CN117121267A - Method for integrally treating waste ternary lithium battery through full chain - Google Patents
Method for integrally treating waste ternary lithium battery through full chain Download PDFInfo
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- CN117121267A CN117121267A CN202380009576.1A CN202380009576A CN117121267A CN 117121267 A CN117121267 A CN 117121267A CN 202380009576 A CN202380009576 A CN 202380009576A CN 117121267 A CN117121267 A CN 117121267A
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- Prior art keywords
- acid
- leaching
- lithium
- roasting
- graphite
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 153
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 93
- 239000002699 waste material Substances 0.000 title claims abstract description 41
- 238000002386 leaching Methods 0.000 claims abstract description 205
- 239000002253 acid Substances 0.000 claims abstract description 174
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000010439 graphite Substances 0.000 claims abstract description 93
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 93
- 238000000605 extraction Methods 0.000 claims abstract description 68
- 239000000696 magnetic material Substances 0.000 claims abstract description 65
- 238000007885 magnetic separation Methods 0.000 claims abstract description 46
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 30
- 239000002893 slag Substances 0.000 claims abstract description 29
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 18
- 239000000047 product Substances 0.000 claims description 79
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 49
- 230000008569 process Effects 0.000 claims description 42
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 238000005188 flotation Methods 0.000 claims description 27
- 238000003763 carbonization Methods 0.000 claims description 24
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 239000012535 impurity Substances 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 238000000746 purification Methods 0.000 claims description 20
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 20
- 239000003153 chemical reaction reagent Substances 0.000 claims description 18
- 229940044175 cobalt sulfate Drugs 0.000 claims description 15
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 15
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 15
- 229940099596 manganese sulfate Drugs 0.000 claims description 15
- 239000011702 manganese sulphate Substances 0.000 claims description 15
- 235000007079 manganese sulphate Nutrition 0.000 claims description 15
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 15
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 15
- 229940053662 nickel sulfate Drugs 0.000 claims description 15
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 14
- 229910017604 nitric acid Inorganic materials 0.000 claims description 14
- 239000003575 carbonaceous material Substances 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 12
- 238000005554 pickling Methods 0.000 claims description 12
- 238000010304 firing Methods 0.000 claims description 11
- 235000021110 pickles Nutrition 0.000 claims description 11
- 235000010265 sodium sulphite Nutrition 0.000 claims description 10
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 10
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000003245 coal Substances 0.000 claims description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 6
- 230000008439 repair process Effects 0.000 claims description 6
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 5
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000011295 pitch Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000003809 water extraction Methods 0.000 claims description 3
- 238000004064 recycling Methods 0.000 abstract description 6
- 239000010926 waste battery Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 30
- 230000000052 comparative effect Effects 0.000 description 21
- 239000010941 cobalt Substances 0.000 description 15
- 229910017052 cobalt Inorganic materials 0.000 description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 15
- 238000011084 recovery Methods 0.000 description 12
- 239000010426 asphalt Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 238000001354 calcination Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000004088 foaming agent Substances 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 5
- 229910052748 manganese Inorganic materials 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- -1 extractant P507) Chemical compound 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 4
- 239000003350 kerosene Substances 0.000 description 4
- 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 4
- 235000019353 potassium silicate Nutrition 0.000 description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical group CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 239000002817 coal dust Substances 0.000 description 3
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229940116411 terpineol Drugs 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001698 pyrogenic effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 description 1
- 235000019982 sodium hexametaphosphate Nutrition 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
-
- 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
- Processing Of Solid Wastes (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for integrally treating waste ternary lithium batteries by using a full chain, and belongs to the technical field of waste battery recycling. The method comprises the following steps: roasting battery black powder in the waste ternary lithium battery to be treated and a reducing agent for the first time to obtain a first roasting product; carrying out lithium extraction treatment on the first roasting product, and carrying out magnetic separation on lithium extraction slag obtained by the lithium extraction treatment; carrying out first acid leaching on the non-magnetic materials separated by magnetic separation, and carrying out solid-liquid separation to obtain first acid leaching residues; roasting the first acid leaching slag for the second time to obtain a second roasting product; and floating graphite in the second roasting product. The method at least can efficiently recycle graphite in the waste ternary lithium battery, and avoids resource waste.
Description
Technical Field
The disclosure relates to the technical field of waste battery recycling, in particular to a method for integrally treating waste ternary lithium batteries through a full chain.
Background
With the high-speed development of new energy automobile industry in recent years, the yield and the demand of lithium ion batteries are gradually increased, and the waste lithium ion batteries contain a large amount of heavy metals and organic matters, so that the environment is greatly polluted if the waste lithium ion batteries are not recycled, and the survival of human beings is also endangered. The waste lithium batteries are effectively recycled and green, so that the environmental problem can be solved, and the recycling of valuable components of the waste lithium batteries can create great economic benefits.
The traditional recovery process of the waste ternary lithium battery is mainly divided into a fire process and a wet process, wherein the fire process is that the waste lithium battery is smelted at a high temperature to generate a metal alloy, and then the product is obtained from the alloy by utilizing the wet process or the electrolysis process; the wet process is to disassemble, crush and screen the waste ternary lithium battery to obtain black powder, and then leach, remove impurities and extract the black powder.
However, graphite in waste ternary lithium batteries is difficult to effectively recover, whether by a pyrogenic process or a wet process.
In view of this, the present disclosure is specifically proposed.
Disclosure of Invention
The purpose of the disclosure includes providing a method for integrally treating waste ternary lithium batteries by using a full chain, which can at least effectively recover graphite in the waste ternary lithium batteries and avoid resource waste.
The present disclosure may be implemented as follows:
the disclosure provides a method for integrally treating waste ternary lithium batteries by using a full chain, which comprises the following steps:
roasting battery black powder in the waste ternary lithium battery to be treated and a reducing agent for the first time to obtain a first roasting product; carrying out lithium extraction treatment on the first roasting product, and carrying out magnetic separation on lithium extraction slag obtained by the lithium extraction treatment; carrying out first acid leaching on the non-magnetic materials separated by magnetic separation, and carrying out solid-liquid separation to obtain first acid leaching residues; roasting the first acid leaching slag for the second time to obtain a second roasting product with amorphous carbon removed; and floating graphite in the second roasting product.
In an alternative embodiment, the reducing agent comprises at least one of pulverized coal, carbon powder, and an organic carbon reducing agent;
and/or the mass ratio of the battery black powder to the reducing agent is 100:2-100:15.
In an alternative embodiment, the first firing includes at least one of the following features:
characteristic one: the first roasting is carried out under the anaerobic condition;
and the second characteristic is: the temperature of the first roasting is 500-800 ℃;
and (3) the following characteristics: the time of the first roasting is 30min-240min.
