CN117101599A - Lithium ion sieve adsorbent material and preparation method and application thereof - Google Patents
Lithium ion sieve adsorbent material and preparation method and application thereof Download PDFInfo
- Publication number
- CN117101599A CN117101599A CN202310981986.4A CN202310981986A CN117101599A CN 117101599 A CN117101599 A CN 117101599A CN 202310981986 A CN202310981986 A CN 202310981986A CN 117101599 A CN117101599 A CN 117101599A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium ion
- source
- ion sieve
- adsorbent material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 171
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 239000003463 adsorbent Substances 0.000 title claims abstract description 113
- 239000000463 material Substances 0.000 title claims abstract description 103
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 96
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 35
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000011572 manganese Substances 0.000 claims description 29
- -1 lithium alkali metal Chemical class 0.000 claims description 28
- 150000003624 transition metals Chemical class 0.000 claims description 22
- 238000005245 sintering Methods 0.000 claims description 15
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- 229910052701 rubidium Inorganic materials 0.000 claims description 12
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 12
- 239000007790 solid phase Substances 0.000 claims description 12
- 229910052748 manganese Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 8
- 238000004146 energy storage Methods 0.000 claims description 8
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical compound [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 claims description 2
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910001942 caesium oxide Inorganic materials 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 2
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 2
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 2
- HEQUOWMMDQTGCX-UHFFFAOYSA-L dicesium;oxalate Chemical compound [Cs+].[Cs+].[O-]C(=O)C([O-])=O HEQUOWMMDQTGCX-UHFFFAOYSA-L 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 claims description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 235000014413 iron hydroxide Nutrition 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 229940039748 oxalate Drugs 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 31
- 239000002253 acid Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000007772 electrode material Substances 0.000 abstract description 3
- 238000010828 elution Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- 239000007774 positive electrode material Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000010405 anode material Substances 0.000 description 9
- 239000002243 precursor Substances 0.000 description 9
- 239000012267 brine Substances 0.000 description 8
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 8
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000000605 extraction Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000013505 freshwater Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910003548 Li(Ni,Co,Mn)O2 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 229910014689 LiMnO Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011656 manganese carbonate Substances 0.000 description 2
- 229940093474 manganese carbonate Drugs 0.000 description 2
- 235000006748 manganese carbonate Nutrition 0.000 description 2
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 2
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- RTBHLGSMKCPLCQ-UHFFFAOYSA-N [Mn].OOO Chemical compound [Mn].OOO RTBHLGSMKCPLCQ-UHFFFAOYSA-N 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000010306 acid treatment Methods 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
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- IAQLJCYTGRMXMA-UHFFFAOYSA-M lithium;acetate;dihydrate Chemical compound [Li+].O.O.CC([O-])=O IAQLJCYTGRMXMA-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- CDUFCUKTJFSWPL-UHFFFAOYSA-L manganese(II) sulfate tetrahydrate Chemical compound O.O.O.O.[Mn+2].[O-]S([O-])(=O)=O CDUFCUKTJFSWPL-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/041—Oxides or hydroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3028—Granulating, agglomerating or aggregating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/42—Treatment or purification of solutions, e.g. obtained by leaching by ion-exchange extraction
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
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Abstract
The application discloses a lithium ion sieve adsorbent material, a preparation method and application thereof, and relates to the technical field of energy materials. The chemical molecular formula of the lithium ion sieve adsorbent material is M1 y (Li x M2 1‑x )O 2 The method comprises the steps of carrying out a first treatment on the surface of the M1 is at least one of non-lithium alkali metal elements; m2 is at least one of transition metal elements; li and the transition metal element M2 together occupy one lattice site. The preparation method of the lithium ion sieve adsorbent material is a brand new method, and the use amount of the lithium source in the raw material is only that of the traditional adsorbent materialLess than 50 percent, no acid elution process is needed, the industrial process is simple, and the production cost is low; the prepared lithium ion sieve has high purity and high adsorption quantity; the adsorbent can adsorb lithium ions in the solution, and the material after adsorbing the lithium ions can be used as a raw material for preparing the lithium ion electrode material, so that the raw material source of the lithium ion electrode material is expanded, and the adsorbent has wide prospects when applied to the field of new energy.
Description
Technical Field
The application belongs to the technical field of energy materials, and particularly relates to a lithium ion sieve adsorbent material, and a preparation method and application thereof.
