5-1mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03-0.05mol/L, and the concentration of gallic acid methyl ester is 0.06-0.1mol/L.
Preferably, the mass ratio of the active material to the reducing solution in S3) is 1:15-20.
Preferably, the heating temperature of the heating ball milling in the step S3) is 50-60 ℃, the ball milling rotating speed is 90-120r/min, and the time is 20-40min.
The invention obtains the positive electrode active material through discharging, crushing, screening and separating, and then reduces the positive electrode active material and then carries out acid leaching. The reduction process adopts a reducing solution prepared from hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid, methyl gallate and deionized water, and the acid leaching process adopts a hydrochloric acid solution. Since lithium ions are easily leached by acid liquor and the leaching rate is high, the key to improving the recovery rate is how to improve the leaching rate of high-valence metal ions. The invention adopts the reducing solution to reduce the high valence metal ions in the active material, such as +3 valence manganese, cobalt and nickel, to reduce the high valence metal ions into bivalent oxides or metal simple substances, and adopts the hydrochloric acid solution to leach, so that the bivalent oxides or simple substances of the manganese, cobalt and nickel are easy to react with the hydrochloric acid, thereby obtaining the leaching solution containing various recovered metals. The method can improve the leaching rate of various metals, and especially the leaching rate of high-valence metals is greatly improved.
The reducing solution adopted by the invention contains hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate, which have the capability of reducing metal ions under alkaline conditions, wherein the hydrazine hydrate has strong reducing capability, and the addition of ethylenediamine tetramethylene phosphonic acid and methyl gallate can further improve the complexation with metal ions, thereby improving the reducing efficiency, and the reducing solution can ensure the reducing effect and shorten the reducing time.
Furthermore, the active material and the reducing solution are added into a ball mill, and the reduction reaction is carried out in the heating ball milling process. In the reduction process, divalent oxides or metal simple substances obtained by reducing high-valence metal ions can be stripped from the surface of the active material through ball milling shearing action, so that the divalent oxides or metal simple substances are prevented from being deposited on the surface of the active material, contact between a reducing solution and unreduced active material is prevented, further reduction reaction is prevented, and incomplete reduction is prevented. And the particle size of the active material can be reduced by ball milling, and the specific surface area is increased. Therefore, the reduction reaction can be carried out while ball milling, so that the reduction rate and the reduction effect can be further improved, and the leaching rate of the high-valence metal can be improved.
Compared with the prior art, the invention provides a recovery method of the waste lithium battery anode material, which has the outstanding characteristics and excellent effects that: the recovery method can improve the leaching rate of metals, especially the leaching rate of high-valence metals, and has the advantages of larger improvement range, high ball milling reduction and leaching efficiency and short time consumption.
Detailed Description
In the following, the technical scheme of the invention is further described in detail by taking a nickel cobalt lithium manganate battery and a nickel cobalt lithium aluminate battery as examples, and various technological parameters or operations are replaced or changed without departing from the ideas of the method of the invention, and the method is included in the scope of the invention.
Example 1
S1) placing a waste nickel cobalt lithium aluminate lithium battery in a 2wt% sodium chloride solution until discharge is complete, taking out the battery, crushing and screening the battery, and removing a metal shell, a negative electrode material, an electrolyte and a diaphragm to obtain a positive electrode material;
s2) placing the positive electrode material in N-methyl pyrrolidone, heating to 110 ℃ and soaking for 60min to dissolve the binder, peeling off the active material from the current collector, and then cleaning with 80kHz ultrasonic waves for 10min to obtain the active material; the mass ratio of the positive electrode material to the N-methyl pyrrolidone is 1:6, preparing a base material;
s3) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.5mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.05mol/L, and the concentration of gallic acid methyl ester is 0.1mol/L; the mass ratio of the active material to the reducing solution is 1:20, a step of; the heating temperature of the heating ball milling is 50 ℃, the ball milling rotating speed is 120r/min, and the time is 40min;
s4) filtering the ball-milled material, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, aluminum and lithium.
