CN112158894A - Method for recovering anode material of waste lithium battery - Google Patents
Method for recovering anode material of waste lithium battery Download PDFInfo
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- CN112158894A CN112158894A CN202011013348.6A CN202011013348A CN112158894A CN 112158894 A CN112158894 A CN 112158894A CN 202011013348 A CN202011013348 A CN 202011013348A CN 112158894 A CN112158894 A CN 112158894A
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- 239000002699 waste material Substances 0.000 title claims abstract description 59
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000010405 anode material Substances 0.000 title claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000002386 leaching Methods 0.000 claims abstract description 30
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 19
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000706 filtrate Substances 0.000 claims abstract description 17
- 239000007774 positive electrode material Substances 0.000 claims abstract description 17
- 239000010949 copper Substances 0.000 claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 239000002893 slag Substances 0.000 claims abstract description 14
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 claims abstract description 13
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 12
- KCZFLPPCFOHPNI-UHFFFAOYSA-N alumane;iron Chemical compound [AlH3].[Fe] KCZFLPPCFOHPNI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 8
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000010926 waste battery Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 16
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000002739 metals Chemical class 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001448 ferrous ion Inorganic materials 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 15
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 239000006229 carbon black Substances 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000008901 benefit Effects 0.000 description 5
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- 229910052938 sodium sulfate Inorganic materials 0.000 description 5
- 235000011152 sodium sulphate Nutrition 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001437 manganese ion Inorganic materials 0.000 description 4
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 229910006025 NiCoMn Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910001447 ferric ion Inorganic materials 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000007323 disproportionation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- -1 ferrous oxide ions Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229940073644 nickel Drugs 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Secondary Cells (AREA)
Abstract
The invention belongs to the field of lithium ion battery recovery, and discloses a method for recovering a waste lithium battery anode material, which comprises the following steps: (1) acid leaching is carried out on the positive electrode material of the waste lithium battery to obtain a leaching solution; (2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution; (3) heating the copper-removed solution, adding the waste battery anode powder, mixing, reacting, adjusting the pH value to acidity, and filtering to obtain iron-aluminum slag and filtrate; (4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, and filtering to obtain lithium carbonate. According to the method for recycling the waste lithium battery positive electrode material, ferrous ions in the copper-removed liquid are used as a reducing agent, nickel, cobalt and manganese metal elements in lithium manganate, lithium cobaltate and ternary battery positive electrode flake powder are leached, and lithium in the lithium manganate, lithium cobaltate and ternary battery positive electrode flake powder is efficiently recycled.
Description
Technical Field
The invention belongs to the field of lithium ion battery recovery, and particularly relates to a method for recovering a waste lithium battery anode material.
Background
The recovery of lithium batteries is developed faster in China in recent years, waste ternary lithium batteries are subjected to monomer disassembly (also called crushing and pretreatment), leaching, copper removal, iron and aluminum removal, extraction and coprecipitation to prepare ternary precursors and lithium salts, and a byproduct is anhydrous sodium sulphate, so that good economic benefit is obtained and a large scale is formed.
After the iron powder is used for copper removal, the solution after copper removal contains ferrous ions, and in the process of iron and aluminum removal, because the ferrous ions are not easy to precipitate, the ferrous ions are required to be oxidized into the ferric ions, and then the pH value is adjusted to precipitate the ferric ions. The ferrous ions are tried to be used, but the temperature of the copper-removed solution is generally higher than 70 ℃ and obviously higher than the decomposition temperature of the hydrogen peroxide by 60 ℃, the hydrogen peroxide is added for violent decomposition, so that the groove accident is easy to occur to cause industrial injury, and the effective utilization rate of the hydrogen peroxide is less than ten percent. Therefore, there is an urgent need for a method of oxidizing ferrous ions at low cost and with high safety and without introducing chloride ions.
Valuable metals in the waste ternary pole piece powder battery are nickel, cobalt, manganese and lithium, the valuable metals are raw materials which do not contain copper in the waste ternary battery, and lithium cobaltate is also a raw material recycled from the waste ternary battery. The price of one metal ton of pyrolusite is 54 yuan, manganese in the pyrolusite is considered as a low-value metal, the price of lithium is also at a lower position at present, and the price of battery-grade lithium carbonate is more than 4 ten thousand and one ton. Because the pole piece powder, the lithium manganate and the lithium cobaltate all belong to raw materials of a battery recycling line, the raw materials are wide in source.
