CN111009699A - Method for recycling lithium manganate waste battery - Google Patents
Method for recycling lithium manganate waste battery Download PDFInfo
- Publication number
- CN111009699A CN111009699A CN201911174106.2A CN201911174106A CN111009699A CN 111009699 A CN111009699 A CN 111009699A CN 201911174106 A CN201911174106 A CN 201911174106A CN 111009699 A CN111009699 A CN 111009699A
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- lithium
- waste
- recycling
- source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000004064 recycling Methods 0.000 title claims abstract description 15
- 239000010926 waste battery Substances 0.000 title claims description 16
- 239000000843 powder Substances 0.000 claims abstract description 30
- 238000005245 sintering Methods 0.000 claims abstract description 19
- 239000002699 waste material Substances 0.000 claims abstract description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 15
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 11
- 239000011572 manganese Substances 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 238000012216 screening Methods 0.000 claims abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 230000001172 regenerating effect Effects 0.000 claims description 11
- 238000003837 high-temperature calcination Methods 0.000 claims description 7
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 6
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- 239000011656 manganese carbonate Substances 0.000 claims description 4
- 229940093474 manganese carbonate Drugs 0.000 claims description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- 239000007774 positive electrode material Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 230000018109 developmental process Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- -1 lithium hexafluorophosphate Chemical compound 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62204—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products using waste materials or refuse
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
- C04B2235/3203—Lithium oxide or oxide-forming salts thereof
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3263—Mn3O4
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3262—Manganese oxides, manganates, rhenium oxides or oxide-forming salts thereof, e.g. MnO
- C04B2235/3267—MnO2
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/449—Organic acids, e.g. EDTA, citrate, acetate, oxalate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a method for recycling waste lithium manganate batteries, which comprises the steps of calcining the waste lithium manganate batteries at high temperature in a closed inert atmosphere, cooling, taking out residues, crushing, screening and magnetically separating the residues to obtain lithium manganate coarse powder, obtaining carbon powder and lithium manganate fine powder from the lithium manganate coarse powder through an air flow separation device, adding a manganese source, a lithium source and an additive into the lithium manganate fine powder, and mixing the manganese source, the lithium source and the additive according to the following ratio: lithium element: and mixing the doping ions according to the mol ratio of 2: 1-1.08: 0-0.1, and sintering the mixture in an oxygen atmosphere at a high temperature to obtain the lithium manganate material. According to the method, the waste lithium manganate battery is calcined at high temperature in a closed environment, so that the tail gas treatment is facilitated, the pollution problem in the disassembly process of the waste lithium manganate battery is solved, the production efficiency is improved, the subsequent production process does not need management and control substances such as acid, alkali and the like, the lithium manganate positive electrode material can be obtained by regeneration only through adding raw materials and additives, and the comprehensive utilization and clean production of the waste lithium manganate positive electrode material are realized.
Description
Technical Field
The invention relates to the field of resource utilization and environmental protection of waste batteries, in particular to a method for recycling and regenerating lithium manganate waste batteries.
Background
With the rapid development of the new energy automobile industry and the development of the lithium battery market in China, the power battery market in China will continue to keep the situation of high-speed development for a long time; however, the service life of the lithium battery is long, for the traditional power lithium battery, the cycle life is theoretically required to be more than 2000 times, the service life is 7-8 years, and actually, the battery pack is seriously degraded and scrapped after 5 years, and a large amount of waste batteries can be generated along with the rapid development of the industry; if the scrapped lithium battery cannot be properly treated, not only can resources be wasted, but also huge pollution is caused to the environment, and although the waste lithium ion battery does not contain heavy metal elements with high toxicity such as mercury, cadmium and lead in a dry battery and a lead-acid battery, the waste lithium ion battery contains lithium hexafluorophosphate (LiPF6), benzene compounds and ester compounds and is difficult to degrade by microorganisms;
in the prior art, the recovery mode of the scrapped lithium battery is mainly to separate a shell, a positive pole piece and a negative pole piece in a manual disassembly mode, and then the battery pole pieces are used as raw materials for wet smelting in the subsequent process; because the volatility and toxicity of the electrolyte are greatly harmful to people and environment in the disassembling process, the recovery process of the waste lithium manganate battery needs to be further researched and improved aiming at the problems faced by the waste lithium manganate battery in the recovery process at present.