In an alternative embodiment, the lithium extraction process comprises: and leaching the lithium from the first roasting product by water, and leaching the lithium from the solid obtained by leaching the lithium by acid.
In an alternative embodiment, the mass ratio of the first calcination product to water during water extraction of lithium is 1:3-1:15; and/or leaching lithium in water for 10min-120min.
In an alternative embodiment, the acid leaching lithium process includes at least one of the following features:
characteristic one: the acid used for leaching lithium includes sulfuric acid;
and the second characteristic is: the concentration of acid used in the acid leaching process is 10g/L-100g/L, and the mass ratio of the acid used in the acid leaching process to the solid obtained by water leaching extraction is 2:1-6:1;
and (3) the following characteristics: the time for leaching lithium by acid is 10min-100min.
In an alternative embodiment, the magnetic separation includes at least one of the following features:
characteristic one: magnetic separation is carried out in a magnetic separation column;
and the second characteristic is: the magnetic field intensity used for magnetic separation is 2000GS-12000GS;
and (3) the following characteristics: the magnetic separation is carried out in the presence of water, and the water quantity is 10L/h-100L/h.
In an alternative embodiment, the first acid leaching comprises: the non-magnetic material is pressure leached with a first acid and a first oxidizing agent.
In an alternative embodiment, the first acid leaching process includes at least one of the following features:
characteristic one: the first acid comprises sulfuric acid;
and the second characteristic is: the mass ratio of the non-magnetic material to the first acid is 1:2-1:5, and the concentration of the first acid is 150g/L-400g/L;
and (3) the following characteristics: the amount of the first oxidant is 0.5 to 3 times the molar amount of the metal contained in the non-magnetic material;
and four characteristics: the first oxidant comprises at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
and fifth feature: the pressure of the first acid leaching is 0.4MPa to 1.5MPa;
and six, characteristics: the time of the first acid leaching is 20min-120min.
In an alternative embodiment, the second firing includes at least one of the following features:
characteristic one: the second roasting is carried out under the aerobic condition;
And the second characteristic is: the temperature of the second roasting is 300-550 ℃;
and (3) the following characteristics: the second roasting time is 30min-180min.
In an alternative embodiment, the flotation is performed in a flotation column.
In an alternative embodiment, the floated graphite is repaired to yield battery grade graphite.
In an alternative embodiment, the repair process includes: the graphite is coated with a carbonaceous material and subsequently carbonized at high temperatures.
In an alternative embodiment, the carbonaceous material includes at least one of pitch, glucose, and sucrose.
In an alternative embodiment, the carbonaceous material is present in an amount of 2wt% to 15wt% of graphite.
In alternative embodiments, the high temperature carbonization is at a temperature of 800 ℃ to 1500 ℃ and/or the high temperature carbonization is for a time of 30min to 240min; and/or, the high temperature carbonization is performed in an oxygen-free atmosphere.
In an alternative embodiment, the graphite is further purified prior to repair.
In an alternative embodiment, the reagents used for purification include hydrochloric acid and nitric acid.
In an alternative embodiment, the lithium extraction liquid obtained by the lithium extraction treatment is subjected to lithium precipitation treatment to obtain a lithium-containing product.
In an alternative embodiment, the magnetic material obtained by magnetic separation is subjected to second acid leaching, and solid-liquid separation is carried out to obtain second acid leaching liquid; and extracting and removing impurities from the second pickle liquor to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
In an alternative embodiment, the second acid leaching comprises: and leaching the magnetic material with a second acid and a second oxidant under normal pressure.
In an alternative embodiment, the second acid leaching process includes at least one of the following features:
characteristic one: the second acid comprises sulfuric acid;
and the second characteristic is: the mass ratio of the magnetic material to the second acid is 1:2-1:5, and the concentration of the second acid is 150g/L-400g/L;
and (3) the following characteristics: the dosage of the second oxidant is 0.5-3 times of the molar quantity of the metal contained in the magnetic material;
and four characteristics: the second oxidant comprises at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
and fifth feature: the second acid leaching time is 30min-240min.
In an alternative embodiment, the extraction reagent used in the extraction of the second pickling solution comprises at least one of mono-2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, and di (2, 4-trimethylpentyl) phosphinic acid.
In an alternative embodiment, the first pickling solution obtained after the first pickling is subjected to impurity removal and extraction to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate.
In an alternative embodiment, the extraction reagent used in the extraction of the first pickling solution comprises at least one of mono-2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, and di (2, 4-trimethylpentyl) phosphinic acid.
The beneficial effects of the present disclosure include: the method comprises the steps of roasting battery black powder in a waste ternary lithium battery to be treated and a reducing agent for the first time to obtain a first roasting product; carrying out lithium extraction treatment on the first roasting product, and carrying out magnetic separation on lithium extraction slag obtained by the lithium extraction treatment; carrying out first acid leaching on the non-magnetic materials separated by magnetic separation, and carrying out solid-liquid separation to obtain first acid leaching residues; roasting the first acid leaching slag for the second time to obtain a second roasting product; and floating graphite in the second roasting product. The method at least can efficiently recycle graphite in the waste ternary lithium battery, and avoids resource waste.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present disclosure and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person of ordinary skill in the art.
FIG. 1 is a process flow diagram of the method for integrally treating waste ternary lithium batteries by using a full chain in example 1;
Fig. 2 is an SEM image of the battery grade graphite product obtained in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present disclosure more apparent, the technical solutions in the embodiments of the present disclosure will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method for integrally treating the waste ternary lithium battery through the full chain provided by the disclosure is specifically described below.
The disclosure provides a method for integrally treating waste ternary lithium batteries by using a full chain, which can comprise the following steps: roasting battery black powder in the waste ternary lithium battery to be treated and a reducing agent for the first time to obtain a first roasting product; carrying out lithium extraction treatment on the first roasting product, and carrying out magnetic separation on lithium extraction slag obtained by the lithium extraction treatment; carrying out first acid leaching on the non-magnetic materials separated by magnetic separation, and carrying out solid-liquid separation to obtain first acid leaching residues; roasting the first acid leaching slag for the second time to obtain a second roasting product; and floating graphite in the second roasting product.
As a reference, the waste ternary lithium battery mainly refers to a waste nickel-cobalt-manganese ternary lithium battery, and the battery black powder can be obtained by discharging, crushing, cracking and sieving the waste ternary lithium battery to be treated. Illustratively, the main components in the battery black powder include ternary positive electrode material, graphite negative electrode material, conductive agent, binder and a small amount of current collector (such as copper foil, aluminum foil, etc.).
The reducing agent used in the present disclosure may include, by way of example and not limitation, at least one of pulverized coal, carbon powder, and an organic carbon reducing agent.
