CN115744932B - Extraction method of metallic lithium - Google Patents
Extraction method of metallic lithium Download PDFInfo
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- CN115744932B CN115744932B CN202211376109.6A CN202211376109A CN115744932B CN 115744932 B CN115744932 B CN 115744932B CN 202211376109 A CN202211376109 A CN 202211376109A CN 115744932 B CN115744932 B CN 115744932B
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- lithium
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- nano tube
- liquid ammonia
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 144
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 238000000605 extraction Methods 0.000 title claims abstract description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 52
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 41
- 238000012546 transfer Methods 0.000 claims abstract description 31
- 239000004964 aerogel Substances 0.000 claims abstract description 27
- 238000007600 charging Methods 0.000 claims abstract description 19
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims abstract description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 5
- 238000002791 soaking Methods 0.000 claims abstract description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 60
- 239000002041 carbon nanotube Substances 0.000 claims description 60
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 60
- 238000003756 stirring Methods 0.000 claims description 34
- 239000011268 mixed slurry Substances 0.000 claims description 32
- 239000002002 slurry Substances 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 19
- 239000011230 binding agent Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000010405 anode material Substances 0.000 claims description 14
- 230000018044 dehydration Effects 0.000 claims description 14
- 238000006297 dehydration reaction Methods 0.000 claims description 14
- 239000000758 substrate Substances 0.000 claims description 14
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 claims description 13
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 13
- 230000005540 biological transmission Effects 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000002699 waste material Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052642 spodumene Inorganic materials 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- 239000003292 glue Substances 0.000 claims description 7
- 239000007774 positive electrode material Substances 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 6
- 230000008014 freezing Effects 0.000 claims description 6
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 claims description 4
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 4
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 claims description 4
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 4
- 229910052670 petalite Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 229910052629 lepidolite Inorganic materials 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 claims 2
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 claims 2
- 229940094522 laponite Drugs 0.000 claims 1
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 239000011889 copper foil Substances 0.000 description 18
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 description 6
- 239000011888 foil Substances 0.000 description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 description 6
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical group [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 5
- 239000000443 aerosol Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 238000002386 leaching Methods 0.000 description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000010009 beating Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007667 floating Methods 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 238000010902 jet-milling Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 235000017550 sodium carbonate Nutrition 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910052644 β-spodumene Inorganic materials 0.000 description 2
- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229940072056 alginate Drugs 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- AEMOLEFTQBMNLQ-BKBMJHBISA-N alpha-D-galacturonic acid Chemical class O[C@H]1O[C@H](C(O)=O)[C@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-BKBMJHBISA-N 0.000 description 1
- JRBRVDCKNXZZGH-UHFFFAOYSA-N alumane;copper Chemical compound [AlH3].[Cu] JRBRVDCKNXZZGH-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012320 chlorinating reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000005188 flotation Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- 238000012423 maintenance Methods 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
- 239000002071 nanotube Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910052643 α-spodumene Inorganic materials 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for extracting metallic lithium, which comprises the following steps: preparing three aerogel film electrodes, namely a lithium supply electrode, a transfer electrode and a collecting electrode; forming a three-electrode parallel battery according to a mode of supplying a lithium electrode/a diaphragm/a transfer electrode/a diaphragm/a collecting electrode, and inserting the three-electrode parallel battery into an inert gas-protected lithium hexafluorophosphate-based electrolyte to form a lithium extraction battery system; then charging the collecting electrode (negative electrode)/transferring electrode (positive electrode) battery to transfer lithium ions in the transferring electrode to the collecting electrode; then charging the transfer electrode (negative electrode)/lithium supply electrode (positive electrode) battery to enable lithium ions in the lithium supply electrode to migrate to the transfer electrode, repeating the charging process, and enabling the lithium ions in the lithium supply electrode to continuously migrate to the collecting electrode; and soaking the lithium-containing collecting electrode in liquid ammonia, and evaporating the obtained lithium-containing liquid ammonia solution to obtain metallic lithium and ammonia gas. The method has simple process, can recycle resources, and has wide commercial application prospect.
Description
Technical Field
The invention belongs to the technical field of electrochemistry, and particularly relates to a method for extracting metallic lithium.