Background
Lithium is widely used in the fields of energy, electronics, chemical industry, aerospace and the like, and at present, about three quarters of the world of lithium resources are used for manufacturing lithium ion batteries. With the growth of new energy automobile industry and energy storage industry, the demand of lithium ion batteries and lithium resources is increasing. The salt lake brine contains a great amount of lithium resources, which account for about 60% of the world's lithium resources, and how to efficiently extract lithium from the salt lake brine has become a problem to be solved.
In the aspect of extracting lithium from salt lake brine, an adsorbent method, a solvent extraction method, a membrane method and the like are the most main methods. The adsorption method is considered as one of the most promising lithium extraction methods in salt lakes at present due to the characteristics of good ion selectivity, environmental friendliness, high cyclic utilization rate and the like. The core of the adsorption process is the adsorbent material, with the ion sieve oxide being the most studied and best performing adsorbent at present. Existing ion sieve adsorbents mainly include aluminum, manganese and titanium, especially spinel manganese (HMn 2 O 4 、H 1.33 Mn 1.67 O 4 、H 1.6 Mn 1.6 O 4 Etc.) and titanium-based ion sieve material (H) 2 TiO 3 Etc.) has the characteristics of good selectivity, large adsorption capacity and high cyclic utilization rate, and can obviously improve the efficiency of extracting lithium from brine.
However, conventional lithium ion sieve materials require a lithium source (e.g., lithium hydroxide or lithium carbonate) as a starting material to prepare a lithium-containing precursor, and then washing out the lithium from the lattice with dilute sulfuric acid or dilute hydrochloric acid to obtain the ion sieve material. Not only has complex working procedures and high cost, but also consumes a large amount of fresh water and acid, and has serious pollution. In the subsequent use process, the traditional lithium ion sieve material adopts the working principle of proton-lithium ion exchange to realize the extraction of lithium from brine, and realizes the recycling through acid leaching, thus having the problems of insufficient stability and the like.
Disclosure of Invention
In view of the above, the application provides a lithium ion sieve adsorbent material, a preparation method and application thereof, and mainly aims to solve the technical problems of large lithium source consumption, complex preparation process and serious acid washing pollution in the synthetic raw materials of the lithium ion sieve adsorbent.
In one aspect, the application provides a lithium ion sieve adsorbent material having a chemical formula of formula I;
M1 y (Li x M2 1-x )O 2 a formula I;
m1 in the formula I is selected from at least one of non-lithium alkali metal elements, wherein y is more than 0 and less than or equal to 1;
m2 in the formula I is at least one of transition metal elements;
li and transition metal element M2 occupy a lattice position, and x is more than or equal to 0 and less than 0.5.
X and y in the above formula I of the present application represent the molar ratio between the corresponding metal elements.
Alternatively, y in formula I is selected from any value or range of values between any two of 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0.
Alternatively, x in formula I is selected from any value or range of values between any two of 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3, 0.35, 0.4, 0.45, 0.49.
The inventor discovers that a large amount of lithium sources are needed to be used as raw materials of the molecular sieve in the preparation process of the traditional lithium ion sieve adsorbent in the research and development process of the lithium ion adsorbent, and lithium in crystal lattices of the molecular sieve is needed to be removed through an acid washing process after a lithium-containing precursor is prepared. The method has the advantages that the lithium source is used in a large amount, the production cost is increased, and the pickling water seriously pollutes the environment; in order to solve the problems, the inventor creatively proposes how to reduce the use amount of a lithium source and prepare a lithium ion sieve adsorbent material with high purity, high adsorption capacity and good stability without using an acid washing process; in order to solve the technical problems, the inventor firstly provides a lithium ion sieve adsorbent material which has different element compositions and different working principles compared with the traditional adsorbent; specifically, the application innovatively introduces non-lithium alkali metal M1 on the element composition of the lithium ion sieve adsorbent, and utilizes the working principle that the non-lithium alkali metal M1 and lithium ions in lithium-containing solution can spontaneously perform ion exchange to realize the purpose that the lithium ion sieve adsorbent material can adsorb lithium ions in lithium-containing solution, thereby achieving the purpose that the lithium ion sieve adsorbent material with high purity, high adsorption capacity and good stability can be prepared under the conditions that the lithium source usage amount is reduced (the lithium source usage amount is less than 50% of that of the traditional adsorbent material) and no acid washing process is used.
Alternatively, M1 in formula I is selected from at least one of non-lithium alkali metal elements Na, K, rb, and Cs.
Alternatively, M2 in the formula I is selected from at least one of transition metal elements Fe, co, ni, and Mn.