The mass ratio of the battery black powder to the reducing agent can be 100:2-100:15, such as 100:2, 100:3, 100:4, 100:5, 100:6, 100:7, 100:8, 100:9, 100:10, 100:11, 100:12, 100:13, 100:14 or 100:15, etc., and can be any other value in the range of 100:2-100:15. In some embodiments, the mass ratio of battery black powder to coal fines is 100:6.
In the present disclosure, the first calcination is performed under anaerobic conditions, for example, under inert gas conditions or nitrogen conditions.
The temperature of the first firing may be 500℃to 800℃such as 500℃550℃600℃650℃700℃750℃or 800℃or any other value in the range of 500℃to 800 ℃. In some embodiments, the temperature of the first firing is 650 ℃.
The first calcination time may be 30min-240min, such as 30min, 50min, 80min, 100min, 120min, 150min, 180min, 200min, 220min or 240min, or any other value within 30min-240 min. In some embodiments, the time for the first firing is 180 minutes.
On the premise, most of nickel and cobalt in the battery black powder can be reduced into magnetic nickel simple substance and cobalt simple substance by carrying out reduction roasting (first roasting) on the battery black powder and a reducing agent, so that the subsequent magnetic separation is facilitated to obtain magnetic metal substances, non-magnetic graphite and other substances, and the nickel and cobalt are prevented from influencing the separation of the subsequent graphite. And the lithium contained in the battery black powder can form lithium-containing carbonate in the first roasting process, so that the lithium is effectively leached in the lithium extraction treatment, and the influence of the lithium on the separation of the subsequent graphite is avoided. It should be noted that manganese is still in the form of oxides at the first firing temperature and is not reduced to elemental form.
In the present disclosure, the lithium extraction process includes: and leaching the lithium from the first roasting product by water, and leaching the lithium from the solid obtained by leaching the lithium by acid.
For reference, in the water leaching lithium process, the mass ratio of the first baked product to water may be 1:3-1:15, such as 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, or 1:15, etc., and may be any other value in the range of 1:3-1:15. In some embodiments, the mass ratio of the first calcination product to water is 1:12.
The water extraction time of lithium can be 10min-120min, such as 10min, 20min, 40min, 60min, 80min, 100min or 120min, or any other value within 10min-120 min. In some embodiments, the time for leaching lithium with water is 90 minutes.
By leaching lithium according to the conditions, most of lithium can be leached, and the purity of the leached lithium is high, so that the subsequent impurity removal cost is reduced.
For reference, the acid used in the acid leaching of lithium includes sulfuric acid and the like.
The acid concentration used in the acid leaching process may be 10g/L to 100g/L, such as 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L, etc., and may be any other value in the range of 10g/L to 100 g/L. In some embodiments, the acid concentration used in the acid leaching process is 60g/L.
The mass ratio of the acid used in the acid leaching process to the solids obtained by water leaching extraction can be 2:1-6:1, such as 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1 or 6:1, etc., and can be any other value in the range of 2:1-6:1. In some embodiments, the acid leaching process uses a mass ratio of acid to water extracted solids of 1:3.
The time for leaching lithium with acid may be 10min-100min, such as 10min, 20min, 30min, 40min, 50min, 60min, 70min, 80min, 90min or 100min, or any other value within 10min-100 min. In some embodiments, the time for acid leaching lithium is 60 minutes.
By acid leaching lithium under the above conditions, lithium remaining in the solid obtained by water leaching can be further effectively extracted.
On the premise, by leaching lithium with water, most of lithium can be selectively leached, and nickel, cobalt and manganese cannot be leached in the process; the lithium which is not leached in the water leaching lithium stage can be further leached by acid leaching lithium (nickel, cobalt and manganese are not leached basically because the concentration of acid used in the acid leaching process is low). The lithium is extracted by the mode of leaching with water and then leaching with acid, so that a higher lithium leaching rate can be obtained.
In the present disclosure, the lithium extraction slag obtained by the lithium extraction treatment is the leaching slag obtained by the acid leaching lithium treatment, and the leaching slag includes magnetic materials (such as nickel, cobalt, manganese, etc.) and non-magnetic materials (such as graphite and non-magnetic oxides of nickel, cobalt, manganese, etc.).
As a reference, the magnetic separation of the above-mentioned magnetic material and non-magnetic material may be performed in a magnetic separation column.
The magnetic field strength used for the magnetic separation may be 2000GS-12000GS, such as 2000GS, 4000GS, 6000GS, 8000GS, 10000GS or 12000GS, or any other value within the range of 2000GS-12000 GS. In some embodiments, the magnetic field strength used for the magnetic separation is 10000GS.
The magnetic separation is carried out in the presence of water, namely, the leaching slag obtained after acid leaching lithium treatment is mixed with water and then subjected to magnetic separation. Illustratively, the amount of water used in the magnetic separation process may be 10L/h to 100L/h, such as 10L/h, 20L/h, 30L/h, 40L/h, 50L/h, 60L/h, 70L/h, 80L/h, 90L/h, or 100L/h, and the like, and may be any other value within the range of 10L/h to 100L/h. In some embodiments, the amount of water used in the magnetic separation process is 60L/h.
On the premise of bearing, through the magnetic separation, magnetic materials and non-magnetic materials can be effectively separated by utilizing the magnetic field of the magnetic separation column and the gravity elutriation, the magnetic materials mainly comprise nickel, cobalt and manganese, and the impurity content in the leaching liquid of the magnetic materials is greatly reduced. The non-magnetic material contains, in addition to graphite, nickel and cobalt (e.g., nickel oxide, cobalt oxide), manganese oxide, etc., which are partially unreduced into simple substances.
In the present disclosure, the first acid leaching includes: the non-magnetic material is pressure leached with a first acid and a first oxidizing agent.
The first acid used in this process includes sulfuric acid and the like.
The mass ratio of the non-magnetic material to the first acid may be 1:2-1:5, such as 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, etc., or any other value within the range of 1:2-1:5. In some embodiments, the mass ratio of the non-magnetic material to the first acid is 1:3.
The concentration of the first acid may be 150g/L to 400g/L, such as 150g/L, 200g/L, 250g/L, 300g/L, 350g/L, 400g/L, etc., or any other value in the range of 150g/L to 400 g/L. In some embodiments, the concentration of the first acid is 200g/L.
The amount of the first oxidizing agent may be 0.5 to 3 times, such as 0.5, 1, 1.5, 2, 2.5, or 3 times, the molar amount of the metal contained in the nonmagnetic material, or any other value in the range of 0.5 to 3 times. In some embodiments, the first oxidizing agent is used in an amount of 1.2 times the molar amount of the metal contained in the non-magnetic material.
