CN113839038A - MOF-derived Bi @ C nano composite electrode material and preparation method thereof - Google Patents
MOF-derived Bi @ C nano composite electrode material and preparation method thereof Download PDFInfo
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- CN113839038A CN113839038A CN202110926378.4A CN202110926378A CN113839038A CN 113839038 A CN113839038 A CN 113839038A CN 202110926378 A CN202110926378 A CN 202110926378A CN 113839038 A CN113839038 A CN 113839038A
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- electrode material
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- ion battery
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 48
- 239000007772 electrode material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 32
- 238000001354 calcination Methods 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 24
- 238000004729 solvothermal method Methods 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 12
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 150000001621 bismuth Chemical class 0.000 claims abstract description 9
- 230000035484 reaction time Effects 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 239000012621 metal-organic framework Substances 0.000 claims description 35
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- 239000011149 active material Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 9
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 5
- 159000000000 sodium salts Chemical class 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 4
- -1 sodium hexafluorophosphate Chemical compound 0.000 claims description 4
- ZPFAVCIQZKRBGF-UHFFFAOYSA-N 1,3,2-dioxathiolane 2,2-dioxide Chemical compound O=S1(=O)OCCO1 ZPFAVCIQZKRBGF-UHFFFAOYSA-N 0.000 claims description 3
- WDXYVJKNSMILOQ-UHFFFAOYSA-N 1,3,2-dioxathiolane 2-oxide Chemical compound O=S1OCCO1 WDXYVJKNSMILOQ-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 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
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical compound [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 claims description 2
- MHYFEEDKONKGEB-UHFFFAOYSA-N oxathiane 2,2-dioxide Chemical compound O=S1(=O)CCCCO1 MHYFEEDKONKGEB-UHFFFAOYSA-N 0.000 claims description 2
- 229960003351 prussian blue Drugs 0.000 claims description 2
- 239000013225 prussian blue Substances 0.000 claims description 2
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 claims description 2
- 229910001488 sodium perchlorate Inorganic materials 0.000 claims description 2
- XGPOMXSYOKFBHS-UHFFFAOYSA-M sodium;trifluoromethanesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C(F)(F)F XGPOMXSYOKFBHS-UHFFFAOYSA-M 0.000 claims description 2
- 150000008053 sultones Chemical class 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000014759 maintenance of location Effects 0.000 abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 description 13
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 12
- 239000002131 composite material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- UJMDYLWCYJJYMO-UHFFFAOYSA-N benzene-1,2,3-tricarboxylic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1C(O)=O UJMDYLWCYJJYMO-UHFFFAOYSA-N 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 5
- 229910001451 bismuth ion Inorganic materials 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 230000001376 precipitating effect Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002077 nanosphere Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910017953 NH4Bi3F10 Inorganic materials 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- FSAJRXGMUISOIW-UHFFFAOYSA-N bismuth sodium Chemical compound [Na].[Bi] FSAJRXGMUISOIW-UHFFFAOYSA-N 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 241001274216 Naso Species 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 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
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of sodium ion batteries, and relates to a MOF-derived Bi @ C nano composite electrode material and a preparation method thereof. The preparation method comprises the steps of carrying out solvothermal reaction on bismuth salt and a ligand to obtain an MOF precursor, and calcining the MOF precursor in an inert atmosphere to obtain a Bi @ C nano composite electrode material; wherein the solvothermal reaction time is 23-37 h, and the calcining time is 2-4 h. The MOF-derived Bi @ C nano composite electrode material provided by the invention has the advantage of high cycle stability, and has better long-cycle capacity retention rate and rate capability.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and relates to a MOF-derived Bi @ C nano composite electrode material and a preparation method thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Since the 21 st century, with the continuing development of society and the tremendous pressure on population growth, an inevitable problem is: energy problem, gradually increasing the schedule. Since the lithium ion battery has a series of advantages of high energy and high power density, and is firstly applied to human life on a large scale, although the advantages are very obvious, the high cost of the battery manufacturing process and the limited lithium resources on the earth limit the further application of the large energy storage system. Another opportunity that has emerged under pressure in humans is other metal ion based batteries. Typically, sodium ion batteries are widely studied because of their abundant sodium reserves on the earth, low production costs, and relatively low oxidation-reduction potentials. The inventor studies to understand that the sodium ion negative electrode material published in the literature: carbonaceous materials (such as graphite and hard carbon), transition metal sulfides and oxides generally have the problems of low capacity retention rate in long cycle and poor rate performance, capacity attenuation is fast in large current and long cycle, and charging and discharging efficiency can be always maintained at about 100% in long cycle test by few materials. In addition, some alloy anode materials exhibit good initial properties in terms of sodium storage, such as metal: tin, antimony and bismuth, among others, which have attracted considerable interest to researchers because of their modest potential and high theoretical capacity in electrode materials.