At present, waste lithium cobaltate and waste pole piece powder are used as recovery raw materials. For the waste lithium manganate positive electrode material, the patent number is CN101538655A, which is a method for recovering the waste lithium manganate battery positive electrode material, sulfuric acid is adopted to leach the lithium manganate, lithium is leached into a leaching solution, the manganese in the lithium manganate is subjected to disproportionation reaction, part of the manganese is changed into 4-valent precipitate to be manganese dioxide, and part of the manganese is changed into bivalent manganese and is leached into the leaching solution. If the waste lithium manganate is not used in lithium batteries, the application of manganese dioxide can really realize the method disclosed by the patent, but the waste lithium manganate positive electrode material contains impurities such as carbon black, aluminum oxide and the like, and obviously cannot be used as a super capacitor material. The main components of the leachate are lithium sulfate and manganese sulfate, and expensive caustic soda lye needs to be added to precipitate manganese ions, so that the recovery cost of the leachate is high. Therefore, the economic benefit is low, and the economic benefit of independently constructing a wet recovery production line is low, so that the lithium manganate battery is unmanned to be recovered and is difficult.
Disclosure of Invention
The invention aims to provide a method for recovering a waste lithium battery positive electrode material, which can recover and combine waste lithium manganate, waste lithium cobaltate and a waste ternary positive electrode material for production, can recover valuable metal lithium in the waste lithium manganate and the waste lithium cobaltate at low cost, has high safety and does not introduce chloride ions in the process of oxidizing ferrous ions.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for recovering a waste lithium battery anode material comprises the following steps:
(1) carrying out oxidation acid leaching on the anode material of the waste lithium battery to obtain a leaching solution;
(2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution;
(3) heating the copper-removed solution, adding the waste battery anode powder, mixing, reacting, adjusting the pH value to acidity, and filtering to obtain iron-aluminum slag and filtrate;
(4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, and filtering to obtain lithium carbonate.
Preferably, in the step (1), the waste lithium batteries are also pretreated to obtain the battery positive electrode material powder.
More preferably, the pretreatment comprises discharging, disassembling, crushing, sorting and sintering to obtain the battery cathode material powder.
Preferably, in step (1), the temperature of the acid leaching is 60 ℃ to 90 ℃.
Preferably, in the step (1), the solution used in the oxidation acid leaching is one of sulfuric acid and hydrogen peroxide.
Preferably, in the step (3), the heating is to heat the copper-removed liquid to 90-110 ℃.
Preferably, in the step (3), the pH of the solution after copper removal is 1.0-3.5.
Preferably, in the step (3), the content of ferrous ions in the solution after copper removal is more than 0.5 g/L.
Preferably, in the step (3), the waste battery positive electrode powder is at least one of waste ternary battery positive electrode flake powder, waste lithium manganate powder or waste lithium cobaltate powder.
After removing iron and aluminum from the waste lithium manganate powder or the waste lithium cobaltate powder, the substances which do not participate in the reaction are graphite residues, and the waste ternary battery anode sheet powder can directly remove iron and aluminum and does not contain graphite residues.
More preferably, the waste ternary battery positive plate powder comprises, by mass, 3-5% of lithium, 12-17% of nickel, 15-19% of cobalt and 13-19% of manganese. The waste ternary battery positive plate powder does not contain iron and copper.
Preferably, in the step (3), the reaction time is 4-6 hours, and the reaction temperature is 90-110 ℃.
Preferably, in the step (3), the pH adjustment to acidity is to adjust the pH to 3.5 to 4.5.
Preferably, in the step (3), the solution used for adjusting the pH to acidity is one of sodium hydroxide or sodium carbonate.
Preferably, in the step (3), the iron-aluminum slag is returned to the step (1) for acid leaching.
Preferably, in the step (4), the alkali liquor is sodium carbonate.