The first oxidizing agent may illustratively include at least one of hydrogen peroxide, sodium sulfite, and sodium thiosulfate.
For reference, the pressure of the first acid leaching may be 0.4MPa to 1.5MPa, such as 0.4MPa, 0.5MPa, 0.8MPa, 1.0MPa, 1.2MPa, 1.5MPa, etc., and may be any other value within the range of 0.4MPa to 1.5 MPa. In some embodiments, the pressure of the first acid leach is 1MPa.
The first acid leaching time may be 20min-120min, such as 20min, 40min, 60min, 80min, 100min or 120min, or any other value within 20min-120 min. In some embodiments, the time of the first acid leaching is 90 minutes.
After the first acid leaching, solid-liquid separation is carried out to obtain first acid leaching slag and first acid leaching liquid. The first acid leaching slag mainly comprises graphite slag, and also contains a small part of metal simple substances such as nickel and cobalt which are not completely leached and oxides thereof. The first pickling liquid mainly contains nickel, cobalt and manganese, and comprises nickel sulfate, cobalt sulfate and manganese sulfate.
On the other hand, by carrying out pressurized acid leaching on the nonmagnetic material according to the conditions, most of nickel, cobalt and manganese in the nonmagnetic material can be leached, and the leaching reaction rate is accelerated, and the leaching time is shortened.
In some embodiments, the first pickling solution obtained by the first pickling may be subjected to further impurity removal and extraction to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate.
For reference, the extraction reagent used in the extraction of the first pickling solution may illustratively include at least one of 2-ethylhexyl phosphate mono-2-ethylhexyl ester (i.e., extractant P507), di (2-ethylhexyl) phosphate ester (i.e., extractant P204), and di (2, 4-trimethylpentyl) phosphinic acid (i.e., extractant C272). In some embodiments, the first pickle liquor may be extracted in steps using the extraction reagents described above.
If the first acid leaching residue is directly subjected to flotation, it is difficult to effectively separate graphite and amorphous carbon (such as pulverized coal in a conductive agent and a reducing agent) in the first acid leaching residue, and the oxidation temperature of the graphite is higher than that of the amorphous carbon. Thus, the present disclosure subjects the first acid leaching residue to a second roasting and then to flotation.
The second calcination is carried out under aerobic conditions, which may be, for example, air conditions or oxygen conditions.
The temperature of the second firing may be 300℃to 550℃such as 300℃and 350℃and 400℃and 450℃and 500℃or 550℃or any other value within the range of 300℃to 550 ℃. In some embodiments, the temperature of the second firing is 450 ℃.
The second roasting time is 30min-180min, such as 30min, 50min, 80min, 100min, 120min, 150min or 180min, or any other value within 30min-180 min. In some embodiments, the second firing time is 120 minutes.
On the premise, amorphous carbon in the first acid leaching slag can be effectively removed by performing the second roasting according to the conditions, and the quality of the subsequent graphite concentrate is improved. In addition, after the first acid leaching, a small part of metal simple substances and oxides such as nickel and cobalt which are not leached completely can be baked for the second time to form metal oxides which are easier to react with acid (such as sulfuric acid), so that the subsequent purification and impurity removal are facilitated.
In this disclosure, flotation may be performed in a flotation column, and the flotation reagents used in flotation include collectors, frothers, and modifiers. Wherein the collector comprises kerosene or diesel oil, which may be used in an amount of 300g/t, for example; the foaming agent comprises a pinitol oil or a sec-octanol, which may be used in an amount of, for example, 120g/t; the regulator comprises water glass or sodium hexametaphosphate, which can be used in an amount of 1000g/t, for example.
It should be noted that the flotation using the flotation column of the present disclosure has the following advantages over the conventional flotation using a flotation machine: the grade of the graphite product obtained by the flotation column is higher, and the recovery rate is also higher.
Through the flotation, the recovery of fine-fraction graphite is facilitated and the recovery rate of graphite is improved.
Further, the floated graphite can be repaired, so that the battery grade graphite is obtained.
For reference, the repair process may include: the graphite is coated with a carbonaceous material and subsequently carbonized at high temperatures.
The carbonaceous material may illustratively include at least one of pitch, glucose, and sucrose. In some embodiments, the carbonaceous material is pitch.
Illustratively, the carbonaceous material may be used in an amount of 2wt% to 15wt% of graphite, such as 2wt%, 5wt%, 8wt%, 10wt%, 12wt% or 15wt%, etc., or any other value in the range of 2wt% to 15 wt%. In some embodiments, the carbonaceous material is present in an amount of 6wt% of the graphite.
The high temperature carbonization temperature may be 800-1500 ℃, such as 800 ℃, 900 ℃, 1000 ℃, 1100 ℃, 1200 ℃, 1300 ℃, 1400 ℃, 1500 ℃, or the like, or any other value within the range of 800-1500 ℃. In some embodiments, the high temperature carbonization temperature is 1200 ℃.
The high temperature carbonization time can be 30min-240min, such as 30min, 50min, 80min, 100min, 120min, 150min, 180min, 200min, 220min or 240min, or any other value within 30min-240 min. In some embodiments, the time for high temperature carbonization is 120 minutes.
The high temperature carbonization is performed in an oxygen-free atmosphere (such as an inert atmosphere or a nitrogen atmosphere).
According to the method, the graphite is coated by adopting the carbon-containing substance, and then high-temperature carbonization is carried out, so that a graphite product reaching the battery level can be directly obtained, and the high cost caused by graphitizing the graphite under the condition of more than 2500 ℃ in the prior art is avoided.
In some embodiments, the graphite may be purified prior to repair.
The purification reagents used for purification may include hydrochloric acid and nitric acid.
Wherein, the mass ratio of the purifying reagent to the graphite can be 2:1, the concentration of hydrochloric acid can be 200g/L, the concentration of nitric acid can be 200g/L, and the purifying time can be 100min.
The purity of the purified graphite can reach 99.9% by purification to remove other impurities contained in the graphite.
Further, in order to realize recycling of all components of the waste ternary lithium battery, in the present disclosure, lithium extraction liquid obtained by lithium extraction treatment may be subjected to lithium precipitation treatment to obtain a lithium-containing product.
The lithium extraction liquid obtained by the lithium extraction treatment is leaching liquid obtained by acid leaching lithium treatment, and the main component of the leaching liquid is lithium.
The precipitated lithium can be recovered by adding carbon dioxide or sodium carbonate, etc. to the lithium extraction solution and heating the precipitate.
Further, in order to realize recycling of all components of the waste ternary lithium battery, in the present disclosure, the magnetic material obtained by magnetic separation may be subjected to second acid leaching, solid-liquid separation to obtain a second acid leaching solution, and the second acid leaching solution is subjected to extraction and impurity removal to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
For reference, the second acid leaching includes: the magnetic material is leached with a second acid and a second oxidizing agent at normal pressure (e.g., one atmosphere).