Bismuth is non-toxic, has abundant earth reserves and larger lattice stripes, is a promising cathode material, provides relatively higher theoretical capacity of 385mAh/g by reacting with sodium to form a bismuth-sodium alloy, and has low charge voltage. However, bismuth as a negative electrode material also has some disadvantages: (1) due to the volume change caused by the alloying process from bismuth to bismuth-sodium alloy as high as 244%, it is a great challenge to be applied in reality. (2) The lower conductivity of bismuth metal limits its rate capability.
Solve the above problemsThe most common approach is to design a nanocomposite structure, use a composite material with a conductive agent, and form an alloy or intermetallic material to improve the electrochemical performance of the bismuth negative electrode material. For example, patent CN111769272A discloses a Bi @ C hollow nanosphere composite material and a preparation method and application thereof. The method comprises the following steps: NH evenly mixed in glycol after centrifugal dissolution treatment4F and BiCl3Immediately reacted with each other, and NH is prepared in advance in large amounts by a conventional liquid reaction process4Bi3F10Nanospheres of NH4Bi3F10Adding the mixture into a solvent, adding a carbon source after ultrasonic dispersion, stirring for reaction, centrifuging and drying to obtain NH4Bi3F10And (2) @ PDA is used for compounding a precursor, then the precursor is subjected to thermal reduction treatment in an inert atmosphere, and after natural cooling, the Bi @ C composite material for the lithium ion/sodium ion battery can be obtained.
However, the inventors have found that the method for preparing the Bi @ C hollow nanosphere composite material disclosed in the above patent document inevitably has some problems, and that there are problems: the synthetic method has the advantages of complex process, lack of universality and unsuitability for large-scale production. Meanwhile, the material can not be subjected to long-cycle test in a sodium ion battery, the specific capacity at 1A/g is reduced to about 250mAh/g at the 100 th circle, the rate capability is poor, and the capacity at 5A/g is only 100 mAh/g.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide the MOF-derived Bi @ C nano-composite electrode material and the preparation method thereof.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, the preparation method of the MOF-derived Bi @ C nano composite electrode material comprises the steps of carrying out solvothermal reaction on bismuth salt and a ligand to obtain an MOF precursor, and calcining the MOF precursor in an inert atmosphere to obtain the Bi @ C nano composite electrode material; wherein the solvothermal reaction time is 23-37 h, and the calcining time is 2-4 h.
The method adopts bismuth ions and ligands to combine to form a Metal Organic Framework (MOF) as a precursor, and then forms the carbon structure-coated nano composite electrode material by simple calcination, so that the problems existing at present are well overcome, the carbon structure can enhance the conductivity of the electrode material on one hand, and can provide buffer for deformation in reaction on the other hand, so that the bismuth nano composite electrode material prepared by the method has very good cycle stability, and is safely and effectively applied to the field of sodium ion batteries.