Disclosure of Invention
The invention aims to solve the problems and provides a method for recycling lithium manganate waste batteries.
A method for recycling and regenerating lithium manganate waste batteries comprises the following steps:
step one, performing high-temperature calcination on waste lithium manganate batteries in a closed inert atmosphere, cooling to 20-60 ℃, and then taking out residues;
step two, crushing, screening and magnetically separating the residues obtained in the step one to obtain lithium manganate coarse powder;
thirdly, passing the lithium manganate coarse powder obtained in the second step through an airflow sorting device to obtain carbon powder and lithium manganate fine powder;
adding a manganese source, a lithium source and an additive into the lithium manganate fine powder obtained in the third step, and mixing the manganese element, the lithium element and the doped ions in the manganese source, the lithium source and the additive in a ratio of 2: 1-1.08: 0-0.1 in sequence to form a mixture;
and step five, placing the mixture obtained in the step four in an oxygen atmosphere, and sintering at a high temperature to obtain the lithium manganate material.
Preferably, the temperature of the high-temperature calcination in the first step is 300-650 ℃, and the calcination time is 0.5-6 h.
Preferably, the lithium source is one or a mixture of more than one of lithium carbonate, lithium hydroxide, lithium fluoride and lithium acetate.
Preferably, the manganese source is one or a mixture of more than one of manganese dioxide, trimanganese tetroxide and manganese carbonate.
Preferably, the additive is one or a mixture of more than one of nano aluminum oxide, titanium oxide and magnesium oxide.
Preferably, the temperature of the high-temperature sintering in the fifth step is 650-1000 ℃, and the sintering reaction time is 4-20 h.
The invention has the beneficial effects that:
according to the method, the waste lithium manganate battery is calcined at high temperature in a closed environment, so that the tail gas treatment is facilitated, the pollution problem in the disassembly process of the waste lithium manganate battery is solved, the production efficiency is improved, the subsequent production process does not need management and control substances such as acid, alkali and the like, the lithium manganate positive electrode material can be obtained by regeneration only through adding raw materials and additives, and the comprehensive utilization and clean production of the waste lithium manganate positive electrode material are realized.
Drawings
Fig. 1 is a schematic diagram of a 0.5C first charge-discharge curve of a button cell;
fig. 2 is a schematic diagram of the cycling curve of the button cell performance.
Detailed Description
Example 1
A method for recycling and regenerating lithium manganate waste batteries comprises the following steps:
(1) 100 scrapped 26650 type lithium manganate batteries are put into a box-type atmosphere resistance furnace, the inlet is sealed, nitrogen is introduced, and the gas flow is 10m3Heating to 300 ℃ for high-temperature calcination, wherein the sintering time is 0.5 hour, preserving the heat for 2 hours, naturally cooling, and taking out the waste lithium manganate battery residues after the temperature of a hearth is reduced to 20 ℃;
(2) separating the shell and the powder material by crushing and screening the residues in the step 1 to obtain lithium manganate coarse powder;
(3) passing the lithium manganate coarse powder obtained in the step (2) through an air flow sorting device to obtain carbon powder and lithium manganate fine powder; the manganese content in the lithium manganate fine powder is determined to be 56.5 percent and the lithium content is determined to be 3.5 percent through analysis;
(4) adding 7.33g of electrolytic manganese dioxide and 1.92g of battery-grade lithium carbonate into 100g of lithium manganate fine powder, and adding the mixture into a three-dimensional mixer for dry mixing for 6 hours;
(5) and (4) placing the mixture obtained in the step (4) in an oxygen box type atmosphere furnace for high-temperature sintering to obtain the lithium manganate anode material, wherein the oxygen flow is 5L/min, the sintering temperature is 650 ℃, and the sintering time is 4 hours.