Background
Lithium ion batteries are the absolute mainstream of the current battery industry, develop rapidly, and promote revolutionary progress in various fields such as smart phones, notebook computers, electric automobiles and the like. Along with the entering of many enterprises into the field of new energy automobiles, the power lithium battery enters a rapid development lane, lithium batteries are distributed across multiple enterprises, the demand of lithium serving as a core raw material of the lithium battery is larger and larger, and the 'lithium robbing' war among enterprises is continuously continued. In the industry chain of lithium batteries, lithium resources are critical. Who owns the lithium resource and who owns the pricing right. But at present, the resources are increasingly exhausted, so that the lithium cost is greatly increased.
The lithium source extraction technology for solving the shortage of lithium resources and arranging multiple paths is the development direction of lithium resources in the future.
For a long time, lithium resources have been mainly provided by lithium ores. At present, the method for extracting lithium from ores mainly comprises a sulfuric acid method, a sulfate method, a lime sintering method, a chloridizing roasting method, a soda ash autoclaving method and the like. The method for extracting lithium carbonate from spodumene by sulfuric acid method is a current mature ore extraction process, and the method firstly calcines natural spodumene at 950-1100 ℃ to convert the natural spodumene from monoclinic alpha-spodumene into tetragonal beta-spodumene with high chemical activity, then calcines sulfuric acid and beta-spodumene at 250-300 ℃ and carries out replacement through sulfating calcinationThe method has the advantages that the steps are complicated, high-temperature roasting is needed, a large amount of concentrated sulfuric acid is needed, and great potential safety hazards exist; the sulfate process is a process in which potassium sulfate is sintered with natural spodumene to convert lithium in the ore to lithium sulfate, which is dissolved out of the ore to a solution by clinker, and which is said to decompose almost all of the lithium-bearing ore, but if Na is not used 2 SO 4 Substitute part K 2 SO 4 A large amount of potassium salt is consumed, so that the production cost is high, and the product is often polluted by potassium; the lime sintering method is to sinter lime or limestone with lithium-containing ore, and then dissolve out the sintered cake to prepare lithium carbonate, and the process comprises the main procedures of raw material preparation, roasting, leaching, clarifying, concentrating leaching solution, purifying, crystallizing and the like, and the method has the advantages of complex steps, low solution concentration, high evaporation energy consumption, high material flow, low lithium recovery rate, cohesiveness of the leached ore slurry and difficult maintenance equipment; the chloridizing roasting method is to convert lithium and other valuable metals in the ore into chloride by using a chlorinating agent so as to extract the metals and the compounds thereof, but the collection of LiCl is difficult, the corrosiveness of furnace gas is strong, and the dosage of the reagent is large; the soda ash autoclaving method mainly comprises four processes of crystal form conversion roasting, autoclaving, carbonization leaching and lithium precipitation, the method also has the problem of complicated steps, autoclaving is carried out under the conditions of high pressure and high temperature, the operation technical requirement is relatively high, and no existing lithium salt production factory can be used as a reference at present.
At present, the power battery recycling market is gradually warmed up, and a new channel is opened for lithium resource supply. At present, the waste lithium ion battery is generally recovered by adopting wet leaching and extraction technology to firstly extract metal resources such as nickel, cobalt, manganese, iron and the like from black powder containing the metal resources, and then finally extracting lithium metal resources in a carbonate precipitation mode, so that the metal lithium resources inevitably cause loss of the metal lithium resources in the recovery process through a long process flow, and the recovery rate of lithium is obviously reduced; on the other hand, because a large amount of lithium ions exist in the processes of leaching, extracting and back extracting, the purity of the extracted nickel, cobalt and other salts cannot reach the standard of battery level, and the extracted nickel, cobalt and other salts are difficult to recycle to the remanufacturing of the lithium ion battery.
The present invention has been made to solve the above-mentioned problems occurring in the prior art.