However, in the experimental process, it is found that Bi is easily generated in the process of preparing the Bi @ C nano composite electrode material2O3Impurities, thereby affecting the performance of the nanocomposite electrode material in a sodium ion battery. In this connection, further studies have found that Bi is caused2O3The reasons for the generation of impurities are: 1. after the solvothermal reaction, bismuth ions and ligands form a complex structure through coordination bonds, if the solvothermal reaction time is short, the complex cannot be completely formed in the reaction process, and Bi is caused to be completely formed in the later calcining process2O3(iii) occurrence of (a); 2. the calcination is not only intended to pyrolyze the complex, but also to reduce the bismuth ions by the carbon produced to form bismuth simple substance, and if the calcination time is short, the unreduced bismuth ions will be Bi2O3Exist in the form of (1). The invention avoids Bi in the product by setting the solvothermal reaction time and the calcination time2O3Therefore, the MOF-derived Bi @ C nano composite electrode material provided by the invention has the advantage of high cycle stability and has better long-cycle capacity retention rate and rate capability.
In another aspect, a MOF-derived Bi @ C nanocomposite electrode material is obtained by the preparation method.
In a third aspect, the MOF-derived Bi @ C nanocomposite electrode material is applied to a negative electrode of a sodium-ion battery.
In a fourth aspect, a sodium ion battery negative electrode comprises an active material, a binder and a current collector, wherein the binder binds the active material to the current collector, and the active material is the MOF-derived Bi @ C nanocomposite electrode material.
In a fifth aspect, a sodium ion battery includes a positive electrode, an electrolyte, a separator, and the sodium ion battery negative electrode.
The invention has the beneficial effects that:
(1) the method of firstly synthesizing the metal organic framework and then calcining is adopted to effectively combine the carbon structure and the bismuth element, so that the problem of poor bismuth conductivity is solved, and the Bi @ C prepared by the method has better conductivity and cycling stability.
(2) The preparation method disclosed by the invention is simple in preparation process and low in cost, greatly improves the production efficiency, can better meet the requirements of industrial production, realizes large-scale production, and has great application prospects.
(3) The preparation method is simple, high in conductive efficiency, strong in practicability and easy to popularize.
Experiments show that the MOF-derived Bi @ C nanocomposite electrode material provided by the invention has the following beneficial effects as a sodium ion battery cathode material:<1>when the long-cycle test is carried out, the test temperature is 1A g-1The capacity of 500 cycles of the lower cycle is almost unchanged, the charge-discharge efficiency is as high as 100%, and the stability under the long cycle ensures that the material has very high application prospect in the practical application of the sodium-ion battery.<2>The rate capability of the material is particularly excellent, and the capacity is reduced after small current is switched to large current when the rate test is generally carried out in documents on the aspect of negative electrode materials of sodium-ion batteries, but the rate capability test of the material prepared by the invention finds that when the current is from 0.2A g-1Increased up to 60A g-1When the capacity hardly changes, the current reaches 80A g-1At this time, the capacity also only slightly decreased, 80A g-1Is the fastest rate to date for application in sodium ion batteries, even better than graphite anodes in lithium ion batteries, and also has higher capacity than all bismuth based anode materials previously reported.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a scanning electron micrograph of the Bi @ C nanocomposite prepared in example 1;
FIG. 2 is the XRD results of the Bi @ C nanocomposite prepared in example 1;
FIG. 3 is a charge/discharge curve of 1A/g current for a sodium ion battery assembled from the Bi @ C nanocomposite prepared in example 1;
FIG. 4 is the cycling performance of 1A/g current for a sodium ion battery assembled from the Bi @ C nanocomposite prepared in example 1;
figure 5 is the rate performance of a Bi @ C nanocomposite assembled sodium ion battery prepared in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the problems of low retention rate of long-cycle capacity and poor rate performance of the conventional sodium ion battery cathode, the invention provides an MOF-derived Bi @ C nano-composite electrode material and a preparation method thereof.
The invention provides a preparation method of a Bi @ C nano composite electrode material derived from MOF, which comprises the steps of carrying out solvothermal reaction on bismuth salt and a ligand to obtain an MOF precursor, and calcining the MOF precursor in an inert atmosphere to obtain the Bi @ C nano composite electrode material; wherein the solvothermal reaction time is 23-37 h, and the calcining time is 2-4 h.