Example 2
A method for recycling and regenerating lithium manganate waste batteries comprises the following steps:
(1) 100 scrapped 26650 type lithium manganate batteries are put into a box-type atmosphere resistance furnace, the inlet is sealed, nitrogen is introduced, and the gas flow is 10m3Heating to 500 ℃ for high-temperature calcination, wherein the sintering time is 3 hours, preserving the heat for 2 hours, naturally cooling, and taking out the waste lithium manganate battery residues after the temperature of a hearth is reduced to 40 ℃;
(2) separating the shell and the powder material by crushing and screening the residues in the step 1 to obtain lithium manganate coarse powder;
(3) passing the lithium manganate coarse powder obtained in the step (2) through an air flow sorting device to obtain carbon powder and lithium manganate fine powder; the manganese content in the lithium manganate fine powder is determined to be 56.5 percent and the lithium content is determined to be 3.5 percent through analysis;
(4) adding 9.69g of battery-grade manganese carbonate, 1.92g of battery-grade lithium carbonate and 1g of magnesium oxide into 100g of lithium manganate fine powder, and adding the mixture into a three-dimensional mixer for dry mixing for 6 hours;
(5) and (4) placing the mixture obtained in the step (4) in an oxygen box type atmosphere furnace for high-temperature sintering to obtain the lithium manganate anode material, wherein the oxygen flow is 5L/min, the sintering temperature is 850 ℃, and the sintering time is 12 hours.
Example 3
A method for recycling and regenerating lithium manganate waste batteries comprises the following steps:
(1) 100 scrapped 26650 type lithium manganate batteries are put into a box-type atmosphere resistance furnace, the inlet is sealed, nitrogen is introduced, and the gas flow is 10m3Heating to 650 ℃ for high-temperature calcination, wherein the sintering time is 6 hours, preserving the heat for 2 hours, naturally cooling, and taking out the waste lithium manganate battery residues after the temperature of a hearth is reduced to 60 ℃;
(2) separating the shell and the powder material by crushing and screening the residues in the step 1 to obtain lithium manganate coarse powder;
(3) passing the lithium manganate coarse powder obtained in the step (2) through an air flow sorting device to obtain carbon powder and lithium manganate fine powder; the manganese content in the lithium manganate fine powder is determined to be 56.5 percent and the lithium content is determined to be 3.5 percent through analysis;
(4) adding 9.69g of battery-grade manganese carbonate, 3.43g of battery-grade lithium acetate and 2g of titanium oxide into 100g of lithium manganate fine powder, and adding the mixture into a three-dimensional mixer for dry mixing for 6 hours;
(5) and (4) placing the mixture obtained in the step (4) in an oxygen box type atmosphere furnace for high-temperature sintering to obtain the lithium manganate anode material, wherein the oxygen flow is 5L/min, the sintering temperature is 1000 ℃, and the sintering time is 20 hours.
With reference to fig. 1 and fig. 2, the lithium manganate composite material prepared in this embodiment is used as a positive electrode, a lithium plate is used as a negative electrode, and a 2032 button cell is assembled by using a lithium manganate dedicated electrolyte, wherein the voltage interval of the button cell is 3.0V to 4.3V, the discharge rate of the button cell is 0.5C, the 0.5C initial charge and discharge curve of the button cell is shown in fig. 1, and the cycle curve of the button cell performance is shown in fig. 2.
The ternary waste battery can also be treated by the same process, wherein ternary refers to three elements of nickel, cobalt and manganese, and the ternary materials with the same proportion of 811, 622,333 and 442 can also be implemented by the technology due to different proportions of the ternary materials.
The above description is only a preferred embodiment of the present invention, and any person skilled in the art may modify the present invention or modify it into an equivalent technical solution by using the technical solution described above. Therefore, any simple modifications or equivalent substitutions made in accordance with the technical solution of the present invention are within the scope of the claims of the present invention.