According to the lithium ion sieve adsorbent material, non-lithium alkali metal ions in the material and lithium ions in the solution are subjected to spontaneous ion exchange, so that the aim that the transition metal-containing molecular sieve material can adsorb lithium ions in the solution is fulfilled; the lithium ion sieve adsorbent has the function of adsorbing lithium mainly realized by compounding non-lithium alkali metal element M1 and transition metal element M2, and the compound of the composite metal can be selected from oxides thereof to realize the purpose of adsorbing lithium ions in solution.
In a second aspect, the application provides a method for preparing the lithium ion sieve adsorbent material, which comprises the following steps:
s1: mixing a non-lithium alkali metal source, a lithium source and a transition metal source to obtain a mixture;
s2: and carrying out high-temperature solid-phase sintering on the mixture, and cooling to obtain the lithium ion sieve adsorbent material.
According to the preparation method disclosed by the application, the non-lithium alkali metal source is introduced into the raw materials of the preparation method, so that the use amount of the lithium source can be reduced, an acid washing process is not needed, the preparation process is simplified, and the production cost is reduced.
Optionally, in step S1, the molar ratio of the non-lithium alkali metal source to the transition metal source is 0.3 to 2:1.
optionally, the molar ratio of the non-lithium alkali metal source and the transition metal source is selected from any value or range of values between any two of 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2.
Optionally, in step S1, the molar ratio of the lithium source to the transition metal source is 0 to 0.3:1.
optionally, the molar ratio of the lithium source and the transition metal source is any value or range of values between any two of 0, 0.05, 0.1, 0.15, 0.2, 0.25, 0.3.
Optionally, in step S1, the lithium source is selected from at least one of lithium oxide, lithium carbonate, lithium oxalate, lithium acetate, and lithium hydroxide;
the sodium source in the non-lithium alkali metal source is selected from at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium acetate and sodium hydroxide;
the potassium source in the non-lithium alkali metal source is selected from at least one of potassium oxide, potassium carbonate, potassium oxalate, potassium acetate and potassium hydroxide;
the rubidium source in the non-lithium alkali metal source is selected from at least one of an oxide of rubidium, a carbonate of rubidium, an oxalate of rubidium, an acetate of rubidium, and a hydroxide of rubidium;
the cesium source in the non-lithium alkali metal source is selected from at least one of cesium oxide, cesium carbonate, cesium oxalate, cesium acetate and cesium hydroxide;
the iron source in the transition metal source is selected from at least one of iron oxide, iron carbonate, iron oxalate, iron acetate and iron hydroxide;
the cobalt source in the transition metal source is selected from at least one of cobalt oxide, cobalt carbonate, cobalt oxalate, cobalt acetate and cobalt hydroxide;
the nickel source in the transition metal source is selected from at least one of nickel oxide, nickel carbonate, nickel oxalate, nickel acetate and nickel hydroxide;
the manganese source in the transition metal source is selected from at least one of oxides of manganese, carbonates of manganese, oxalates of manganese, acetates of manganese, and hydroxides of manganese.
Optionally, in step S1, the non-lithium alkali metal source, the lithium source and the transition metal source are mixed by at least one of hand milling, ball milling, solution evaporation and coprecipitation.
Optionally, in the step S2, the temperature of the high-temperature solid-phase sintering is 500-1000 ℃, and the time of the high-temperature solid-phase sintering is 0.5-24 h.
Preferably, the high-temperature solid-phase sintering temperature is 500-850 ℃, and the high-temperature solid-phase sintering time is 0.5-6 h.
Further preferably, the high temperature solid phase sintering temperature is 500 ℃ to 700 ℃.
Optionally, the high temperature solid phase sintering temperature is selected from any value or range of values between any two of 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃.
Optionally, the high temperature solid phase sintering time is selected from any value or range between any two of 0.5h, 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, 7.5h, 8h, 8.5h, 9h, 9.5h, 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h, 15h, 15.5h, 16h, 16.5h, 17h, 17.5h, 18h, 18.5h, 19h, 19.5h, 20h, 20.5h, 21h, 21.5h, 22h, 22.5h, 23h, 23.5h, 24h.
Optionally, the cooling in step S2 is natural cooling to room temperature.
In a third aspect, the application provides an application of the lithium ion sieve adsorbent material in adsorbing lithium ions in a lithium-containing solution; the non-lithium alkali metal ion M1 in the lithium ion sieve adsorbent material spontaneously exchanges ions with lithium ions in the lithium-containing solution.