Disclosure of Invention
Aiming at least one of the technical problems, the invention aims to provide a method for extracting metal lithium, which comprises the steps of firstly preparing three aerogel film electrodes with different purposes by utilizing a freeze drying technology, assembling three-electrode parallel batteries for a lithium electrode/a diaphragm/a transit electrode/a diaphragm/a collecting electrode, and then sequentially charging the collecting electrode (negative electrode)/the transit electrode (positive electrode) battery, the transit electrode (negative electrode)/the lithium electrode (positive electrode) battery and the collecting electrode (negative electrode)/the transit electrode (positive electrode) battery to enable lithium ions in the lithium electrode to migrate to a collector, thereby realizing the extraction of the metal lithium in lithium-containing ore or waste lithium ion positive electrode materials.
The technical scheme of the invention is as follows:
the invention provides a method for extracting metallic lithium, which comprises the following steps:
step one, preparing three electrodes:
preparing a carbon nano tube (CNTp) into an aerogel film serving as a lithium extraction collecting electrode;
uniformly mixing a carbon nano tube (CNTp) with a lithium ion battery anode material to prepare a composite aerogel film A serving as a transfer electrode for extracting lithium;
pulverizing lithium-containing ore or waste lithium ion battery anode material into submicron-sized fine powder by air flow, and uniformly mixing with carbon nanotubes (CNTp) to prepare a composite aerogel film B serving as a lithium supply electrode;
step two, forming a three-electrode parallel battery according to a mode of supplying a lithium electrode/a diaphragm/a transfer electrode/a diaphragm/a collecting electrode, and inserting the three-electrode parallel battery into a lithium-based electrolyte protected by inert gas to form a lithium-extracting battery system;
thirdly, charging the collecting electrode (negative electrode)/transferring electrode (positive electrode) battery to enable lithium ions in the positive electrode material of the lithium ion battery of the transferring electrode to migrate to the collecting electrode;
step four, charging a transfer electrode (negative electrode)/lithium supply electrode (positive electrode) battery, so that lithium ions in the lithium supply electrode migrate to the transfer electrode;
step five, repeating the step three and the step four in sequence, so that lithium ions in the lithium supply electrode continuously migrate to the collecting electrode through the transfer electrode until the lithium ions in the lithium supply electrode completely migrate, and extracting metal lithium in lithium-containing ore or waste lithium ion anode materials is realized;
step six, soaking and cleaning the lithium-containing collecting electrode with liquid ammonia to dissolve lithium in the liquid ammonia, and evaporating the obtained lithium-containing liquid ammonia solution to obtain metal lithium and ammonia.
Preferably, after the extraction of metallic lithium is completed, the carbon nanotubes (CNTp) are recovered by mechanical stirring, flotation of the lithium electrode.
Preferably, in the first step, the preparation method of the aerogel film corresponding to the collecting electrode comprises the following steps: dispersing the carbon nano tube in a solvent, adding a binder and a stabilizer, and continuously stirring to fully and uniformly mix the carbon nano tube to obtain carbon nano tube slurry; coating the carbon nano tube slurry on the surface of a substrate, conveying the carbon nano tube slurry into a liquid ammonia freezing dehydration pond through a transmission machine, then conveying the carbon nano tube slurry into a low-temperature drying bin (the temperature range is controlled to be minus 33 ℃ to 0 ℃), drying and stripping the substrate to obtain the carbon nano tube.
Preferably, in the preparation method of the aerogel film, the solid content of the nanotube slurry is 10% -15%, and the mass ratio of the carbon nanotubes to the binder and the stabilizer is 20-10:0.7:0.3;
wherein the solvent is at least one of deionized water, alcohol, glycol, propanol, isopropanol, acetone and N-methyl pyrrolidone;
the binder is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polytetrafluoroethylene (PTFE), alginate (Li) + Salts), pectate salts (Li + Salts) at least one of the following;
the stabilizer is sodium carboxymethyl cellulose (CMC).
Preferably, in the first step, the preparation method of the composite aerogel film a corresponding to the transfer electrode comprises the following steps: mixing the carbon nano tube slurry, the water-based binder and deionized water, stirring and sizing, adding the positive electrode material of the lithium ion battery into the sized glue, and stirring to fully and uniformly mix the materials to prepare mixed slurry; coating the mixed slurry on the surface of a substrate, conveying the mixed slurry into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the mixed slurry into a low-temperature drying bin (the temperature range is controlled to be minus 33 ℃ to 0 ℃), drying, and stripping the substrate to obtain the composite material.