Claims (6)
1. A method for recycling and regenerating waste lithium manganate batteries is characterized by comprising the following steps: the method comprises the following steps:
step one, performing high-temperature calcination on waste lithium manganate batteries in a closed inert atmosphere, cooling to 20-60 ℃, and then taking out residues;
step two, crushing, screening and magnetically separating the residues obtained in the step one to obtain lithium manganate coarse powder;
thirdly, passing the lithium manganate coarse powder obtained in the second step through an airflow sorting device to obtain carbon powder and lithium manganate fine powder;
adding a manganese source, a lithium source and an additive into the lithium manganate fine powder obtained in the third step, and mixing the manganese element, the lithium element and the doped ions in the manganese source, the lithium source and the additive in a ratio of 2: 1-1.08: 0-0.1 in sequence to form a mixture;
and step five, placing the mixture obtained in the step four in an oxygen atmosphere, and sintering at a high temperature to obtain the lithium manganate material.
2. The method for recycling and regenerating the lithium manganate waste battery as set forth in claim 1, wherein: the temperature of the high-temperature calcination in the first step is 300-650 ℃, and the time of the oxidation calcination is 0.5-6 h.
3. The method for recycling and regenerating the lithium manganate waste battery as set forth in claim 1, wherein: the lithium source is one or a mixture of more than one of lithium carbonate, lithium hydroxide, lithium fluoride and lithium acetate.
4. The method for recycling and regenerating the lithium manganate waste battery as set forth in claim 1, wherein: the manganese source is one or more of manganese dioxide, trimanganese tetroxide and manganese carbonate.
5. The method for recycling and regenerating the lithium manganate waste battery as set forth in claim 1, wherein: the additive is one or more of nano aluminum oxide, titanium oxide and magnesium oxide.
6. The method for recycling and regenerating the lithium manganate waste battery as set forth in claim 1, wherein: the temperature of the high-temperature sintering in the fifth step is 650-1000 ℃, and the sintering reaction time is 4-20 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911174106.2A CN111009699A (en) | 2019-11-26 | 2019-11-26 | Method for recycling lithium manganate waste battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911174106.2A CN111009699A (en) | 2019-11-26 | 2019-11-26 | Method for recycling lithium manganate waste battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111009699A true CN111009699A (en) | 2020-04-14 |
Family
ID=70112021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911174106.2A Pending CN111009699A (en) | 2019-11-26 | 2019-11-26 | Method for recycling lithium manganate waste battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111009699A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574219A (en) * | 2020-05-09 | 2020-08-25 | 河南中顺过滤研究院有限公司 | Preparation method of photocatalytic lithium ferrate-titanium oxide composite block and composite block |
| CN112679192A (en) * | 2020-12-29 | 2021-04-20 | 广东金意陶陶瓷集团有限公司 | High-fire-resistance limit foamed ceramic, preparation method and application |
| CN113644332A (en) * | 2021-08-02 | 2021-11-12 | 北京理工大学 | Method for repairing and regenerating cathode material of waste lithium manganate battery, cathode material and lithium ion battery |
| CN116093476A (en) * | 2022-11-30 | 2023-05-09 | 山东华劲电池材料科技有限公司 | Method for repairing lithium manganate positive electrode material with stable performance and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078719A (en) * | 2014-06-20 | 2014-10-01 | 奇瑞汽车股份有限公司 | Method for preparing nickel lithium manganate by using waste lithium manganate battery |
| CN109326843A (en) * | 2018-11-26 | 2019-02-12 | 荆门市格林美新材料有限公司 | A kind of recycling process of waste battery cathode material |
| CN109881008A (en) * | 2019-02-27 | 2019-06-14 | 广西银亿新材料有限公司 | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery |
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
-
2019
- 2019-11-26 CN CN201911174106.2A patent/CN111009699A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104078719A (en) * | 2014-06-20 | 2014-10-01 | 奇瑞汽车股份有限公司 | Method for preparing nickel lithium manganate by using waste lithium manganate battery |