The reaction mechanism of the step (3) is as follows:
2LiNiXCoYMn(1-x-y)O2+4H2SO4+2FeSO4＝Fe2(SO4)3+2NiXCoYMn(1-X-Y)SO4+Li2SO4+H2o is represented by the formula (I),
8H2SO4+2LiMn2O4+6FeSO4＝Li2SO4+8H2O+3Fe2(SO4)3+4MnSO4the compound of the formula (II),
8H2SO4+2LiCo2O4+6FeSO4＝Li2SO4+8H2O+3Fe2(SO4)3+4CoSO4formula (III).
When only the waste ternary battery anode sheet powder is added, the mechanism is shown as the formula (I), and when the waste ternary battery anode sheet powder, the waste lithium manganate powder or the waste lithium cobaltate powder is added, the mechanism is shown as the formula (I), the formula (II) or the formula (III).
The invention also provides application of the recovery method in recovering valuable metals from the waste lithium battery positive electrode material.
The invention has the advantages that:
according to the method for recycling the waste lithium battery positive electrode material, provided by the invention, ferrous ions in the copper-removed liquid are used as a reducing agent, nickel, cobalt and manganese metal elements in lithium manganate, lithium cobaltate and ternary battery positive electrode flake powder are leached, lithium in the nickel, cobalt and manganese metal elements is efficiently recycled, the parallel production of the waste ternary positive electrode material, the waste lithium manganate and the waste lithium cobaltate is realized, and a method for safely and low-cost ferrous oxide ions without introducing chloride ions is provided.
Drawings
FIG. 1 is a process flow diagram of example 1 of the present invention;
FIG. 2 is a process flow diagram of example 2 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below with reference to the examples to further illustrate the features and advantages of the invention, and any changes or modifications that do not depart from the gist of the invention will be understood by those skilled in the art to which the invention pertains, the scope of which is defined by the scope of the appended claims.
Example 1
A method for recovering a waste lithium battery anode material comprises the following steps:
(1) acid leaching is carried out on the positive electrode material of the waste lithium battery to obtain a leaching solution and carbon black slag;
(2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution;
(3) the total content of nickel, cobalt and manganese ions is 90g/L, the content of ferrous ions is 8.0g/L, the pH value is 1.6, and the volume is 24m3Heating the copper-removed solution to 100 ℃, adding 0.32 ton of waste ternary battery anode sheet powder with 3.2 percent of lithium content, 16.8 percent of nickel content, 16.0 percent of cobalt content and 14.1 percent of manganese content, mixing, reacting for 4 hours, adding sodium hydroxide to adjust the pH value to 4.5, and performing filter pressing and washing to obtain 2.4 tons of iron-aluminum slag and ferrous ion content less than or equal to 10mg/L of filtrate;
(4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, filtering, taking filter residues to obtain lithium carbonate, and concentrating the filtrate to obtain anhydrous sodium sulphate.
And (4) drying the iron-aluminum slag obtained in the step (3) to obtain about 1.36 tons of dry filter residue, wherein the content of nickel is 0.02 percent, the content of cobalt is 0.03 percent, the content of manganese is 0.04 percent, and the content of lithium is 0.035 percent.
The reaction mechanism of the step (3) is as follows:
2LiNiXCoYMn(1-x-y)O2+4H2SO4+2FeSO4＝Fe2(SO4)3+2NiXCoYMn(1-X-Y)SO4+Li2SO4+H2o is shown as formula (I).
FIG. 1 is a process flow diagram of example 1 (black boxes indicate the steps of treatment, white boxes indicate the resulting material or added material, such as acid leaching of the cell to obtain a leachate).