Example 2
S1) placing a waste nickel cobalt lithium aluminate battery in a 3wt% sodium chloride solution until discharge is complete, taking out the battery, crushing and screening the battery, and removing a metal shell, a negative electrode material, an electrolyte and a diaphragm to obtain a positive electrode material;
s2) placing the positive electrode material in N-methyl pyrrolidone, heating to 120 ℃ and soaking for 40min to dissolve the binder, peeling off the active material from the current collector, and then cleaning with 100kHz ultrasonic waves for 5min to obtain the active material; the mass ratio of the positive electrode material to the N-methyl pyrrolidone is 1:6, preparing a base material;
s3) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 1mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03mol/L, and the concentration of gallic acid methyl ester is 0.06mol/L; the mass ratio of the active material to the reducing solution is 1:20, a step of; the heating temperature of the heating ball milling is 60 ℃, the ball milling rotating speed is 90r/min, and the time is 30min;
s4) filtering the ball-milled material, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, aluminum and lithium.
Example 3
S1) placing a waste nickel cobalt lithium manganate lithium battery in a 3wt% sodium chloride solution until discharge is complete, taking out the battery, crushing and screening the battery, and removing a metal shell, a negative electrode material, an electrolyte and a diaphragm to obtain a positive electrode material;
s2) placing the positive electrode material in N-methyl pyrrolidone, heating to 120 ℃ and soaking for 40min to dissolve the binder, peeling the active material from the current collector, and then cleaning with 80kHz ultrasonic waves for 10min to obtain the active material; the mass ratio of the positive electrode material to the N-methyl pyrrolidone is 1:8, 8;
s3) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.8mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.04mol/L, and the concentration of gallic acid methyl ester is 0.08mol/L; the mass ratio of the active material to the reducing solution is 1:18; the heating temperature of the heating ball milling is 55 ℃, the ball milling rotating speed is 120r/min, and the time is 30min;
s4) filtering the ball-milled material, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, manganese and lithium.
Example 4
S1) placing a waste nickel cobalt lithium manganate lithium battery in a 2wt% sodium chloride solution until discharge is complete, taking out the battery, crushing and screening the battery, and removing a metal shell, a negative electrode material, an electrolyte and a diaphragm to obtain a positive electrode material;
s2) placing the positive electrode material in N-methyl pyrrolidone, heating to 115 ℃ and soaking for 50min to dissolve the binder, peeling off the active material from the current collector, and then cleaning with 90kHz ultrasonic waves for 8min to obtain the active material; the mass ratio of the positive electrode material to the N-methyl pyrrolidone is 1:6, preparing a base material;
s3) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.8mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03mol/L, and the concentration of gallic acid methyl ester is 0.06mol/L; the mass ratio of the active material to the reducing solution is 1:15; the heating temperature of the heating ball milling is 60 ℃, the ball milling rotating speed is 120r/min, and the time is 20min;
s4) filtering the ball-milled material, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, manganese and lithium.
Comparative example 1
S1) is as in example 4;
s2) is as in example 4;
s3) adding the active material and deionized water into a ball mill, ball-milling for 20min at a rotating speed of 120r/min, discharging and filtering; the mass ratio of the active material to deionized water is 1:15;
s4) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding the active material subjected to ball milling into the reducing solution, heating to 60 ℃ for reaction for 20min, and reducing high-valence metal in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.8mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03mol/L, and the concentration of gallic acid methyl ester is 0.06mol/L; the mass ratio of the active material to the reducing solution is 1:15;
s5) filtering the reacted materials, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, manganese and lithium.
Comparative example 2
S1) is as in example 4;
s2) is as in example 4;
s3) adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9.5, preparing a reducing solution, adding an active material into the reducing solution, heating to 60 ℃ for reaction for 20min, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.8mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03mol/L, and the concentration of gallic acid methyl ester is 0.06mol/L; the mass ratio of the active material to the reducing solution is 1:15;
s4) filtering the reacted materials, washing filter residues with deionized water for 3 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 20min, and filtering to obtain leaching liquid containing nickel, cobalt, manganese and lithium.
Performance test: the mass M and the mass fraction omega of each metal are measured before the recovery of the active material, the volume V of the leaching solution and the concentration c of each metal are measured after the recovery, and the leaching rate of each metal is calculated by V.c.100%/M.omega. The data obtained are shown in Table 1.