The second acid used in this process includes sulfuric acid and the like.
The mass ratio of the magnetic material to the second acid may be 1:2-1:5, such as 1:2, 1:2.5, 1:3, 1:3.5, 1:4, 1:4.5, or 1:5, etc., or any other value within the range of 1:2-1:5. In some embodiments, the mass ratio of the magnetic material to the second acid is 1:4.
The concentration of the second acid may be 150g/L to 400g/L, such as 150g/L, 200g/L, 250g/L, 300g/L, 350g/L, 400g/L, etc., or may be any other value in the range of 150g/L to 400 g/L. In some embodiments, the concentration of the second acid is 300g/L.
The amount of the second oxidizing agent may be 0.5 to 3 times, such as 0.5, 1, 1.5, 2, 2.5, or 3 times, the molar amount of the metal contained in the magnetic material, or any other value in the range of 0.5 to 3 times. In some embodiments, the second oxidizing agent is used in an amount of 1.5 times the molar amount of the metal contained in the magnetic material.
The second oxidizing agent may illustratively include at least one of hydrogen peroxide, sodium sulfite, and sodium thiosulfate.
As a reference, the second acid leaching time may be 30min-240min, such as 30min, 50min, 80min, 100min, 120min, 150min, 180min, 200min, 220min or 240min, or any other value within 30min-240 min. In some embodiments, the second acid leaching time is 180 minutes.
On the contrary, the risk caused by hydrogen generated when the nickel metal simple substance and the cobalt metal simple substance react with sulfuric acid can be avoided by carrying out the second acid leaching on the magnetic material.
For reference, the extraction reagent used in the extraction of the second pickle liquor may illustratively include at least one of P507, P204, and C272. In some embodiments, the second pickle liquor may be extracted in steps using the extraction reagents described above.
In conclusion, the general process and principles of the above method provided by the present disclosure may be summarized as follows:
according to the method, after the battery black powder and the reducing agent are subjected to first roasting (anaerobic roasting), lithium is extracted by leaching step by step through water leaching and acid leaching, lithium in lithium extracting liquid obtained by extracting lithium is recovered through lithium precipitation, and magnetic separation is carried out on lithium extracting slag obtained by extracting lithium through a magnetic separation column to obtain magnetic materials and non-magnetic materials. The magnetic material is subjected to second acid leaching (acid leaching by adding an oxidant under normal pressure) to obtain second acid leaching liquid, and the second acid leaching liquid is subjected to extraction and impurity removal to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate. The non-magnetic material is subjected to first acid leaching (pressurized and oxidant acid leaching) to obtain a first leaching solution, and the first leaching solution is subjected to impurity removal and extraction to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate. The first leaching slag is subjected to secondary roasting (low-temperature aerobic roasting) to remove amorphous carbon and residual organic matters, then a primary graphite product is obtained through flotation of a flotation column, and after purification and purification of the primary graphite product, a carbonaceous substance (such as asphalt) is added for coating, and then high-temperature carbonization is carried out to obtain the battery grade graphite. The method can realize the full resource utilization of valuable components of the battery black powder.
For reference, the method can have a recovery rate of lithium greater than 94%, nickel and cobalt greater than 97%, manganese greater than 96%, and battery grade graphite product greater than 80%.
The features and capabilities of the present disclosure are described in further detail below in connection with the examples.
Example 1
The embodiment provides a method for integrally processing waste ternary lithium batteries by using a full chain, referring to fig. 1, the method comprises the following steps:
s1: discharging, crushing, cracking and screening the waste nickel-cobalt-manganese ternary lithium battery recovered by a company in Hunan to obtain battery black powder.
S2: and uniformly mixing the battery black powder with the pulverized coal, and performing first roasting treatment to obtain a first roasting product.
In the first roasting process, inert gas (argon) is introduced to maintain an anaerobic environment, the addition amount of coal dust is 6wt% of the black powder of the battery, the temperature of the first roasting is 650 ℃, and the time of the first roasting is 180min.
S3: and (3) putting the first roasting product into a container for leaching lithium by water, and carrying out solid-liquid separation to obtain a solid.
The mass ratio of the first roasting product to water is 1:12, and the time for leaching lithium by water is 90min.
S4: mixing the solid obtained by leaching lithium with sulfuric acid, leaching lithium by acid, and separating solid from liquid to obtain leaching slag and leaching liquid.
The mass ratio of sulfuric acid used in the acid leaching process to solids obtained by water leaching extraction is 1:3, the concentration of sulfuric acid is 60g/L, and the time for leaching lithium by acid leaching is 60min.
S5: introducing carbon dioxide into the leaching solution, heating to precipitate, and recovering.
S6: and adding the leaching slag and water into a magnetic separation column to separate, so as to obtain the magnetic material and the non-magnetic material.
The magnetic field intensity of the magnetic separation column is 10000GS, and the water consumption is 60L/h.
S7: and (3) carrying out second acid leaching (normal pressure leaching) on the magnetic material, sulfuric acid and hydrogen peroxide, and carrying out solid-liquid separation to obtain a second acid leaching solution.
In the step, the mass ratio of the magnetic material to sulfuric acid is 1:4, the concentration of sulfuric acid is 200g/L, the dosage of hydrogen peroxide is 1.5 times of the molar quantity of metal contained in the magnetic material, the pressure of the second acid leaching is 1 atmosphere, and the time of the second acid leaching is 180min.
S8: and extracting and removing impurities from the second pickle liquor to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
The step extraction is a stepwise extraction with P507, P204 and C272.
S9: and carrying out first acid leaching (pressure leaching) on the non-magnetic material, sulfuric acid and hydrogen peroxide, and carrying out solid-liquid separation to obtain first acid leaching slag and first acid leaching liquid.
In the step, the mass ratio of the nonmagnetic material to sulfuric acid is 1:3, the concentration of sulfuric acid is 200g/L, the dosage of hydrogen peroxide is 1.2 times of the molar quantity of metal contained in the nonmagnetic material, the pressure of the first acid leaching is 1MPa, and the time of the first acid leaching is 90min.
S10: and removing impurities and extracting the first pickle liquor to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate.
This step is a stepwise extraction with P507, P204 and C272.
S11: the first acid leaching residue is subjected to a second roasting (low-temperature aerobic roasting).
Air is introduced during the second roasting, the temperature of the second roasting is 450 ℃, and the time of the second roasting is 120min.
S12: and (3) floating the material (second roasting product) obtained after the second roasting by a floating column to obtain a graphite primary product.