| CN109326843A (en) * | 2018-11-26 | 2019-02-12 | 荆门市格林美新材料有限公司 | A kind of recycling process of waste battery cathode material |
| CN109881008A (en) * | 2019-02-27 | 2019-06-14 | 广西银亿新材料有限公司 | A kind of method that reduction roasting-water quenching recycles lithium in waste and old lithium ion battery |
| CN110165324A (en) * | 2019-06-24 | 2019-08-23 | 中国科学院青海盐湖研究所 | A kind of method and system recycling anode and Regeneration and Repair from waste lithium cell |
Non-Patent Citations (1)
| Title |
|---|
| 赵东江等: "废旧锌锰电池回收利用的研究", 《应用化工》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111574219A (en) * | 2020-05-09 | 2020-08-25 | 河南中顺过滤研究院有限公司 | Preparation method of photocatalytic lithium ferrate-titanium oxide composite block and composite block |
| CN112679192A (en) * | 2020-12-29 | 2021-04-20 | 广东金意陶陶瓷集团有限公司 | High-fire-resistance limit foamed ceramic, preparation method and application |
| CN112679192B (en) * | 2020-12-29 | 2023-08-29 | 广东金意陶陶瓷集团有限公司 | High-fire-resistance limit foaming ceramic, preparation method and application |
| CN113644332A (en) * | 2021-08-02 | 2021-11-12 | 北京理工大学 | Method for repairing and regenerating cathode material of waste lithium manganate battery, cathode material and lithium ion battery |
| CN116093476A (en) * | 2022-11-30 | 2023-05-09 | 山东华劲电池材料科技有限公司 | Method for repairing lithium manganate positive electrode material with stable performance and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112490527B (en) | Method for regenerating lithium ion battery positive electrode material, positive electrode material and lithium ion battery | |
| CN112142029B (en) | Method for repairing and regenerating anode material of waste lithium iron phosphate battery | |
| CN111009699A (en) | Method for recycling lithium manganate waste battery | |
| CN102208706A (en) | A method for recycling and regenerating positive electrode materials of waste lithium iron phosphate batteries | |
| CN112886084B (en) | Method for repairing layered oxide positive electrode material of sodium ion battery | |
| CN111003700A (en) | Method for recycling waste lithium iron phosphate batteries | |
| CN105375079A (en) | Solid-phase sintering regeneration method for positive electrode material of waste lithium iron phosphate battery | |
| CN114784271B (en) | A regenerated lithium iron phosphate positive electrode material, preparation method and application | |
| CN116093482A (en) | Recycling method and application of waste lithium ion battery anode material | |
| CN113948788B (en) | Lithium cobalt oxide positive electrode material and regeneration and repair method and application thereof | |
| CN115140785A (en) | Method for recycling and reusing anode of waste lithium ion battery | |
| GB2621300A (en) | Method for regenerating lithium battery positive electrode material | |
| CN112777648B (en) | High-performance cathode material regenerated by simple solid phase recovery method and preparation method thereof | |
| WO2023040010A1 (en) | Method for repairing cathode material of spent lithium ion battery | |
| CN117096486A (en) | Repairing and regenerating method for waste lithium ion battery anode material | |
| CN1234177C (en) | Method for improving high-temperature performance of lithium ion battery positive material LiMn2O4 | |
| CN116177621B (en) | Method for preparing high nickel positive electrode material using Li2CO3, positive electrode material and application | |
| CN114824544B (en) | Lithium iron phosphate cathode material, preparation method and application | |
| CN111129469A (en) | FexOy-FeS2-zComposite material and preparation method and application thereof | |
| CN102263241B (en) | Preparation method of positive electrode material of lithium ion battery for electric vehicle | |
| CN112607787B (en) | Method for recycling lithium cobaltate high-iron material | |
| CN1234180C (en) | Modifying method for lithium ion cell positive pole material LiMn2O4 | |
| CN105047869A (en) | A kind of synthetic method of lithium ion cathode material LiNiO2/C | |
| WO2020118716A1 (en) | Method for ultrasonic hydrothermal repair of waste ternary battery cathode material | |
| CN109494362B (en) | Positive electrode material for thermal battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200414 |
|
| RJ01 | Rejection of invention patent application after publication |