Preferably, in the preparation method of the composite aerogel film A, the solid content of the mixed slurry is 50% -60%, the aqueous binder in the mixed slurry accounts for 2% -3% of the total mass of all solids, the carbon nano tube accounts for 5% -10%, and the balance is the anode material of the lithium ion battery;
wherein the aqueous binder is an aqueous gel prepared from acrylonitrile multipolymer;
the lithium ion battery anode material is at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, ternary material, lithium cobaltate, lithium manganate and lithium nickelate.
Preferably, in the first step, the preparation method of the composite aerogel film B corresponding to the lithium electrode comprises the following steps: mixing and stirring the carbon nano tube slurry, the water-based binder and deionized water for sizing, crushing lithium-containing ore or waste lithium ion battery anode materials into submicron fine powder, adding the fine powder into the sized glue, and stirring to fully and uniformly mix the fine powder to prepare mixed slurry; coating the mixed slurry on the surface of a substrate, conveying the mixed slurry into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the mixed slurry into a low-temperature drying bin (the temperature range is controlled to be minus 33 ℃ to 0 ℃), drying, and stripping the substrate to obtain the composite material.
Preferably, in the preparation method of the composite aerogel film B, the solid content of the mixed slurry is 50% -60%, the aqueous binder in the mixed slurry accounts for 2% -3% of the total mass of all solids, the carbon nano tube accounts for 5% -10%, and the balance is lithium-containing ore or waste lithium ion battery anode material;
wherein the aqueous binder is an aqueous gel prepared from acrylonitrile multipolymer;
the lithium-containing ore is at least one of spodumene, lepidolite, phospholepidolite, petalite and petalite;
the waste lithium ion battery material contains at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, ternary material, lithium cobaltate, lithium manganate and lithium nickelate.
The collecting electrode, the transferring electrode and the lithium supplying electrode are all provided with carbon nano tube aerogel films, so that the electrodes can be directly prepared without current collectors such as copper aluminum foil and the like.
Preferably, in the first step, the carbon nanotubes are at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes;
the purity of the carbon nano tube is more than 99%, the diameter is 10-200 nm, and the length is 5-20 mu m.
Preferably, in the second step, the assembled three-electrode parallel cell is a flat plate or wound into a cylinder.
Preferably, in the second step, the lithium-based electrolyte is lithium hexafluorophosphate and/or lithium perchlorate.
Preferably, in the third and fourth steps, a constant-current constant-voltage charging method is adopted for charging the battery.
Preferably, in the fifth step, the lithium-containing collecting electrode can be recycled after being cleaned by liquid ammonia; the ammonia gas obtained by evaporation can be compressed to prepare liquid ammonia for recycling.
The beneficial effects of the invention are as follows:
1) The method is simple, has strong operability, is beneficial to industrial production, and has wide commercial application prospect;
2) The lithium-containing collecting electrode can be recycled after being soaked and cleaned by liquid ammonia; the lithium supply electrode after extracting lithium is mechanically stirred and floated to recover CNTp, and the CNTp can be recycled; the collecting electrode containing lithium is soaked and cleaned by liquid ammonia to enable lithium to be dissolved in the liquid ammonia, a liquid ammonia solution containing lithium can be obtained, the liquid ammonia solution containing lithium is evaporated, high-purity metallic lithium and pure ammonia can be obtained, and the ammonia obtained through evaporation can be compressed to prepare liquid ammonia for recycling;
3) The carbon nano tube (CNTp) is a good lithium ion conductor and an electronic conductor, and meanwhile, the carbon nano tube aerogel film prepared by the carbon nano tube is of a three-dimensional porous structure, has large porosity (50-80%), large pore volume, is beneficial to storage and transportation of lithium ions and is beneficial to infiltration of electrolyte; the carbon nano tube is added into the composite aerogel membrane electrode (lithium electrode and transfer electrode), so that the mechanical strength and the electrical conductivity of the membrane electrode are greatly enhanced, other conductive additives (such as carbon black and the like) are not required to be added, a large amount of adhesive is not required, and current collectors such as copper, aluminum foil and the like are also omitted;
4) The method only needs a power supply, does not need high-temperature roasting or use chemical reagents such as strong acid, strong alkali and the like, does not have other chemical reactions, can recycle resources, is efficient, energy-saving, environment-friendly and pollution-free, and can realize green and efficient extraction of the metal lithium at room temperature.