Optionally, the lithium-containing solution comprises salt lake brine, ore lithium extraction and precipitation mother liquor, lithium-containing waste liquor, lithium-containing solution generated in lithium ion battery recovery and purified high-lithium-containing solution thereof.
Optionally, the salt lake is a salt lake of various types such as a plateau.
Optionally, after being mixed with other materials, the lithium ion sieve adsorbent material can be used as a filler of an adsorption tower for extracting lithium ions in salt lake raw brine or old brine.
The lithium ion sieve adsorbent material can be applied to any type or composition of lithium ion-containing solution, and can achieve the purpose of adsorbing lithium ions.
In a fourth aspect, the application provides the use of the above-described lithium ion sieve adsorbent material in an energy storage material.
Optionally, after the lithium ion sieve adsorbent material adsorbs lithium ions, the lithium ion sieve adsorbent material is directly used as one of raw materials for synthesizing the anode material of the lithium ion battery.
The lithium ion sieve adsorbent material of the application forms a new material containing a large amount of transition metal compounds of lithium ions after adsorbing the lithium ions.
The application is based on the novel lithium ion material formed after the lithium ion sieve adsorption material adsorbs lithium ions, fully considers the application value of a large amount of lithium ions contained in the novel lithium ion material, and creatively provides that the novel lithium ion material can be applied to the field of energy storage or power, and is particularly suitable for the anode material of a lithium ion battery.
In a fifth aspect, the present application provides the use of the above lithium ion material in an energy storage material.
Alternatively, the lithium ion material can be directly used as a raw material for preparing a positive electrode material of transition metal oxide of a lithium ion battery.
In a sixth aspect, the present application provides a positive electrode material of a lithium ion battery, wherein the raw material of the positive electrode material includes the lithium ion material.
Alternatively, the positive electrode material comprises a ternary positive electrode material of a lithium ion battery, such as Li (Ni, co, mn) O 2 Etc.
Optionally, the positive electrode material comprises a lithium ion battery manganese-based material, such as LiMn 2 O 4 Etc.
Optionally, the positive electrode material comprises a lithium ion battery lithium cobalt oxide material.
The application at least comprises the following innovative technologies:
(1) The molecular formula of the lithium ion sieve adsorbent material is M1 y (Li x M2 1-x )O 2 The method comprises the steps of carrying out a first treatment on the surface of the It has different element composition and different working principle with the traditional lithium ion sieve adsorbent material.
(2) In the preparation process of the lithium ion sieve adsorbent material, the used lithium source is less than half of that of the traditional adsorbent material, and the lithium ion sieve adsorbent material can be prepared by one-step sintering without acid washing.
(3) The lithium ion sieve adsorbent material can be used for adsorbing lithium ions in a solution.
(4) The lithium ion sieve adsorbent material can be used for forming a new lithium ion material after adsorbing lithium ions in a solution, can be used in the field of energy storage, and can be particularly directly used as a raw material for preparing a lithium battery anode material.
Compared with the prior art, the application has the following beneficial effects:
(1) The usage amount of the raw material lithium source of the lithium ion sieve adsorbent material is less than 50% of that of the traditional adsorbent material, and the cost is reduced.
(2) The preparation method of the lithium ion sieve adsorbent material is a brand new method, adopts one-step sintering, does not need acid treatment, can reduce cost, does not need consumption of fresh water and acid, and is environment-friendly.
(3) The lithium ion sieve adsorbent material has excellent lithium ion selectivity and very high lithium absorption capacity (30-40 mg/g), can be used for direct extraction of raw halogen of lithium extracted from salt lakes, and has very good application prospect.
(4) The lithium ion sieve adsorbent material can be directly used for preparing the high-performance lithium ion battery anode material after adsorbing lithium ions, does not need to carry out lithium removal, avoids the consumption of fresh water and acid in the lithium removal process, and realizes the real green lithium extraction and lithium utilization.
Drawings
FIG. 1 is an X-ray powder diffraction pattern of a multi-element lithium ion sieve adsorbent material prepared in example 1 of the present application;
FIG. 2 is a scanning electron microscope image of a multi-element lithium ion sieve adsorbent material prepared in example 1 of the present application;
FIG. 3 is an X-ray powder diffraction pattern of a ternary positive electrode material prepared in example 1 of the present application;
fig. 4 is a first-turn charge-discharge graph of the ternary cathode material prepared in example 1 of the present application.
