CN114094062B - Preparation method and application of high-performance lithium and sodium storage material for synthesizing tin dioxide nanoparticle composite graphene with assistance of oxalic acid - Google Patents
Preparation method and application of high-performance lithium and sodium storage material for synthesizing tin dioxide nanoparticle composite graphene with assistance of oxalic acid Download PDFInfo
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- CN114094062B CN114094062B CN202111177997.4A CN202111177997A CN114094062B CN 114094062 B CN114094062 B CN 114094062B CN 202111177997 A CN202111177997 A CN 202111177997A CN 114094062 B CN114094062 B CN 114094062B
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- tin dioxide
- oxalic acid
- tin
- storage material
- acid
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 206
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 82
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 235000006408 oxalic acid Nutrition 0.000 title claims abstract description 55
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- 239000011734 sodium Substances 0.000 title claims abstract description 50
- 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 title claims abstract description 47
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 47
- 239000011232 storage material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 24
- 150000007524 organic acids Chemical class 0.000 claims abstract description 6
- 239000007773 negative electrode material Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 239000010405 anode material Substances 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 10
- 238000003786 synthesis reaction Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910001415 sodium ion Inorganic materials 0.000 claims description 9
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 6
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 6
- -1 small molecule organic acid Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-UHFFFAOYSA-N D-OH-Asp Natural products OC(=O)C(N)CC(O)=O CKLJMWTZIZZHCS-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-UWTATZPHSA-N L-Aspartic acid Natural products OC(=O)[C@H](N)CC(O)=O CKLJMWTZIZZHCS-UWTATZPHSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- 229960005261 aspartic acid Drugs 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- PNOXNTGLSKTMQO-UHFFFAOYSA-L diacetyloxytin Chemical compound CC(=O)O[Sn]OC(C)=O PNOXNTGLSKTMQO-UHFFFAOYSA-L 0.000 claims description 3
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 3
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N malic acid Chemical compound OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 3
- 229960004889 salicylic acid Drugs 0.000 claims description 3
- 239000000661 sodium alginate Substances 0.000 claims description 3
- 235000010413 sodium alginate Nutrition 0.000 claims description 3
- 229940005550 sodium alginate Drugs 0.000 claims description 3
- 229940079864 sodium stannate Drugs 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 claims description 3
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 14
- 229910006404 SnO 2 Inorganic materials 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 9
- GZNAASVAJNXPPW-UHFFFAOYSA-M tin(4+) chloride dihydrate Chemical compound O.O.[Cl-].[Sn+4] GZNAASVAJNXPPW-UHFFFAOYSA-M 0.000 abstract description 6
- FWPIDFUJEMBDLS-UHFFFAOYSA-L tin(II) chloride dihydrate Substances O.O.Cl[Sn]Cl FWPIDFUJEMBDLS-UHFFFAOYSA-L 0.000 abstract description 6
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 5
- 239000012716 precipitator Substances 0.000 abstract description 3
- 238000010298 pulverizing process Methods 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 239000012798 spherical particle Substances 0.000 abstract description 3
- 238000003860 storage Methods 0.000 description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 12
- 230000001351 cycling effect Effects 0.000 description 8
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 238000013112 stability test Methods 0.000 description 5
- 238000001027 hydrothermal synthesis Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229960004106 citric acid Drugs 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 230000000670 limiting effect Effects 0.000 description 2
- 229910052751 metal Chemical class 0.000 description 2
- 239000002184 metal Chemical class 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 1
- 229940012189 methyl orange Drugs 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011206 ternary composite Substances 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- 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
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method and application of a high-performance lithium and sodium storage material for synthesizing tin dioxide nano-particle composite graphene by oxalic acid. The invention adopts a simple one-step solvothermal method to synthesize spherical particle aggregate tin dioxide of about 30 nanometers by taking tin (II) chloride dihydrate, small molecular organic acid and oxalic acid as raw materials, and the material uses oxalic acid as a precipitator and utilizes the conversion process of tin oxalate micron rods to tin dioxide nano particles to obtain SnO 2 Nanoparticles, which are spherical nanoparticles. Then SnO is added 2 The nano particles are compounded with the conductive graphene, the nanoscale tin dioxide particles are uniformly wrapped in the graphene oxide, so that pulverization and falling of the material caused by volume expansion of the material in a circulation process are relieved, meanwhile, the conductivity of the material is improved, and the high capacity and high circulation stability of the high-performance lithium and sodium storage material of the tin dioxide nano particle-graphene composite are realized.