According to the preparation method, bismuth ions and ligands are combined to form a Metal Organic Framework (MOF) as a precursor, and then the Bi @ C nano composite electrode material is obtained by a simple method of calcining to form a carbon structure-coated nano composite electrode material. Meanwhile, the invention avoids Bi in the product by setting the solvothermal reaction time and the calcination time2O3Therefore, the MOF-derived Bi @ C nano composite electrode material provided by the invention has the advantage of high cycle stability and has better long-cycle capacity retention rate and rate capability.
In some embodiments of this embodiment, the bismuth salt is one of a nitrate, a sulfate, an oxalate, a chloride. Preferably, the bismuth salt is bismuth nitrate or bismuth chloride.
In some embodiments of this embodiment, the ligand is one of 1,3, 5-benzenetricarboxylic acid, terephthalic acid, pyromellitic acid, isophthalic acid, phthalic acid. Preferably, the ligand is 1,3, 5-benzenetricarboxylic acid.
In some examples of this embodiment, the solvent of the solvothermal reaction is a mixture of methanol and N, N-Dimethylformamide (DMF). Preferably, the mass ratio of the methanol to the DMF is 1-5: 1. More preferably, the mass ratio of methanol to DMF is 2-3: 1.
In some examples of this embodiment, the solvothermal reaction is at a temperature of 100 to 180 ℃. Preferably, the temperature of the solvothermal reaction is 118-122 ℃.
In some examples of this embodiment, the solvothermal reaction time is 23.5 to 24.5 hours.
The inert gas atmosphere described in the present invention is, for example, a nitrogen gas atmosphere, a helium gas atmosphere, an argon gas atmosphere, or the like.
In some examples of this embodiment, the calcination temperature is 400 to 1000 ℃. Preferably, the calcination temperature is 500-700 ℃.
The preferred steps of the invention are as follows:
(1) stirring the ligand and bismuth salt in a mixed solution of methanol and N, N-dimethylformamide;
(2) transferring the obtained uniform solution into a reaction kettle, heating, cooling, washing to obtain a product, and drying to obtain an MOF precursor;
(3) and calcining the MOF precursor in inert gas to obtain the Bi @ C nano composite electrode material.
In another embodiment of the invention, a MOF-derived Bi @ C nanocomposite electrode material is provided, which is obtained by the preparation method.
In a third embodiment of the invention, the application of the MOF-derived Bi @ C nanocomposite electrode material in a negative electrode of a sodium-ion battery is provided.
In a fourth embodiment of the invention, a sodium ion battery negative electrode is provided, which comprises an active material, a binder and a current collector, wherein the binder binds the active material to the current collector, and the active material is the MOF-derived Bi @ C nanocomposite electrode material.
In some embodiments of this embodiment, a conductive agent is included. The mass ratio of the active material to the conductive agent to the binder is 8: 0.9-1.1.
In a fifth embodiment of the present invention, a sodium ion battery is provided, which includes a positive electrode, an electrolyte, a separator, and the sodium ion battery negative electrode.
In some examples of this embodiment, the electrolyte solvent is a mixture of any one or more of ethylene glycol dimethyl ether (DME), tetraethylene glycol dimethyl ether (TETRAGLYME), 1, 3-Dioxolane (DOL), Ethylene Carbonate (EC), Propylene Carbonate (PC), dimethyl carbonate (DMC), ethylene carbonate (DEC), diethyl carbonate (EMC), Vinylene Carbonate (VC), ethylene carbonate (VEC), fluoroethylene carbonate (FEC), 1, 3-Propane Sultone (PS), 1, 4-Butane Sultone (BS), 1,3- (1-Propene) Sultone (PST), Ethylene Sulfite (ESI), and Ethylene Sulfate (ESA) with a sodium salt.
In some examples of this embodiment, the sodium salt in the electrolyte is sodium hexafluorophosphate (NaPF)6) Sodium perchlorate (NaClO)4) Sodium trifluoromethanesulfonate (NaSO)3CF3) Any one of them.
In some examples of this embodiment, the positive electrode material is sodium vanadium fluorophosphate, sodium vanadium phosphate, prussian blue, an organic positive electrode material, or the like.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1:
(1) 0.84g of 1.3.5 benzenetricarboxylic acid and 0.97g of bismuth nitrate pentahydrate were weighed, and the weighed sample was added to a mixture of 10 ml of DMF and 20 ml of methanol, and stirred for 20 minutes.