Detailed Description
The following description of the embodiments of the present application will be made in detail and without limitation, the embodiments described are only some, but not all embodiments of the present application. All other embodiments, based on the embodiments of the application, which a person of ordinary skill in the art would achieve without inventive faculty, are within the scope of the application.
Unless otherwise indicated, all starting materials in the examples of the present application were purchased commercially.
The following examples 1-4 prepare compounds of formula I;
M1 y (Li x M2 1-x )O 2 a formula I;
m1 in the formula I is selected from at least one of non-lithium alkali metal elements, and y is more than or equal to 0 and less than or equal to 1.
M2 is at least one of transition metal elements;
li and transition metal element M2 occupy a lattice position, x is more than or equal to 0 and less than 0.5;
x and y represent the molar ratio between the corresponding metallic elements.
Example 1
Preparing an adsorbent: weighing 0.370g of analytically pure lithium carbonate, 4.597g of manganese carbonate, 1.059g of sodium carbonate and 2.073g of potassium carbonate, mixing and fully grinding for 2 hours in a mortar, transferring to a corundum crucible, heating to 700 ℃ at a speed of 10 ℃/min in a box-type muffle furnace, preserving heat for 10 hours, and naturally cooling to room temperature to obtain the lithium ion sieve compound. The X-ray diffraction diagram is shown in figure 1, the scanning electron microscope diagram is shown in figure 2, and the molecular formula of the lithium ion sieve adsorbent is (Na 0.4 K 0.6 )(Li 0.2 Mn 0.8 )O 2 。
Adsorbing lithium ions in the solution: 0.5g of the lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 200mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 30.8mg/g.
The equilibrium adsorption capacity refers to the ratio of the mass of lithium ions in the adsorption solution to the mass of the adsorbent after adsorption reaches equilibrium.
Mass of lithium ion reduction= (initial concentration of lithium ion in solution-concentration of lithium ion after adsorption equilibrium) ×volume of solution.
Preparing a positive electrode material: weighing 0.611g of adsorbent material, 0.747g of nickel oxide, 0.321g of cobaltosic oxide and 0.517g of lithium carbonate after adsorbing lithium ions, ball milling for 12 hours at 400 r/min, sintering for 12 hours at 900 ℃, and cooling to obtain a nickel-cobalt-manganese ternary anode material Li (Ni, co, mn) O 2 . The X-ray diffraction diagram is shown in figure 3, and the first-circle charge-discharge curve is shown in figure 4.
Example 2
Preparing an adsorbent: 0.370g of analytically pure lithium carbonate was weighed out, (Ni) 0.5 Co 0.2 Mn 0.3 )CO 3 10.586g, 2.118g of sodium carbonate and 4.146g of potassium carbonate are ball-milled in a ball mill at 400rpm for 10 hours, transferred to a corundum crucible, heated to 750 ℃ in a box-type muffle furnace at the speed of 10 ℃/min, kept for 10 hours, and naturally cooled to room temperature, thus obtaining the lithium ion sieve compound; the molecular formula of the lithium ion sieve adsorbent is (Na 0.4 K 0.6 )(Li 0.1 Ni 0.45 Co 0.18 Mn 0.27 )O 2 。
Adsorbing lithium ions in the solution: 0.5g of the lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 100mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 33.5mg/g.
Example 3
Preparing an adsorbent: to 100mL of deionized water were added 2.213g of potassium acetate, 4.159g of nickel sulfate hexahydrate, 1.004g of manganese sulfate tetrahydrate and 0.235g of lithium acetate dihydrate, and the mixture was thoroughly stirred and dissolved. Evaporating the solution in an 80-DEG C oven, loading the powder into a corundum crucible, transferring the corundum crucible into a muffle furnace, continuously heating to 800 ℃ at a speed of 5 ℃/min, preserving heat for 10 hours, and naturally cooling to room temperature to obtain the lithium ion sieve compound; the molecular formula of the lithium ion sieve adsorbent is K (Li 0.1 Ni 0.7 Mn 0.2 )O 2 。
Adsorbing lithium ions in the solution: 0.5g of the lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 150mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 37.4mg/g.