Drawings
The invention is further described below with reference to the accompanying drawings and examples:
FIG. 1 is a schematic view of the internal structure of an assembled three-electrode parallel cell of the present invention;
fig. 2 is a cross-sectional SEM photograph of a collector of a carbon nanotube aerogel film prepared in accordance with an embodiment of the present invention.
In the figure: 1-1 is a lithium supply electrode, 1-2 is a transfer electrode, 1-3 is a collecting electrode, and 1-4 is a diaphragm.
Detailed Description
The objects, technical solutions and advantages of the present invention will become more apparent by the following detailed description of the present invention with reference to the accompanying drawings. It should be understood that the description is only illustrative and is not intended to limit the scope of the invention. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the present invention.
Example 1
Adding carbon nano tubes (CNTp, the same applies below) into an alcohol water solution with the concentration of 40%, after ultrasonic treatment, adding a polyvinyl alcohol solution and a sodium carboxymethyl cellulose solution with the mass ratio of 7:3 and the mass fraction of 10%, wherein the total mass of the polyvinyl alcohol and the sodium carboxymethyl cellulose is 1/10 of the mass of the carbon nano tubes, and continuously stirring for 30min at the speed of 200 rpm to fully and uniformly mix the materials, so as to obtain carbon nano tube slurry with the solid content of 12.5%; coating the slurry on the surface of a copper foil, conveying the copper foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the copper foil into a low-temperature drying bin at-10 ℃, drying and stripping to obtain a carbon nano tube aerosol film, and taking the carbon nano tube aerosol film as a collecting electrode for extracting lithium;
mixing carbon nanotube slurry, an aqueous binder (aqueous gel prepared from acrylonitrile multipolymer) and deionized water, stirring and sizing, adding a lithium iron phosphate anode material into the sized gel, stirring at a low speed, and stirring at a high speed to fully and uniformly mix the materials, thereby preparing the mixed slurry with the solid content of 55%. The acrylonitrile multipolymer in the mixed slurry accounts for 2.5 percent of the total mass of all solids, the carbon nano tube accounts for 7.5 percent, and the balance is lithium iron phosphate. Coating the slurry on the surface of a copper foil, conveying the copper foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the copper foil into a low-temperature drying bin at-10 ℃, and stripping the copper foil after drying to obtain a composite aerogel film A which is used as a transfer electrode for extracting lithium;
mixing carbon nanotube slurry, an aqueous binder (aqueous gel prepared from acrylonitrile multipolymer) and deionized water, stirring and sizing; and (3) carrying out jet milling on spodumene to submicron-sized fine powder, adding the fine powder into the prepared glue, stirring at a low speed, and stirring at a high speed to fully and uniformly mix the fine powder with the spodumene to obtain the mixed slurry with the solid content of 55%. The acrylonitrile multipolymer in the mixed slurry accounts for 2.5 percent of the total mass of all solids, the carbon nano tube accounts for 7.5 percent, and the balance is lithium iron phosphate. Coating the slurry on the surface of an aluminum foil, conveying the aluminum foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the aluminum foil into a low-temperature drying bin at-10 ℃, and stripping the aluminum foil after drying to obtain a composite aerogel film B which is used as a lithium supply electrode for extracting lithium;
wherein, the stirring, glue-beating and revolution are 25rmp, the dispersion rotating speed is 3000rmp, and the stirring time is 60min; the revolution of the slurry mixing and low-speed stirring is 15rmp, the revolution of the slurry mixing and high-speed stirring is 30rmp, the dispersion rotating speed is 3000rmp, and the stirring time is 120min.