(2) And transferring the uniform solution to a 50 ml reaction kettle, heating at 120 ℃ for 24h, centrifuging, washing and precipitating, and vacuum drying at 80 ℃ for 24h to obtain a precursor.
(3) And calcining the precursor at 600 ℃ for 2h under the argon atmosphere to obtain the Bi @ C nanocomposite.
Scanning Electron Microscope (SEM) analysis of the composite material obtained in example 1 shows that the SEM photograph of the Bi @ C composite material obtained in this example is shown in FIG. 1, and it can be seen from FIG. 1 that the Bi @ C composite material is a rod-shaped structure composed of bismuth spheres and a carbon framework. The XRD spectrum of FIG. 2 has only diffraction peaks of Bi, and Bi is not present2O3The diffraction peak of (especially around 30 degrees) demonstrates the successful preparation of the Bi @ C composite.
Preparing a negative electrode of the Bi @ C composite material sodium ion battery and analyzing electrochemical properties: according to the following steps of 8: 1: 1, mixing the Bi @ C composite material prepared in the example 1, conductive carbon black Super P, a binder PVDF and 1-methyl-2 pyrrolidone in a mass ratio, stirring, then coating the slurry on a current collector copper foil, drying at 60 ℃ to prepare a negative plate, taking a metal sodium plate as a positive electrode, taking polypropylene and glass fiber as diaphragms and taking NaPF6Is sodium salt and DME asAnd (4) assembling the solvent in a glove box filled with argon to obtain the CR2025 type button experimental battery. The first charge-discharge curve of the battery is shown in figure 3, when the battery is used as a negative electrode material of a sodium ion battery, the first discharge specific capacity of the obtained Bi @ C nano composite material is 628.5mAh/g, and the charge specific capacity is 340.3 mAh/g. As shown in FIG. 4, the reversible specific capacity was 319.3mAh/g after 500 cycles at 25 ℃ with a current density of 1A/g. As shown in FIG. 5, the reversible capacity of 311 mAh/g can be still preserved under the high current density of 80A/g, the capacity retention rate is high, the stability is good, and the electrochemical performance is excellent.
Example 2:
(1) 0.84g of 1.3.5 benzenetricarboxylic acid and 0.85g of bismuth chloride were weighed, and the weighed sample was added to a mixture of 5 ml of DMF and 15 ml of methanol, and stirred for 20 minutes.
(2) And pouring the uniform solution into a 50 ml reaction kettle, heating for 24h at 120 ℃, centrifuging, washing and precipitating, and vacuum-drying for 24h at 80 ℃ to obtain a precursor.
(3) And calcining the precursor at 600 ℃ for 2h under the argon atmosphere to obtain the Bi @ C nanocomposite.
Example 3:
(1) 0.84g of 1.3.5 benzenetricarboxylic acid and 1.412g of bismuth sulfate were weighed, and the weighed sample was added to a mixture of 10 ml of DMF and 20 ml of methanol, and stirred for 20 minutes.
(2) And pouring the uniform solution into a 50 ml reaction kettle, heating for 24h at 120 ℃, centrifuging, washing and precipitating, and vacuum-drying for 24h at 80 ℃ to obtain a precursor.
(3) And calcining the precursor at 700 ℃ for 3h under the argon atmosphere to obtain the Bi @ C nanocomposite.
Example 4:
(1) 0.664g of phthalic acid and 0.85g of bismuth chloride were weighed, and the weighed sample was added to a mixture of 10 ml of DMF and 20 ml of methanol, and stirred for 20 minutes.
(2) And pouring the uniform solution into a 50 ml reaction kettle, heating at 120 ℃ for 36h, centrifuging, washing and precipitating, and vacuum drying at 80 ℃ for 24h to obtain a precursor.
(3) And calcining the precursor at 600 ℃ for 2h under the argon atmosphere to obtain the Bi @ C nanocomposite.