Example 2
A method for recovering a waste lithium battery anode material comprises the following steps:
(1) acid leaching is carried out on the positive electrode material of the waste lithium battery to obtain a leaching solution and carbon black slag;
(2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution;
(3) heating the copper-removed liquid with the total content of nickel, cobalt and manganese ions of 93g/L, the content of ferrous ions of 5.9g/L, the pH value of 1.5 and the volume of 189L to 95 ℃, adding 2.01 kg of waste mixed powder (waste ternary battery positive plate powder, waste lithium manganate and waste lithium cobaltate powder) with the lithium content of 3.3%, the nickel content of 13.4%, the cobalt content of 15.2%, the manganese content of 18.1% and the carbon content of 12.7% for mixing, reacting for 4 hours, adding sodium hydroxide to adjust the pH value to 4.5, and performing filter pressing and washing to obtain 0.34 kg of iron-aluminum slag and filtrate with the ferrous ion content of less than or equal to 10 mg/L;
(4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, filtering, taking filter residues to obtain lithium carbonate, and concentrating the filtrate to obtain anhydrous sodium sulphate.
0.34 kg of filter residue in the step (3), wherein the manganese content is 6.8%, the lithium content is 0.45%, the proportion of nickel, cobalt and manganese entering the filtrate is more than 98%, the proportion of lithium entering the filtrate is 97%, and the economy is good; and (2) returning the filter residue to the step (1), and carrying out reduction acid leaching on the filter residue by using sulfuric acid and hydrogen peroxide to obtain 0.22 kg of carbon black residue, wherein the manganese content in the carbon black residue is 0.14%, the lithium content in the carbon black residue is 0.003%, and the total metal leaching rate is more than 99%.
The reaction mechanism is as follows:
2LiNiXCoYMn(1-x-y)O2O2+4H2SO4+2FeSO4＝Fe2(SO4)3+2NiXCoYMn(1-X-Y)SO4+Li2SO4+H2o is represented by the formula (I),
8H2SO4+2LiMn2O4+6FeSO4＝Li2SO4+8H2O+3Fe2(SO4)3+4MnSO4the compound of the formula (II),
8H2SO4+2LiCo2O4+6FeSO4＝Li2SO4+8H2O+3Fe2(SO4)3+4CoSO4formula (III).
Fig. 2 is a process flow diagram of example 2 (black boxes indicate the process steps to be carried out, white boxes indicate the resulting materials or added materials, such as battery powders obtained by pretreating the batteries).
Comparative example 1
A method for recovering a waste lithium battery anode material comprises the following steps:
(1) acid leaching is carried out on the positive electrode material of the waste lithium battery to obtain a leaching solution and carbon black slag;
(2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution;
(3) the total content of nickel, cobalt and manganese ions is 90g/L, the content of ferrous ions is 8.0g/L, the pH value is 1.6, and the volume is 24m3Heating the copper-removed solution to 100 ℃, adding sodium chlorate for mixing, reacting for 4 hours, adding sodium hydroxide to adjust the pH value to 4.5, and performing filter pressing and washing to obtain iron-aluminum slag and iron-aluminum-removed filtrate;
(4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, filtering, taking filter residues to obtain lithium carbonate, and concentrating the filtrate to obtain anhydrous sodium sulphate.
Elemental compositions of the solutions after copper removal in examples 1 to 2 and comparative example 1 were measured, and the results are shown in table 1:
TABLE 1
| Li(g/L) | NiCoMn(g/L) | Ferrous ion (g/L) | |
| Example 1 | 7.0 | 90 | 8.0 |
| Example 2 | 7.1 | 93 | 5.9 |
| Comparative example 1 | 7.1 | 90 | 8.0 |
The elemental composition of sponge copper in examples 1-2 and comparative example 1 was measured, and the results are shown in Table 2:
TABLE 2
| NiCoMn(％) | Cu(％) | Fe(％) | Al(％) | |
| Example 1 | 0.04 | 85.1 | 1.37 | 0 |
| Example 2 | 0.04 | 85.2 | 1.36 | 0 |
| Comparative example 1 | 0.04 | 85.1 | 1.37 | 0 |
The elemental compositions of the iron-aluminum slag in examples 1-2 and comparative example 1 were measured, and the results are shown in Table 3:
table 3: content of iron-aluminium slag elements
From table 3, it can be seen that the lithium content of the residue was not significantly different from that of the sodium chlorate-added residue, the content of the main element nickel cobalt was substantially the same, the content of nickel cobalt manganese was about 5 times the average value of the manganese content of the sodium chlorate-added residue, and the residue was mainly graphite due to the high reaction degree and the thorough reaction.