Example 4
Preparing an adsorbent: 0.740g of analytically pure lithium carbonate was weighed out, (Ni) 0.5 Co 0.2 Mn 0.3 )(OH) 2 7.330g, 3.177g of sodium carbonate and 2.764g of potassium carbonate are ball-milled in a ball mill at 400rpm for 10 hours, transferred to a corundum crucible, heated to 750 ℃ in a box-type muffle furnace at a speed of 10 ℃/min, kept for 10 hours, and naturally cooled to room temperature, thus obtaining the lithium ion sieve-type adsorbent compound; the molecular formula of the adsorbent is (Na 0.6 K 0.4 )(Li 0.2 Ni 0.4 Co 0.16 Mn 0.24 )O 2 。
Adsorbing lithium ions in the solution: 0.5g of lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 100mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 36.5mg/g.
Comparative example 1
Preparing an adsorbent: weighing 0.739g of analytically pure lithium carbonate and 4.597g of manganese carbonate, mixing and fully grinding for 2 hours in a mortar, transferring to a corundum crucible, heating to 800 ℃ at a speed of 10 ℃ per minute in a box-type muffle furnace, and keepingNaturally cooling to room temperature after 10 hours to obtain the traditional lithium ion sieve compound (HMn) 2 O 4 ) LiMn, precursor of (c) 2 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Adding the precursor into 300mL of 0.1mol/L dilute hydrochloric acid, stirring at room temperature for 6 hours, completing the pickling process, and drying at 80 ℃ after suction filtration to obtain the traditional lithium ion sieve compound HMn 2 O 4 。
Adsorbing lithium ions in the solution: 0.5g of the lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 200mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 15.8mg/g.
Comparative example 2
Preparing an adsorbent: weighing 1.200g of analytically pure lithium hydroxide and 3.518g of manganese oxyhydroxide, adding into a 50mL hydrothermal tank containing 20mL of deionized water, preserving heat at 120 ℃ for 1 day, filtering, washing and drying to obtain an intermediate product LiMnO 2 . LiMnO is added to 2 Placing in a box-type muffle furnace, heating to 600 ℃ at a speed of 10 ℃/min, preserving heat for 4 hours, naturally cooling to room temperature to obtain the traditional lithium ion sieve type compound (H) 1.6 Mn 1.6 O 4 ) Precursor Li of (2) 1.6 Mn 1.6 O 4 . Adding the precursor into 2L of 0.5mol/L dilute hydrochloric acid, stirring at room temperature for 24 hours, finishing the pickling process, and drying at 60 ℃ after suction filtration to obtain the traditional lithium ion sieve compound H 1.6 Mn 1.6 O 4 。
Adsorbing lithium ions in the solution: 0.5g of the lithium ion sieve adsorbent material is weighed and placed in 400mL of solution with the lithium ion concentration of 200mg/L, adsorption equilibrium is reached after 8 hours, and the equilibrium adsorption capacity is measured to be 28.2mg/g.
The lithium ion sieve adsorbent materials are successfully prepared in all the examples 1-4; when the adsorbent material is used for adsorbing lithium ions in a solution, the adsorption effect is obvious; the new material after absorbing lithium ions by the adsorbent is used for successfully preparing the anode material, and the anode material has good charge and discharge performance.
The application takes the lithium ion sieve adsorbent material prepared in the embodiment 1 as an example, and the molecular formula of the adsorbent is as follows: (Na) 0.4 K 0.6 )(Li 0.2 Mn 0.8 )O 2 The method comprises the steps of carrying out a first treatment on the surface of the The structure of the adsorbent is shown in an X-ray powder diffraction diagram in fig. 1, and the microscopic morphology of the surface of the adsorbent particles is shown in a scanning electron microscope diagram in fig. 2.
The X-ray diffraction patterns of examples 2-4 of the present application are similar to those of fig. 1, and analysis shows that the lithium ion sieve adsorbent materials of examples 2-4 have the following molecular formula structures in order:
(Na 0.4 K 0.6 )(Li 0.1 Ni 0.45 Co 0.18 Mn 0.27 )O 2 ，
K(Li 0.1 Ni 0.7 Mn 0.2 )O 2 ，
(Na 0.6 K 0.4 )(Li 0.2 Ni 0.4 Co 0.16 Mn 0.24 )O 2 ；
the lithium ion sieve adsorbent material prepared by the application has the following chemical general formula:
M1 y (Li x M2 1-x )O 2 ；
wherein M1 is selected from at least one of non-lithium alkali metal elements, 0< y < 1;
m1 is preferably at least one of the alkali metal elements Na, K, rb and Cs;
m2 is selected from at least one of transition metal elements, preferably at least one of Fe, co, ni and Mn; li and transition metal element M2 occupy a lattice position, x is more than or equal to 0 and less than 0.5; x and y represent the molar ratio between the corresponding metallic elements.