As can be seen from table 1:
first, the leaching rates of various metals in examples 1-4 are all high, which indicates that the method of the invention has good recovery effect on various metals in the positive electrode.
Second, the leaching rate of nickel, cobalt, and manganese is significantly reduced in comparative example 1 compared with example 4, because comparative example 1 does not employ a reduction reaction in the course of heat ball milling, but ball milling is performed first and then heat reduction reaction is performed, although the particle size of the active material can be reduced, divalent oxides or metal simple substances obtained by reduction cannot be effectively peeled off from the surface of the active material, resulting in insufficient reduction, and thus the leaching rate of nickel, cobalt, and manganese is reduced.
Third, the leaching rate of nickel, cobalt, and manganese is significantly lower than that of example 4 and the reduction range is higher than that of comparative example 1, because comparative example 2 does not perform reduction reaction in the process of heating ball milling, and directly omits the ball milling process, not only can divalent oxides or metal simple substances obtained by reduction not be effectively peeled off from the surface of the active material, but also the particle size of the active material is larger, the reduction effect of trivalent nickel, cobalt, and manganese is further reduced, and the leaching rate is also further reduced.
Fourth, the leaching rate of lithium is slightly reduced in comparative examples 1 and 2 as compared with example 4, but the degree of the reduction is small because lithium ions themselves are easily leached, no reduction is required, and lithium ions are also difficult to reduce, so that the leaching rate is little affected by the reduction process.
Table 1:
Claims (6)
1. the process of the recovery method comprises S1) discharging, crushing and screening, S2) separating active materials, S3) ball milling reduction and S4) acid leaching recovery, and is characterized in that: adding hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and methyl gallate into deionized water, stirring until the hydrazine hydrate, ethylenediamine tetramethylene phosphonic acid and the methyl gallate are completely dissolved, regulating the pH value to 9-10 to prepare a reducing solution, adding an active material and the reducing solution into a ball mill, heating and ball milling, and reducing high-valence metals in the active material; in the reducing solution, the concentration of hydrazine hydrate is 0.5-1mol/L, the concentration of ethylenediamine tetramethylene phosphonic acid is 0.03-0.05mol/L, and the concentration of gallic acid methyl ester is 0.06-0.1mol/L; the mass ratio of the active material to the reducing solution is 1:15-20 parts; the heating temperature of the heating ball milling is 50-60 ℃, the ball milling rotating speed is 90-120r/min, and the time is 20-40min.
2. The method for recycling the anode material of the waste lithium battery according to claim 1, wherein the specific processes of discharging, crushing and screening are that the waste lithium battery is placed in a sodium chloride solution with the weight percent of 2-3 until the discharging is complete, the battery is taken out for crushing and screening, and the metal shell, the anode material, the electrolyte and the diaphragm are removed, so that the anode material is obtained.
3. The method for recycling the positive electrode material of the waste lithium battery according to claim 1, wherein the method comprises the following steps: the specific process of separating the active material is that the positive electrode material is placed in N-methyl pyrrolidone, heated and soaked to dissolve the binder, the active material is peeled off from the current collector, and then ultrasonic cleaning is carried out to obtain the active material.
4. The method for recycling the positive electrode material of the waste lithium battery according to claim 3, wherein the method comprises the following steps: the temperature of the heating and soaking is 110-120 ℃ and the time is 40-60min; the ultrasonic frequency of the ultrasonic cleaning is 80-100kHz, and the time is 5-10min.
5. The method for recycling the positive electrode material of the waste lithium battery according to claim 3, wherein the method comprises the following steps: the mass ratio of the positive electrode material to the N-methyl pyrrolidone is 1:4-8.
6. The method for recycling the positive electrode material of the waste lithium battery according to claim 1, wherein the method comprises the following steps: the specific process of acid leaching recovery comprises the steps of filtering materials after ball milling, washing filter residues with deionized water for 3-5 times, then adding the filter residues into a 20wt% hydrochloric acid solution, stirring for 10-20min, and filtering to obtain leaching liquid containing recovered metals.
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