The flotation reagents used in this step include collectors, frothers and conditioners. Wherein the collecting agent is kerosene, and the dosage of the collecting agent is 300g/t; the foaming agent is terpineol oil, and the dosage of the foaming agent is 120g/t; the regulator is water glass, and the dosage is 1000g/t.
S13: adding hydrochloric acid and nitric acid into the graphite primary product for purification to obtain high-purity graphite.
Wherein the concentration of hydrochloric acid is 200g/L, the concentration of nitric acid is 200g/L, the mass ratio of the total amount of hydrochloric acid and nitric acid to the primary product of graphite is 2:1, and the purification time is 100min.
S14: and mixing the high-purity graphite with asphalt to coat the high-purity graphite by the asphalt, and carbonizing the high-purity graphite at high temperature after coating to finally obtain the battery-grade graphite product.
The addition amount of the asphalt is 6wt% of high-purity graphite, high-temperature carbonization is carried out under the anaerobic condition, the high-temperature carbonization temperature is 1200 ℃, and the high-temperature carbonization time is 120min.
The SEM image of the obtained battery grade graphite product is shown in fig. 2, and it can be seen from the image that the graphite is in a flake and chip shape, has little impurity content and has a smoother surface.
Example 2
The differences between this embodiment and embodiment 1 are: the temperature of the first calcination was 500 ℃.
Example 3
The differences between this embodiment and embodiment 1 are: the temperature of the second calcination was 300 ℃.
Example 4
The differences between this embodiment and embodiment 1 are: the temperature of the second calcination was 550 ℃.
Example 5
The differences between this embodiment and embodiment 1 are: the high temperature carbonization temperature was 1500 ℃.
Example 6
The differences between this embodiment and embodiment 1 are: the high temperature carbonization temperature was 800 ℃.
Example 7
The embodiment provides a method for integrally treating waste ternary lithium batteries by using a full chain, which comprises the following steps:
s1: and discharging, crushing, cracking and screening the waste nickel-cobalt-manganese ternary lithium battery to obtain battery black powder.
S2: and uniformly mixing the battery black powder with the pulverized coal, and performing first roasting treatment to obtain a first roasting product.
In the first roasting process, inert gas (nitrogen) is introduced to maintain an anaerobic environment, the addition amount of coal dust is 2wt% of the black powder of the battery, the temperature of the first roasting is 500 ℃, and the time of the first roasting is 240min.
S3: and (3) putting the first roasting product into a container for leaching lithium by water, and carrying out solid-liquid separation to obtain a solid.
The mass ratio of the first roasting product to water is 1:5, and the time for leaching lithium by water is 120min.
S4: mixing the solid obtained by leaching lithium with sulfuric acid, leaching lithium by acid, and separating solid from liquid to obtain leaching slag and leaching liquid.
The mass ratio of sulfuric acid used in the acid leaching process to solids obtained by water leaching extraction is 1:2, the concentration of sulfuric acid is 10g/L, and the time for leaching lithium by acid leaching is 100min.
S5: and introducing sodium carbonate into the leaching solution, heating for precipitation and then recycling.
S6: and adding the leaching slag and water into a magnetic separation column to separate, so as to obtain the magnetic material and the non-magnetic material.
The magnetic field strength of the magnetic separation column is 5000GS, and the water consumption is 100L/h.
S7: and (3) carrying out second acid leaching (normal pressure leaching) on the magnetic material, sulfuric acid and sodium sulfite, and carrying out solid-liquid separation to obtain a second acid leaching solution.
In the step, the mass ratio of the magnetic material to sulfuric acid is 1:2, the concentration of sulfuric acid is 150g/L, the dosage of sodium sulfite is 0.5 times of the molar quantity of metal contained in the magnetic material, the pressure of the second acid leaching is 1 atmosphere, and the time of the second acid leaching is 240min.
S8: and extracting and removing impurities from the second pickle liquor to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
This step is a stepwise extraction with P507, P204 and C272.
S9: and carrying out first acid leaching (pressure leaching) on the non-magnetic material, sulfuric acid and sodium sulfite, and carrying out solid-liquid separation to obtain first acid leaching slag and first acid leaching liquid.
In the step, the mass ratio of the non-magnetic material to sulfuric acid is 1:2, the concentration of sulfuric acid is 150g/L, the dosage of sodium sulfite is 0.5 times of the molar quantity of metal contained in the non-magnetic material, the pressure of the first acid leaching is 0.4MPa, and the time of the first acid leaching is 120min.
S10: and removing impurities and extracting the first pickle liquor to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate.
This step is a stepwise extraction with P507, P204 and C272.
S11: the first acid leaching residue is subjected to a second roasting (low-temperature aerobic roasting).
Oxygen is introduced during the second roasting, the temperature of the second roasting is 300 ℃, and the time of the second roasting is 180min.
S12: and (3) floating the material (second roasting product) obtained after the second roasting by a floating column to obtain a graphite primary product.
The flotation reagents used in this step include collectors, frothers and conditioners. Wherein the collecting agent is kerosene, and the dosage of the collecting agent is 300g/t; the foaming agent is terpineol oil, and the dosage of the foaming agent is 120g/t; the regulator is water glass, and the dosage is 1000g/t.
S13: adding hydrochloric acid and nitric acid into the graphite primary product for purification to obtain high-purity graphite.
Wherein the concentration of hydrochloric acid is 200g/L, the concentration of nitric acid is 200g/L, the mass ratio of the total amount of hydrochloric acid and nitric acid to the primary product of graphite is 2:1, and the purification time is 100min.
S14: and mixing the high-purity graphite with asphalt to coat the high-purity graphite by the asphalt, and carbonizing the high-purity graphite at high temperature after coating to finally obtain the battery-grade graphite product.
The addition amount of the asphalt is 2wt% of the high-purity graphite, the high-temperature carbonization is carried out under the anaerobic condition, the high-temperature carbonization temperature is 800 ℃, and the high-temperature carbonization time is 240min.
Example 8
The embodiment provides a method for integrally treating waste ternary lithium batteries by using a full chain, which comprises the following steps:
s1: and discharging, crushing, cracking and screening the waste nickel-cobalt-manganese ternary lithium battery to obtain battery black powder.
S2: and uniformly mixing the battery black powder with the pulverized coal, and performing first roasting treatment to obtain a first roasting product.
In the first roasting process, inert gas (argon) is introduced to maintain an anaerobic environment, the addition amount of coal dust is 15wt% of the black powder of the battery, the temperature of the first roasting is 800 ℃, and the time of the first roasting is 30min.
S3: and (3) putting the first roasting product into a container for leaching lithium by water, and carrying out solid-liquid separation to obtain a solid.