Taking the lithium ion sieve adsorbent material prepared in example 1 as an example, the charge-discharge curve of the positive electrode material prepared by the adsorbent after adsorbing lithium ions in solution is shown in fig. 4, which illustrates that the positive electrode material prepared by the adsorbent in example 1 has good electrical properties.
The charge-discharge curves of examples 2-4 of the application are similar to those of fig. 4, and analysis shows that the positive electrode materials prepared by the lithium ion sieve adsorbent materials of examples 2-4 have good charge-discharge performance after adsorbing lithium ions; the novel material obtained after the lithium ion adsorbent material is used as one of the raw materials, and the lithium ion battery anode material with good electrical property can be successfully prepared.
The experiment and the result show that the lithium ion sieve adsorbent material and the novel lithium ion material formed after adsorbing lithium ions can be applied to the field of energy storage or power, and can be particularly used for preparing the anode material of a lithium ion battery.
In the preparation of the lithium ion sieve adsorbent material, the usage amount of the lithium source in the total amount of the raw materials is about 4.5wt%, 2.1wt%, 3.1wt% and 5.2wt% in sequence; the lithium source usage amounts of comparative example 1 and comparative example 2 were about 13.8wt% and 25.4wt% in this order, based on the total amount of the raw materials; as can be seen by comparison, the lithium source usage amount of the lithium ion sieve adsorbent material prepared by the method of the application is about 0.08-0.38 times of the lithium source usage amount in the traditional method, and is far smaller than that in the methods of comparative examples 1 and 2.
In the preparation methods of comparative examples 1 and 2, only the precursor of the adsorbent such as LiMn was obtained after mixing and roasting the lithium source and the manganese source 2 O 4 、Li 1.6 Mn 1.6 O 4 The precursor cannot be used for adsorbing lithium ions in a solution, and the precursor is subjected to acid washing by a large amount of hydrochloric acid for 6 hours and 24 hours to obtain the traditional lithium ion sieve compound HMn 2 O 4 、H 1.6 Mn 1.6 O 4 Reuse of HMn 2 O 4 、H 1.6 Mn 1.6 O 4 Adsorbing lithium ions in the solution. In the traditional method, firstly, a large amount of lithium source is needed, secondly, acid washing is needed, sewage is generated after the acid washing, the method is not friendly to the environment, the preparation method is relatively complex, and the cost is relatively high.
The method for preparing the lithium ion sieve adsorbent material in the embodiment 1-4 comprises the following steps:
s1: mixing a non-lithium alkali metal source, a lithium source and a transition metal source to obtain a mixture;
s2: and (3) carrying out high-temperature solid-phase sintering on the mixture, and cooling to obtain the lithium ion sieve adsorbent material.
Preferably, the molar ratio of the non-lithium alkali metal source to the transition metal source is from 0.3 to 2:1.
preferably, the molar ratio of the lithium source to the transition metal source is 0 to 0.3:1.
as can be seen from the above examples 1-4 and comparative examples 1-2, the present application has the advantages of greatly reducing the amount of lithium source used, simplifying the preparation process and directly reducing the production cost by introducing a non-lithium alkali metal source into the raw materials of the above preparation method. Therefore, the above-mentioned preparation method of the present application has very remarkable technical effects as compared with the conventional art.
The adsorption capacity of the lithium ion sieve adsorbent materials prepared in the embodiments 1-4 of the application is 30.8mg/g, 33.5mg/g, 37.4mg/g and 36.5mg/g in sequence; the adsorbents prepared in the conventional methods of comparative example 1 and comparative example 2 had adsorption amounts of 15.8mg/g and 28.2mg/g in this order under substantially the same test conditions; as is clear from comparison, the lithium ion adsorption amount of the adsorbent of the application is about 1.5-2 times of that of the adsorbents of comparative examples 1 and 2, which shows that the adsorbent of the application has stronger adsorption capacity for lithium ions. Meanwhile, the lithium ion adsorbent can be recycled.
The lithium ion adsorbent material prepared by the brand-new preparation method and reasonable raw material proportion has lithium ion adsorption capacity and electrical property.
The lithium ion sieve adsorbent material provided by the application has the advantages of stable structure and large adsorption capacity, and can be directly used for preparing the positive electrode material of the lithium ion battery after adsorbing lithium ions, and the positive electrode material has good electrical properties, so that the lithium ion sieve adsorbent material provides a novel material for the field of energy storage.