The nickel cobalt manganese sulfate components of examples 1-2 and comparative example 1 were measured, and the results are shown in table 4:
table 4: table of nickel, cobalt and manganese sulfate elements
The elemental compositions of the lithium carbonates of examples 1-2 and comparative example 1 were measured, and the results are shown in table 5:
table 5: lithium carbonate elemental composition table
The elemental compositions of the anhydrous sodium sulfate in examples 1-2 and comparative example 1 were measured, and the results are shown in Table 6:
table 6: list of elements of anhydrous sodium sulphate
From table 6, it can be seen that sodium chlorate is used for ferrous oxide, anhydrous sodium sulfate contains chloride ions, the value of the anhydrous sodium sulfate is changed from hundreds of yuan per ton to tens of yuan per ton, and the anhydrous sodium sulfate is difficult to sell, but the anhydrous sodium sulfate is sold directly without chloride ions in the embodiment of the invention.
The recovery rates and costs of the respective elements in examples 1-2 and comparative example 1 were as shown in Table 7:
TABLE 7
| Element(s) | Ni | Co | Mn | Li | Fe | Cu |
| Example 1 | 99.49％ | 99.2％ | 98.79％ | 95.35％ | 99.8％ | 99.85％ |
| Example 2 | 99.49％ | 99.2％ | 98.79％ | 95.85％ | 99.8％ | 99.85％ |
| Comparative example 1 | 97.50％ | 96.0％ | 95.2％ | 94.2％ | 99.2％ | 99.3％ |
As can be seen from Table 7, while the production raw materials are converted into the production auxiliary materials, the recovery rates of nickel, cobalt and manganese are higher than that of the comparative example 1, the reaction is completely carried out, and good practical application effects are obtained.
The foregoing detailed description of the method for recycling a positive electrode material of a used lithium battery according to the present invention has been presented, and the principles and embodiments of the present invention are described herein using specific examples, which are provided only to help understand the method and its core ideas of the present invention, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any combination of the methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A method for recovering a positive electrode material of a waste lithium battery is characterized by comprising the following steps:
(1) carrying out oxidation acid leaching on the anode material of the waste lithium battery to obtain a leaching solution;
(2) adding iron powder into the leaching solution for reduction to obtain sponge copper and copper-removed solution;
(3) heating the copper-removed solution, adding the waste battery anode powder, mixing, reacting, adjusting the pH value to acidity, and filtering to obtain iron-aluminum slag and filtrate;
(4) extracting the filtrate to obtain a nickel cobalt manganese sulfate solution and a raffinate, co-precipitating the nickel cobalt manganese sulfate solution to obtain a ternary precursor, adding an alkali liquor into the raffinate, and filtering to obtain lithium carbonate.
2. The recovery method according to claim 1, wherein the temperature of the acid leaching in the step (1) is 60 ℃ to 90 ℃.
3. The recovery method according to claim 1, wherein in the step (1), the solution used in the oxidation acid leaching is one of sulfuric acid and hydrogen peroxide.
4. The recycling method according to claim 1, wherein in the step (3), the waste battery positive electrode powder is at least one of waste ternary battery positive electrode flake powder, waste lithium manganate powder or waste lithium cobaltate powder.
5. The recovery method according to claim 4, wherein the lithium content of the waste ternary battery positive electrode flake powder is 3-5%, the nickel content is 12-17%, the cobalt content is 15-19%, and the manganese content is 13-19% by mass.
6. The recovery method according to claim 1, wherein in the step (3), the reaction time is 4 to 6 hours, and the reaction temperature is 90 ℃ to 110 ℃.
7. The recycling method according to claim 1, wherein in the step (3), the solution for adjusting pH is one of sodium hydroxide or sodium carbonate.
8. The recycling method according to claim 1, wherein in the step (3), the iron-aluminum slag is returned to the step (1) for acid leaching.
9. The recycling method according to claim 1, wherein in the step (4), the alkali solution is sodium carbonate.
10. Use of the recovery method according to any one of claims 1 to 9 for recovering valuable metals from positive electrode materials of used lithium batteries.
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