The mass ratio of the first roasting product to water is 1:14, and the time for leaching lithium by water is 10min.
S4: mixing the solid obtained by leaching lithium with sulfuric acid, leaching lithium by acid, and separating solid from liquid to obtain leaching slag and leaching liquid.
The mass ratio of sulfuric acid used in the acid leaching process to solids obtained by water leaching extraction is 6:1, the concentration of sulfuric acid is 100g/L, and the time for leaching lithium by acid leaching is 10min.
S5: introducing carbon dioxide into the leaching solution, heating to precipitate, and recovering.
S6: and adding the leaching slag and water into a magnetic separation column to separate, so as to obtain the magnetic material and the non-magnetic material.
The magnetic field intensity of the magnetic separation column is 12000GS, and the water consumption is 10L/h.
S7: and (3) carrying out second acid leaching (normal pressure leaching) on the magnetic material, sulfuric acid and sodium thiosulfate, and carrying out solid-liquid separation to obtain a second acid leaching solution.
In the step, the mass ratio of the magnetic material to sulfuric acid is 1:5, the concentration of sulfuric acid is 400g/L, the dosage of sodium thiosulfate is 3 times of the molar quantity of metal contained in the magnetic material, the pressure of the second acid leaching is 1 atmosphere, and the time of the second acid leaching is 30min.
S8: and extracting and removing impurities from the second pickle liquor to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
This step is a stepwise extraction with P507, P204 and C272.
S9: and carrying out first acid leaching (pressure leaching) on the non-magnetic material, sulfuric acid and sodium thiosulfate, and carrying out solid-liquid separation to obtain first acid leaching residues and first acid leaching liquid.
In the step, the mass ratio of the non-magnetic material to sulfuric acid is 1:5, the concentration of sulfuric acid is 400g/L, the dosage of sodium thiosulfate is 3 times of the molar quantity of metal contained in the non-magnetic material, the pressure of the first acid leaching is 1.5MPa, and the time of the first acid leaching is 20min.
S10: and removing impurities and extracting the first pickle liquor to obtain a second product containing nickel sulfate, cobalt sulfate and manganese sulfate.
This step is a stepwise extraction with P507, P204 and C272.
S11: the first acid leaching residue is subjected to a second roasting (low-temperature aerobic roasting).
Air is introduced during the second roasting, the temperature of the second roasting is 550 ℃, and the time of the second roasting is 30min.
S12: and (3) floating the material (second roasting product) obtained after the second roasting by a floating column to obtain a graphite primary product.
The flotation reagents used in this step include collectors, frothers and conditioners. Wherein the collecting agent is kerosene, and the dosage of the collecting agent is 300g/t; the foaming agent is terpineol oil, and the dosage of the foaming agent is 120g/t; the regulator is water glass, and the dosage is 1000g/t.
S13: adding hydrochloric acid and nitric acid into the graphite primary product for purification to obtain high-purity graphite.
Wherein the concentration of hydrochloric acid is 200g/L, the concentration of nitric acid is 200g/L, the mass ratio of the total amount of hydrochloric acid and nitric acid to the primary product of graphite is 2:1, and the purification time is 100min.
S14: and mixing the high-purity graphite with asphalt to coat the high-purity graphite by the asphalt, and carbonizing the high-purity graphite at high temperature after coating to finally obtain the battery-grade graphite product.
The addition amount of the asphalt is 15wt% of high-purity graphite, high-temperature carbonization is carried out under the anaerobic condition, the high-temperature carbonization temperature is 1500 ℃, and the high-temperature carbonization time is 30min.
Comparative example 1
The difference between this comparative example and example 1 is: and S1, reducing agent is not added to reduce the battery black powder, and the battery black powder is directly subjected to primary roasting treatment.
Comparative example 2
The difference between this comparative example and example 1 is: the lithium extraction mode is a two-stage water leaching process, namely, 2 times of water leaching lithium are repeatedly carried out (each time of water leaching lithium is carried out under the same process conditions as in S3 in the embodiment 1), and the acid leaching lithium is not carried out.
Comparative example 3
The difference between this comparative example and example 1 is: the leached slag obtained in S4 is not subjected to magnetic separation but is directly subjected to second acid leaching (atmospheric leaching). The procedure for graphite recovery in this comparative example is generally: first roasting, lithium extraction treatment, first acid leaching, second roasting, floatation, purification and graphite restoration.
Comparative example 4
The difference between this comparative example and example 1 is: the first acid leaching residue obtained in S9 is not subjected to the second roasting (low-temperature aerobic roasting) but is directly subjected to flotation. The procedure for graphite recovery in this comparative example is generally: first roasting, lithium extraction treatment, magnetic separation, first acid leaching, floatation, purification and graphite restoration.
Comparative example 5
The difference between this comparative example and example 1 is: the second calcination product obtained in S11 is not subjected to flotation but is directly purified. The procedure for graphite recovery in this comparative example is generally: first roasting, lithium extraction treatment, magnetic separation, first acid leaching, second roasting, purification and graphite restoration.
Comparative example 6
The difference between this comparative example and example 1 is: in S13, the graphite primary product is directly subjected to high-temperature purification at 2600 ℃, and no purification reagents such as hydrochloric acid, nitric acid and the like are added.
Comparative example 7
The difference between this comparative example and example 1 is: instead of a flotation column, the flotation was performed using a conventional flotation machine (XFD iv single cell flotation machine from gilin prospecting machines).
Comparative example 8
The difference between this comparative example and example 1 is: and S11, directly repairing graphite of the graphite primary product without a purification process. The procedure for graphite recovery in this comparative example is generally: first roasting, lithium extraction treatment, magnetic separation, first acid leaching, second roasting, floatation and graphite restoration.
Test examples
(1) Recovery rates of Li, ni, co, mn and C corresponding to examples 1 to 8 and comparative examples 1 to 8 were measured, and the results are shown in Table 1.
Table 1 example test results
As can be seen from table 1, the method provided by the embodiments of the present disclosure can obtain higher recovery rates of Li, ni, co, mn and C at the same time as the cost is lower.
(2) The battery grade graphite product obtained in example 1 was subjected to impurity content analysis, specific surface area measurement, and electrochemical analysis, and the results are shown in table 2.
The test method of the electrical properties is as follows: the battery is assembled by taking a metal lithium sheet as a counter electrode, PZ12 as a diaphragm, 50 mu L of E30 as electrolyte, the battery size being CR2430, a battery structure cathode shell-foam nickel-lithium sheet-electrolyte-diaphragm-electrolyte-graphite pole piece-anode shell, and a constant current cycle test is carried out between 0.005V and 1.5V by using a blue electric test cabinet under the current density of 10mA/g to evaluate the electrochemical performance of the battery.