The preparation method of the lithium ion sieve adsorbent material provided by the application is convenient to operate, the use amount of a lithium source is greatly reduced, an acid washing process is omitted, the production efficiency is improved, the production cost is reduced, and the preparation method is environment-friendly; the preparation method expands the raw material sources of new energy materials, especially lithium battery electrode materials, and has great industrial prospect.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. The lithium ion sieve adsorbent material is characterized by having a chemical molecular formula of formula I;
M1 y (Li x M2 1-x )O 2 a formula I;
m1 in the formula I is selected from at least one of non-lithium alkali metal elements; y is more than 0 and less than or equal to 1;
m2 in the formula I is at least one of transition metal elements;
li and transition metal element M2 occupy a lattice position, and x is more than or equal to 0 and less than 0.5.
2. A lithium ion sieve adsorbent material according to claim 1,
m1 in the formula I is selected from at least one of non-lithium alkali metal elements Na, K, rb and Cs;
m2 in the formula I is selected from at least one of transition metal elements Fe, co, ni and Mn.
3. A method for preparing a lithium ion sieve adsorbent material according to claim 1 or 2, characterized in that the preparation method comprises the steps of:
s1: mixing a non-lithium alkali metal source, a lithium source and a transition metal source to obtain a mixture;
s2: and carrying out high-temperature solid-phase sintering on the mixture, and cooling to obtain the lithium ion sieve adsorbent material.
4. A method of preparing a lithium ion sieve adsorbent material according to claim 3, wherein in step S1, the molar ratio of the non-lithium alkali metal source to the transition metal source is 0.3-2: 1, a step of; the molar ratio of the lithium source to the transition metal source is 0 to 0.3:1.
5. a method of preparing a lithium ion sieve adsorbent material according to claim 3, wherein the lithium source is selected from at least one of lithium oxide, lithium carbonate, lithium oxalate, lithium acetate and lithium hydroxide;
the sodium source in the non-lithium alkali metal source is selected from at least one of sodium oxide, sodium carbonate, sodium oxalate, sodium acetate and sodium hydroxide;
the potassium source in the non-lithium alkali metal source is selected from at least one of potassium oxide, potassium carbonate, potassium oxalate, potassium acetate and potassium hydroxide;
the rubidium source in the non-lithium alkali metal source is selected from at least one of an oxide of rubidium, a carbonate of rubidium, an oxalate of rubidium, an acetate of rubidium, and a hydroxide of rubidium;
the cesium source in the non-lithium alkali metal source is selected from at least one of cesium oxide, cesium carbonate, cesium oxalate, cesium acetate and cesium hydroxide;
the iron source in the transition metal source is selected from at least one of iron oxide, iron carbonate, iron oxalate, iron acetate and iron hydroxide;
the cobalt source in the transition metal source is selected from at least one of cobalt oxide, cobalt carbonate, cobalt oxalate, cobalt acetate and cobalt hydroxide;
the nickel source in the transition metal source is selected from at least one of nickel oxide, nickel carbonate, nickel oxalate, nickel acetate and nickel hydroxide;
the manganese source in the transition metal source is selected from at least one of oxides of manganese, carbonates of manganese, oxalates of manganese, acetates of manganese, and hydroxides of manganese.
6. The method of claim 3, wherein in step S1, the non-lithium alkali metal source, the lithium source and the transition metal source are mixed by at least one of manual grinding, ball milling, solution evaporation and coprecipitation.
7. The method for preparing a lithium ion sieve adsorbent material according to claim 3, wherein in step S2, the high-temperature solid phase sintering temperature is 500-1000 ℃, and the high-temperature solid phase sintering time is 0.5-24 h.
8. Use of the lithium ion sieve adsorbent material of claim 1 or 2 or the lithium ion sieve adsorbent material prepared by the preparation method of any one of claims 3 to 7 for adsorbing lithium ions in a lithium-containing solution; wherein non-lithium alkali metal ions M1 in the lithium ion sieve adsorbent material spontaneously exchange ions with lithium ions in the lithium-containing solution.
9. Use of the lithium ion sieve adsorbent material of claim 1 or 2 or the lithium ion sieve adsorbent material prepared by the preparation method of any one of claims 3 to 7 in the field of energy storage.
10. The use according to claim 9, wherein the lithium ion sieve adsorbent material is used as a raw material for synthesizing a lithium ion battery cathode material after adsorbing lithium ions.
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