And sequentially stacking and assembling three-electrode parallel batteries by taking glass fiber as a diaphragm according to a mode of supplying a lithium electrode/the diaphragm/a transfer electrode/the diaphragm/a collecting electrode, and inserting the three-electrode parallel batteries into lithium hexafluorophosphate-based electrolyte protected by inert gas to form a lithium extraction battery system.
Switching on a power supply to charge a collecting electrode (negative electrode)/transferring electrode (positive electrode) battery, and charging the battery with a constant current of 1A, changing to constant voltage charging when the voltage of the battery reaches 3.65V, and automatically stopping charging when the charging current is reduced to 0, so that lithium ions in lithium iron phosphate of the transferring electrode migrate to the collecting electrode; then, the same charging mode is adopted to charge the transfer electrode (negative electrode)/lithium supply electrode (positive electrode), so that lithium ions in the lithium supply electrode migrate to the transfer electrode, and the charging steps are repeated in sequence until the lithium ions in the lithium supply electrode migrate completely, and the extraction of the lithium ions in spodumene is completed.
Taking down the lithium-containing collecting electrode, soaking the collecting electrode into liquid ammonia to dissolve out the lithium completely, and cleaning the electrode for reuse; evaporating the lithium-containing liquid ammonia to obtain high-purity metallic lithium and pure ammonia gas; collecting ammonia gas, compressing into liquid ammonia for recycling.
And (3) mechanically stirring and floating the lithium-supplied electrode after extracting lithium, and recycling CNTp.
The carbon nanotube aerosol obtained in this example has a film thickness of 50 μm and an areal density of 19g/m 2 The porosity is 80%, the SEM image of the section is shown in figure 2, and the image shows that the sample is in a spongy three-dimensional porous structure, the pore size is in the order of nanometers to micrometers, the pore volume is large, and the metal lithium can be effectively stored.
Example 2
Adding carbon nano tubes into 40% alcohol water solution, carrying out ultrasonic treatment, adding a polyvinyl alcohol solution and a sodium carboxymethyl cellulose solution with mass ratio of 7:3 and mass fraction of 10%, wherein the total amount of the polyvinyl alcohol and the sodium carboxymethyl cellulose is 1/10 of the mass of the carbon nano tubes, and continuously stirring for 30min at the speed of 200 rpm to fully and uniformly mix the materials, so as to obtain carbon nano tube slurry with the solid content of 12.5%; coating the slurry on the surface of a copper foil, conveying the copper foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the copper foil into a low-temperature drying bin at-10 ℃, drying and stripping to obtain a carbon nano tube aerosol film, and taking the carbon nano tube aerosol film as a collecting electrode for extracting lithium;
mixing carbon nanotube slurry, an aqueous binder (aqueous gel prepared from acrylonitrile multipolymer) and deionized water, stirring and sizing, adding a lithium iron phosphate anode material into the sized gel, stirring at a low speed, and stirring at a high speed to fully and uniformly mix the materials, thereby preparing the mixed slurry with the solid content of 55%. The acrylonitrile multipolymer in the mixed slurry accounts for 2.5 percent of the total mass of all solids, the carbon nano tube accounts for 7.5 percent, and the balance is lithium iron phosphate. Coating the slurry on the surface of a copper foil, conveying the copper foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the copper foil into a low-temperature drying bin at-10 ℃, and stripping the copper foil after drying to obtain a composite aerogel film A which is used as a transfer electrode for extracting lithium;
mixing carbon nanotube slurry, an aqueous binder (aqueous gel prepared from acrylonitrile multipolymer) and deionized water, stirring and sizing; and (3) carrying out jet milling on the waste lithium ion positive electrode material consisting of lithium iron phosphate to submicron fine powder, adding the fine powder into the prepared glue, stirring at a low speed, and stirring at a high speed to fully and uniformly mix the fine powder and the glue to obtain the mixed slurry with the solid content of 55%. The acrylonitrile multipolymer in the mixed slurry accounts for 2.5 percent of the total solid, the carbon nano tube accounts for 7.5 percent, and the balance is lithium iron phosphate. Coating the slurry on the surface of a copper foil, conveying the copper foil into a liquid ammonia freeze dehydration pond through a transmission machine, then conveying the copper foil into a low-temperature drying bin at-10 ℃, and stripping the copper foil after drying to obtain a composite aerogel film B which is used as a lithium-providing lithium electrode;
wherein, the stirring, glue-beating and revolution are 25rmp, the dispersion rotating speed is 3000rmp, and the stirring time is 60min; the revolution of the slurry mixing and low-speed stirring is 15rmp, the revolution of the slurry mixing and high-speed stirring is 30rmp, the dispersion rotating speed is 3000rmp, and the stirring time is 120min.