Example 5:
(1) 0.664g of phthalic acid and 0.97g of bismuth nitrate pentahydrate were weighed, and the weighed sample was added to a mixture of 10 ml of DMF and 20 ml of methanol, and stirred for 20 minutes.
(2) And pouring the uniform solution into a 50 ml reaction kettle, heating for 24h at 120 ℃, centrifuging, washing and precipitating, and vacuum-drying for 24h at 80 ℃ to obtain a precursor.
(3) And calcining the precursor at 600 ℃ for 2h under the argon atmosphere to obtain the Bi @ C nanocomposite.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (10)
1. A preparation method of a Bi @ C nano-composite electrode material derived from MOF is characterized in that bismuth salt and a ligand are subjected to solvothermal reaction to obtain an MOF precursor, and the MOF precursor is calcined in an inert atmosphere to obtain the Bi @ C nano-composite electrode material; wherein the solvothermal reaction time is 23-37 h, and the calcining time is 2-4 h.
2. The method of making the MOF-derived Bi @ C nanocomposite electrode material of claim 1, wherein the bismuth salt is one of a nitrate, a sulfate, an oxalate, a chloride; preferably, the bismuth salt is bismuth nitrate or bismuth chloride;
or the ligand is one of 1,3, 5-benzene tricarboxylic acid, terephthalic acid, pyromellitic acid, isophthalic acid and phthalic acid; preferably, the ligand is 1,3, 5-benzenetricarboxylic acid;
or the solvent of the solvent thermal reaction is a mixture of methanol and DMF; preferably, the mass ratio of methanol to DMF is 1-5: 1; more preferably, the mass ratio of methanol to DMF is 2-3: 1.
3. The method for preparing the MOF-derived Bi @ C nanocomposite electrode material of claim 1, wherein the temperature of the solvothermal reaction is 100-180 ℃; preferably, the temperature of the solvothermal reaction is 118-122 ℃;
or the solvothermal reaction time is 23.5-24.5 h.
4. The method for preparing the MOF-derived Bi @ C nanocomposite electrode material of claim 1, wherein the calcination temperature is 400-1000 ℃; preferably, the calcination temperature is 500-700 ℃.
5. An MOF-derived Bi @ C nanocomposite electrode material, which is characterized by being obtained by the preparation method of any one of claims 1 to 4.
6. Use of the MOF-derived Bi @ C nanocomposite electrode material of claim 5 in a sodium ion battery negative electrode.
7. A sodium ion battery negative electrode comprising an active material, a binder and a current collector, the binder binding the active material to the current collector, the active material being the MOF derived Bi @ C nanocomposite electrode material of claim 5.
8. The negative electrode of a sodium ion battery of claim 7, comprising a conductive agent; preferably, the mass ratio of the active material to the conductive agent to the binder is 8: 0.9-1.1.
9. A sodium ion battery comprising a positive electrode, an electrolyte, a separator and the negative electrode of the sodium ion battery according to claim 7 or 8.