Table 2 example 1 analysis of graphite products
As can be seen from table 2, the graphite product recovered in example 1 of the present disclosure can meet the battery preparation requirement, and a battery with better capacity and initial efficiency can be further prepared.
Industrial applicability
The method for integrally treating the waste ternary lithium battery through the full chain is simple to operate, can realize full resource utilization of valuable components of the battery black powder, and achieves higher recovery rates of Li, ni, co, mn and C while the cost is low.
Claims (25)
1. The method for integrally treating the waste ternary lithium battery by using the full chain is characterized by comprising the following steps of:
roasting battery black powder in the waste ternary lithium battery to be treated and a reducing agent for the first time to obtain a first roasting product; carrying out lithium extraction treatment on the first roasting product, and carrying out magnetic separation on lithium extraction slag obtained by the lithium extraction treatment; carrying out first acid leaching on the non-magnetic materials separated by magnetic separation, and carrying out solid-liquid separation to obtain first acid leaching residues; carrying out secondary roasting on the first acid leaching slag to obtain a second roasting product with amorphous carbon removed; and floating graphite in the second roasting product.
2. The method of claim 1, wherein the reducing agent comprises at least one of coal fines, carbon fines, and organic carbon reducing agents;
and/or the mass ratio of the battery black powder to the reducing agent is 100:2-100:15.
3. The method of claim 1 or 2, wherein the first firing comprises at least one of the following features:
characteristic one: the first roasting is carried out under the anaerobic condition;
and the second characteristic is: the temperature of the first roasting is 500-800 ℃;
and (3) the following characteristics: the time of the first roasting is 30min-240min.
4. A method according to any one of claims 1-3, wherein the lithium extraction treatment comprises: and leaching the lithium from the first roasting product by water, and leaching the lithium from a solid obtained by leaching the lithium by acid.
5. The method of claim 4, wherein the mass ratio of the first calcined product to water in the water extraction lithium process is 1:3-1:15; and/or leaching lithium in water for 10min-120min.
6. The method of claim 4, wherein the acid leaching lithium process comprises at least one of the following features:
characteristic one: the acid used for leaching lithium includes sulfuric acid;
And the second characteristic is: the concentration of acid used in the acid leaching process is 10g/L-100g/L, and the mass ratio of the acid used in the acid leaching process to the solid obtained by water leaching extraction is 2:1-6:1;
and (3) the following characteristics: the time for leaching lithium by acid is 10min-100min.
7. The method of any one of claims 1-6, wherein the magnetic separation comprises at least one of the following features:
characteristic one: magnetic separation is carried out in a magnetic separation column;
and the second characteristic is: the magnetic field intensity used for magnetic separation is 2000GS-12000GS;
and (3) the following characteristics: the magnetic separation is carried out in the presence of water, and the water quantity is 10L/h-100L/h.
8. The method according to any one of claims 1 to 7, wherein the first acid leaching comprises: the non-magnetic material is pressure leached with a first acid and a first oxidizing agent.
9. The method of claim 8, wherein the first acid leaching process comprises at least one of the following features:
characteristic one: the first acid comprises sulfuric acid;
and the second characteristic is: the mass ratio of the non-magnetic material to the first acid is 1:2-1:5, and the concentration of the first acid is 150g/L-400g/L;
and (3) the following characteristics: the dosage of the first oxidant is 0.5-3 times of the molar quantity of the metal contained in the non-magnetic material;
And four characteristics: the first oxidant comprises at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
and fifth feature: the pressure of the first acid leaching is 0.4MPa to 1.5MPa;
and six, characteristics: the time of the first acid leaching is 20min-120min.
10. The method of any of claims 1-7, wherein the second firing comprises at least one of the following features:
characteristic one: the second roasting is carried out under the aerobic condition;
and the second characteristic is: the temperature of the second roasting is 300-550 ℃;
and (3) the following characteristics: the second roasting time is 30min-180min.
11. The method according to any one of claims 1-10, characterized in that the flotation is performed in a flotation column.
12. The method of any one of claims 1-11, wherein the floated graphite is repaired to yield battery grade graphite.
13. The method of claim 12, wherein the repair process comprises: the graphite is coated with a carbonaceous material and subsequently carbonized at high temperatures.
14. The method of claim 13, wherein the carbonaceous material comprises at least one of pitch, glucose, and sucrose.
15. The method of claim 13 or 14, wherein the carbonaceous material is present in an amount of 2wt% to 15wt% of the graphite.
16. The method according to any one of claims 13 to 15, wherein the high temperature carbonization is at a temperature of 800 ℃ to 1500 ℃ and/or the high temperature carbonization is for a time of 30min to 240min; and/or, the high temperature carbonization is performed in an oxygen-free atmosphere.
17. The method of any one of claims 12-16, further comprising purifying the graphite prior to performing the repair.
18. The method of claim 17, wherein the reagents used for the purification comprise hydrochloric acid and nitric acid.
19. The method according to any one of claims 1 to 18, wherein the lithium extraction liquid obtained by the lithium extraction treatment is subjected to a lithium precipitation treatment to obtain a lithium-containing product.
20. The method according to any one of claims 1 to 19, wherein the magnetic material obtained by the magnetic separation is subjected to a second acid leaching, and solid-liquid separation to obtain a second acid leaching solution; and extracting and removing impurities from the second pickle liquor to obtain a first product containing nickel sulfate, cobalt sulfate and manganese sulfate.
21. The method of claim 20, wherein the second acid leaching comprises: and leaching the magnetic material with a second acid and a second oxidant under normal pressure.
22. The method of claim 21, wherein the second acid leaching process comprises at least one of the following features:
characteristic one: the second acid comprises sulfuric acid;
and the second characteristic is: the mass ratio of the magnetic material to the second acid is 1:2-1:5, and the concentration of the second acid is 150g/L-400g/L;
and (3) the following characteristics: the dosage of the second oxidant is 0.5-3 times of the molar quantity of the metal contained in the magnetic material;
and four characteristics: the second oxidant comprises at least one of hydrogen peroxide, sodium sulfite and sodium thiosulfate;
and fifth feature: the second acid leaching time is 30min-240min.
23. The process of any one of claims 20 to 22, wherein the extraction reagent used in the extraction of the second pickling solution comprises at least one of mono-2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, and di (2, 4-trimethylpentyl) phosphinic acid.
24. The method according to any one of claims 1 to 23, wherein the first pickling solution obtained after the first pickling is subjected to impurity removal and extraction to obtain a second product comprising nickel sulfate, cobalt sulfate and manganese sulfate.
25. The process of claim 24, wherein the extraction reagent used in the extraction of the first pickling solution comprises at least one of mono-2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate, and di (2, 4-trimethylpentyl) phosphinic acid.
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