And sequentially stacking and assembling three-electrode parallel batteries by taking glass fiber as a diaphragm according to a mode of supplying a lithium electrode/the diaphragm/a transfer electrode/the diaphragm/a collecting electrode, and inserting the three-electrode parallel batteries into an inert gas-protected lithium perchlorate-based electrolyte to form a lithium extraction battery system.
Switching on a power supply to charge the collecting electrode (negative electrode)/transferring electrode (positive electrode) battery, and charging with 1A constant current until the battery voltage reaches 3.65V, and automatically stopping charging until the charging current is reduced to 0, so that lithium ions in the transferring electrode lithium iron phosphate migrate to the collecting electrode; then, the same charging mode is adopted to charge the transfer electrode (negative electrode)/lithium supply electrode (positive electrode), so that lithium ions in the lithium supply electrode migrate to the transfer electrode, and the charging steps are repeated in sequence until the lithium ions in the lithium supply electrode migrate completely, and the extraction of the lithium ions in spodumene is completed.
Taking down the lithium-containing collecting electrode, soaking the collecting electrode into liquid ammonia to dissolve out the lithium completely, and cleaning the electrode for reuse; evaporating the lithium-containing liquid ammonia to obtain high-purity metallic lithium and pure ammonia gas; collecting ammonia gas, compressing into liquid ammonia for recycling.
And (3) mechanically stirring and floating the lithium-supplied electrode after extracting lithium, and recycling CNTp.
According to the concentration change condition of electrolyte in the lithium extraction battery system, the lithium extraction battery system can be replaced or supplemented regularly.
It is to be understood that the above-described embodiments of the present invention are merely illustrative of or explanation of the principles of the present invention and are in no way limiting of the invention. Accordingly, any modification, equivalent replacement, improvement, etc. made without departing from the spirit and scope of the present invention should be included in the scope of the present invention. Furthermore, the appended claims are intended to cover all such changes and modifications that fall within the scope and boundary of the appended claims, or equivalents of such scope and boundary.
Claims (8)
1. A method for extracting metallic lithium, comprising the steps of:
step one, preparing three electrodes:
preparing the carbon nano tube into an aerogel film which is used as a collecting electrode for extracting lithium; the preparation method of the aerogel film corresponding to the collecting electrode comprises the following steps: dispersing the carbon nano tube in a solvent, adding a binder and a stabilizer, and continuously stirring to fully and uniformly mix the carbon nano tube to obtain carbon nano tube slurry; coating the carbon nano tube slurry on the surface of a substrate, conveying the carbon nano tube slurry into a liquid ammonia freezing dehydration pond through a transmission machine, then conveying the carbon nano tube slurry into a low-temperature drying bin, and stripping the substrate after drying to obtain the carbon nano tube;
uniformly mixing the carbon nano tube with a lithium ion battery anode material to prepare a composite aerogel film A serving as a transfer electrode for extracting lithium; the preparation method of the composite aerogel film A corresponding to the transfer electrode comprises the following steps: mixing the carbon nano tube slurry, the water-based binder and deionized water, stirring and sizing, adding the positive electrode material of the lithium ion battery into the sized glue, and stirring to fully and uniformly mix the materials to prepare mixed slurry; coating the mixed slurry on the surface of a substrate, conveying the mixed slurry into a liquid ammonia freezing dehydration pond through a transmission machine, then conveying the mixed slurry into a low-temperature drying bin, and stripping the substrate after drying to obtain the liquid ammonia freezing dehydration substrate;
in the preparation method of the composite aerogel film A, the solid content of the mixed slurry is 50% -60%, the aqueous binder in the mixed slurry accounts for 2% -3% of the total mass of all solids, the carbon nano tube accounts for 5% -10%, and the rest is the anode material of the lithium ion battery;