10. The sodium ion battery of claim 9, wherein the electrolyte solvent is a mixture of sodium salt and any one or more of ethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 1, 3-dioxolane, ethylene carbonate, propylene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate, vinylene carbonate, ethylene carbonate, fluoroethylene carbonate, 1, 3-propane sultone, 1, 4-butane sultone, 1,3- (1-propene) sultone, ethylene sulfite, and ethylene sulfate;
or the sodium salt in the electrolyte is any one of sodium hexafluorophosphate, sodium perchlorate and sodium trifluoromethanesulfonate;
or the positive electrode material is sodium vanadium fluorophosphate, sodium vanadium phosphate, Prussian blue or an organic positive electrode material.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114122407A (en) * | 2022-01-27 | 2022-03-01 | 暨南大学 | Preparation method and application of bi-carbon layer-protected bismuth nanoparticle composite material |
| CN114335484A (en) * | 2022-01-05 | 2022-04-12 | 徐州博磊达新能源科技有限公司 | Negative electrode composite material for alkali metal ion battery, preparation method of negative electrode composite material and alkali metal ion battery |
| CN114335497A (en) * | 2022-01-05 | 2022-04-12 | 中山大学 | High-performance bismuth-carbon negative electrode material and preparation method and application thereof |
| CN114405499A (en) * | 2022-02-14 | 2022-04-29 | 辽宁石油化工大学 | Bismuth oxide and preparation method and application thereof |
| CN114551828A (en) * | 2022-01-28 | 2022-05-27 | 同济大学 | Bi-MOF derived bismuth oxide-based negative electrode material and preparation and application thereof |
| CN114588907A (en) * | 2022-02-28 | 2022-06-07 | 五邑大学 | Catalyst and preparation method and application thereof |
| CN114672831A (en) * | 2022-04-29 | 2022-06-28 | 华中科技大学 | Two-dimensional bismuth nanosheet material with atomic-scale thickness and preparation method and application thereof |
| CN114778636A (en) * | 2022-04-26 | 2022-07-22 | 昆明理工大学 | Preparation method of composite electrode for simultaneously measuring hydroquinone and catechol |
| CN115196674A (en) * | 2022-07-06 | 2022-10-18 | 广州大学 | Battery electrode composite material and preparation method and application thereof |
| CN116573607A (en) * | 2023-05-05 | 2023-08-11 | 长春理工大学 | Hydrogen storage material and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601756A (en) * | 2013-11-06 | 2014-02-26 | 江苏华富储能新技术股份有限公司 | Bismuth metal organic framework material, preparation method and lead storage battery anode additives thereof |
| CN109888206A (en) * | 2019-01-23 | 2019-06-14 | 江苏理工学院 | A kind of lithium ion battery negative material Bi/Bi2O3/ C and its preparation and application |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN111732147A (en) * | 2020-06-23 | 2020-10-02 | 东莞理工学院 | Method for treating phosphate in water body by using Bi-MOF-polymer compound |
| CN111729662A (en) * | 2020-06-23 | 2020-10-02 | 东莞理工学院 | Preparation method and application of MXene membrane material for in-situ growth of Bi-MOF |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN113130873A (en) * | 2021-05-20 | 2021-07-16 | 武汉科技大学 | Porous bismuth-carbon material, preparation method and application thereof |
-
2021
- 2021-08-12 CN CN202110926378.4A patent/CN113839038A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103601756A (en) * | 2013-11-06 | 2014-02-26 | 江苏华富储能新技术股份有限公司 | Bismuth metal organic framework material, preparation method and lead storage battery anode additives thereof |
| CN109888206A (en) * | 2019-01-23 | 2019-06-14 | 江苏理工学院 | A kind of lithium ion battery negative material Bi/Bi2O3/ C and its preparation and application |
| CN110048099A (en) * | 2019-03-28 | 2019-07-23 | 天津大学 | Electrode material of sodium-ion battery and its preparation method and application |
| CN111732147A (en) * | 2020-06-23 | 2020-10-02 | 东莞理工学院 | Method for treating phosphate in water body by using Bi-MOF-polymer compound |
| CN111729662A (en) * | 2020-06-23 | 2020-10-02 | 东莞理工学院 | Preparation method and application of MXene membrane material for in-situ growth of Bi-MOF |
| CN111769272A (en) * | 2020-07-28 | 2020-10-13 | 广西师范大学 | Bi @ C hollow nanosphere composite material and preparation method and application thereof |
| CN113130873A (en) * | 2021-05-20 | 2021-07-16 | 武汉科技大学 | Porous bismuth-carbon material, preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| MIN-KUN KIM 等: "Bi-MOF derived micro/meso-porous Bi@C nanoplates for high performance lithium-ion batteries" * |
| SAILAN SU 等: "Control of SEI Formation for Stable Potassium-Ion Battery Anodes by Bi-MOF-Derived Nanocomposites", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| 张琰 等: "金属有机框架衍生的Bi/C复合材料作为钠离子电池负极材料的研究", 《金属功能材料》 * |
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|---|---|---|---|---|
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| CN114335497A (en) * | 2022-01-05 | 2022-04-12 | 中山大学 | High-performance bismuth-carbon negative electrode material and preparation method and application thereof |
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