Description
Technical Field
The invention belongs to the technical field of battery materials, and particularly relates to a preparation method and application of a high-performance lithium and sodium storage material for synthesizing tin dioxide nano-particle composite graphene by oxalic acid.
Background
The Lithium Ion Battery (LIB) has the advantages of high energy density, long cycle life, environmental friendliness and the like, and plays a leading role in a wide application field. However, the theoretical capacity of LIB commercial graphite negative electrode is only 372 mAh g -1 In order to further remarkably improve the energy density of the LIB, a novel lithium storage anode material with high performance is actively explored. Furthermore, the scarcity of lithium resources in the crust results in high costs of LIB, which limits its widespread use in smart grids and large-scale energy storage systems. Thus, sodium Ion Batteries (SIB) are widely studied because of their similar principles of operation as LIB, while sodium has abundant resources and lower prices. However, the radius of sodium ions is larger than that of lithium ions, so that the commercialized LIB negative electrode graphite cannot be directly used for SIB, and no known SIB negative electrode material capable of being produced in large quantities and commercialized exists at present, so that development of an inexpensive and commercialized SIB negative electrode material is urgent.
Tin dioxide (SnO) 2 ) Due to the relatively high theoretical reversible capacity of storing lithium and sodium (lithium storing capacity 1494 mAh g -1 Sodium storage capacity 1378 mAh g -1 ) The advantages of low cost, high abundance, easy synthesis, high safety and the like are paid attention to. Tin dioxide is known as LIBs cathode material, having a medium lithiation potential (. Apprxeq.1.0V vs Li/Li) + ) And store Li through two reaction processes + In a first conversion reaction (SnO 2 + 4Li + +4e-↔Sn + 2Li 2 O) produces 711 mAh g -1 Is subjected to a second alloying reaction (Sn+4.4Li) + +4.4e-↔Li 4.4 Sn) contributed 783 mAh g -1 Is a function of the capacity of the battery. Tin dioxide as SIBs negative electrode material stores Na through two reaction processes + In a first conversion reaction (SnO 2 +4Na + + 4e - ↔Sn + 2Na 2 O) produces 711 mAh g -1 Is carried out in the second alloying step (Sn+3.75Na) + + 3.75e - ↔Na 3.75 Sn（Na 15 Sn 4 ) 667 mAh g is contributed to -1 Is a function of the capacity of the battery. However, snO is realized 2 The high lithium and sodium storage performance of (a) is hindered by two major problems. The first is SnO in the intercalation and deintercalation process of lithium sodium 2 The large volume change of the particles causes pulverization of the electrodes and loss of electrical contact, resulting in a rapid decrease in capacity. The second key problem is that during cycling, metallic Sn particles coarsen continuously, leading to a progressive decay in the reversibility of the electrochemical reaction, leading to a gradual decrease in capacity. These factors severely limit SnO 2 Practical application in LIBs and SIBs.
An effective improvement strategy is to anchor nanoscale tin dioxide particles in a conductive carbon matrix. Reducing the size of tin dioxide can achieve high reactivity to increase capacity, anchoring in the conductive carbon material matrix can increase conductivity and inhibit coarsening of metallic tin particles to increase cycling stability. Graphene is considered one of the most effective conductive carbon matrices because it has a unique two-dimensional structure, a high specific surface area, excellent conductivity, and a unique surface electronic structure.
Therefore, in order to further improve the electrochemical performance of the tin dioxide lithium-sodium storage anode, it is particularly critical to explore and prepare nanoscale tin dioxide.