pulverizing lithium-containing ore or waste lithium ion battery anode material into submicron-sized fine powder by air flow, and uniformly mixing with carbon nano tubes to prepare a composite aerogel film B serving as a lithium supply electrode; the preparation method of the composite aerogel film B corresponding to the lithium electrode comprises the following steps: mixing and stirring the carbon nano tube slurry, the water-based binder and deionized water for sizing, crushing lithium-containing ore or waste lithium ion battery anode materials into submicron fine powder, adding the fine powder into the sized glue, and stirring to fully and uniformly mix the fine powder to prepare mixed slurry; coating the mixed slurry on the surface of a substrate, conveying the mixed slurry into a liquid ammonia freezing dehydration pond through a transmission machine, then conveying the mixed slurry into a low-temperature drying bin, and stripping the substrate after drying to obtain the liquid ammonia freezing dehydration substrate;
in the preparation method of the composite aerogel film B, the solid content of the mixed slurry is 50-60%, the aqueous binder in the mixed slurry accounts for 2-3% of the total mass of all solids, the carbon nano tube accounts for 5-10%, and the rest is lithium-containing ore or waste lithium ion battery anode material
Step two, forming a three-electrode parallel battery according to a mode of supplying a lithium electrode/a diaphragm/a transfer electrode/a diaphragm/a collecting electrode, and inserting the three-electrode parallel battery into a lithium-based electrolyte protected by inert gas to form a lithium-extracting battery system;
step three, charging the collecting electrode/transfer electrode battery to enable lithium ions in the positive electrode material of the lithium ion battery of the transfer electrode to migrate to the collecting electrode;
step four, charging the transfer electrode/lithium-supplying electrode battery to enable lithium ions in the lithium-supplying electrode to migrate to the transfer electrode;
step five, repeating the step three and the step four in sequence, so that lithium ions in the lithium supply electrode continuously migrate to the collecting electrode through the transfer electrode;
step six, soaking and cleaning the lithium-containing collecting electrode with liquid ammonia to dissolve lithium in the liquid ammonia, and evaporating the obtained lithium-containing liquid ammonia solution to obtain metal lithium and ammonia gas;
the collecting electrode in the third step is used as a negative electrode, and the transferring electrode is used as a positive electrode; and step four, the transfer electrode is used as a negative electrode, and the lithium electrode is used as a positive electrode.
2. The method for extracting metallic lithium as claimed in claim 1, wherein after the metallic lithium extraction is completed, the carbon nanotubes are recovered by mechanical stirring and floatation of the lithium electrode.
3. The method according to claim 1, wherein in the first step, the carbon nanotubes are at least one of single-walled carbon nanotubes and multi-walled carbon nanotubes;
the purity of the carbon nano tube is more than 99%, the diameter is 10-200 nm, and the length is 5-20 mu m.
4. The method for extracting metal lithium as claimed in claim 1, wherein in the first step, the positive electrode material of the lithium ion battery used for preparing the transfer electrode is at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium cobalt oxide, lithium manganate and lithium nickelate.
5. The method according to claim 1, wherein in the first step, the lithium-containing ore used for the lithium electrode is prepared as at least one of spodumene, lepidolite, laponite, petalite, and petalite;
the waste lithium ion battery material used for preparing the lithium electrode contains at least one of lithium iron phosphate, lithium manganese phosphate, lithium iron manganese phosphate, lithium vanadium phosphate, lithium cobalt oxide, lithium manganate and lithium nickelate.
6. The method according to claim 1, wherein in the second step, the assembled three-electrode parallel battery is a flat plate or is wound into a cylinder.
7. The method according to claim 1, wherein in the second step, the lithium-based electrolyte is lithium hexafluorophosphate and/or lithium perchlorate.
8. The method for extracting metal lithium according to claim 1, wherein in the fifth step, the lithium-containing collecting electrode is recycled after being washed with liquid ammonia; the ammonia gas obtained by evaporation can be compressed to prepare liquid ammonia for recycling.
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