The Chinese patent of patent No. 201910784530.2 discloses that tin salt and metal salt are used as raw materials, a tin dioxide/metal simple substance/graphene ternary composite material is obtained by a one-pot method in an electrostatic adsorption mode as a lithium battery anode material, and after 200 times of circulation under the current density of 0.1A/g, the specific capacity is 891 mAh g -1 ；
The Chinese patent of patent No. 201410737538.0 discloses that hollow tin dioxide and graphene oxide prepared by hydrothermal method are used as raw materials, and the graphene coiled hollow tin dioxide composite material is obtained by cold quenching, freeze drying and reduction under inert atmosphere conditions and is used as a lithium battery anode material, wherein the specific discharge capacity after 50 cycles is 1156 mAh/g at a charge and discharge rate of 100 mA/g, and the specific discharge capacities are respectively as follows at charge and discharge rates of 200 mA/g, 500 mA/g, 1A/g, 1A/g, 2A/g and 5A/g: 954. 762, 610, 490, 395 mAh/g.
The Chinese patent of patent number 202110542148.8 discloses that a carbon-coated tin dioxide material is synthesized by a hydrothermal method by taking tin salt, urea and an organic carbon source as raw materials to serve as a sodium-electricity negative electrode material, and the initial charge-discharge specific capacity is 603 mAh/g under the current density of 0.1A/g. Linlin Fan et al synthesized amorphous SnO by hydrothermal method using tin (II) chloride dihydrate, graphene oxide and ethylene glycol as raw materials 2 Graphene aerogel (a-SnO) 2 GA) nanocomposite as a sodium electrical negative electrode material at 50 mA g -1 The capacity after 100 times of circulation at the current density is 380.2 mAh g -1 （Adv. Energy Mater. 2016, 6, 1502057）；
Fanghua Tian et al prepared from polyvinylpyrrolidone, tin (II) chloride dihydrate and N, N-dimethylformamidePreparation of SnO by using amide as raw material and electrostatic spinning method 2 When the Carbon nanowire is used as a lithium battery anode material, the temperature is 100 mA g -1 The capacity after 50 cycles at the current density is 680 mAh g -1 （Materials Letters 284 (2021) 129019）；
The quick Nhat Tran et al prepared SnO from nanocrystalline cellulose (CNC), tin (II) chloride dihydrate and sodium citrate dihydrate by hydrothermal method and annealing technique 2 Nanoflower used as active LIB negative electrode material at 100 mA g -1 The initial reversible capacity at current density of (3) is 891 mAh g -1 （Materials 2020, 13, 3165）；
The Xianfeng Du et al uses methyl orange, ferric (III) chloride hexahydrate, pyrrole, ethylene glycol, tin (II) chloride dihydrate, polyvinylidene fluoride and N-methyl-2-pyrrolidone as raw materials by using mesoporous SnO 2 Anchored to strong polypyrrole nanotubes to produce nanostructured SnO 2 The composite material is used as LIB negative electrode material, and the concentration of the LIB negative electrode material is 2000 mA g -1 Has about 770 mAh g at current density -1 Specific capacity of 200 mA g -1 Under the current density, the capacity after 200 times of charge and discharge is about 790 mAh g -1 （ACS Appl. Mater. Interfaces 2016, 8, 15598−15606）；
Xinxin Chen to K 2 SnO 3 ·3H 2 O, urea, ethanol and deionized water are used as raw materials to prepare SnO first 2 Nanospheres, and Graphene Oxide (GO), vitamin C and SnO 2 Reduced graphene oxide and SnO are prepared in the solution of (1) 2 The nanosphere composite material is used as LIB negative electrode material and is 1000 mA g -1 The capacity after 100 cycles at current density is 400 mAh g -1 As an SIB negative electrode material, at 100 mA g -1 The capacity after 100 cycles at current density was 212 mAh g -1 （ChemistrySelect 2021, 6, 3192–3198）；
The tin dioxide particles synthesized by the conventional method have complex operation and unsatisfactory performance.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings in the prior art and provides a preparation method and application of a high-performance lithium and sodium storage material for synthesizing tin dioxide nano-particle composite graphene by oxalic acid.
The technical scheme adopted by the invention is as follows: a preparation method of a high-performance lithium and sodium storage material for synthesizing tin dioxide nano-particle composite graphene by oxalic acid assistance comprises the following steps:
s1: adding soluble tin salt and small molecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B to obtain a solution C;
s3: heating the solution C to 60-200 ℃ in a closed space for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nano particles;
s4: dispersing the tin dioxide nano-particles and graphene oxide in water, ball-milling, and removing liquid to obtain a tin dioxide nano-particle composite graphene high-performance lithium and sodium storage material;
the organic solvent is ethanol, glycol or glycerol.
The soluble tin-containing compound is sodium stannate, potassium stannate, tin sulfate, stannous chloride, stannous acetate or stannic chloride.
The small molecule organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid or L-aspartic acid.
The graphene is prepared by an optimized Hummers method.
The ratio of the tin dioxide nano particles to the graphene oxide is 4-8:1.
The preparation method of the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material prepared by the preparation method of the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material assisted by oxalic acid.
The negative electrode material containing the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material.
The preparation method comprises the following steps: weighing oxalic acid-assisted synthesized tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
A lithium ion battery comprising the negative electrode material as described above.
A sodium ion battery comprising the negative electrode material as described above.
The beneficial effects of the invention are as follows: according to the invention, the tin oxide nanoparticle composite graphene prepared by utilizing the solution heat reaction of converting tin oxalate into tin oxide nanoparticles, which is initiated by precipitator oxalic acid, through regulating and controlling the morphology of the tin oxide by small molecular organic acid, and then uniformly compounding the tin oxide nanoparticles with graphene through ball milling shows excellent lithium and sodium storage performance. The added small-molecule organic acid, organic solvent and precipitant can regulate the shape of the tin dioxide to a certain extent, and the existence of oxalic acid can lead to the generation of unique conversion from tin oxalate micron rods to tin dioxide nano-particles in solvothermal reaction, so that the small-molecule organic acid can be adsorbed on the surfaces of the tin dioxide nano-particles to play a stabilizing role, and can stabilize small crystal areas. And then, uniformly compounding the synthesized tin dioxide nano particles with a graphene conductive matrix, improving conductivity, relieving volume expansion effect and inhibiting coarsening of tin particles, and being used as a negative electrode material of a lithium ion battery and a sodium ion battery, the composite material has high specific capacity and long cycle life, and realizes high lithium and sodium storage performance.
In some embodiments of the invention, the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material is prepared into a LIB negative electrode at 100 mA g -1 The capacity of the current after 50 times of circulation is up to 1378 mAh g -1 At 1000 mA g -1 The capacity of the current reaches 1739 mAh g after 500 times of circulation -1 The method comprises the steps of carrying out a first treatment on the surface of the Preparing a tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material into an SIB negative electrode and SnO 2 GO nanocomposite at 50 mA g -1 The capacity of the current reaches 485 mAh g after 60 times of circulation -1 At 200 mA g -1 The capacity of the capacitor is kept to be 337 mAh g after 100 times of circulation under current -1 . The performance is significantly higher than the results reported in the prior art patents and published articles.
The invention adopts a simple one-step solvothermal method to synthesize spherical particle aggregate tin dioxide of about 30 nanometers by taking tin (II) chloride dihydrate, small molecular organic acid and oxalic acid as raw materials, and the material uses oxalic acid as a precipitator and utilizes the conversion process of tin oxalate micron rods to tin dioxide nano particles to obtain SnO 2 Nanoparticles, which are spherical nanoparticles. Then SnO is added 2 The nano particles are compounded with the conductive graphene, the nanoscale tin dioxide particles are uniformly wrapped in the graphene oxide, so that pulverization and falling of the material caused by volume expansion of the material in a circulation process are relieved, meanwhile, the conductivity of the material is improved, and the high capacity and high circulation stability of the high-performance lithium and sodium storage material of the tin dioxide nano particle-graphene composite are realized. The invention firstly provides the method for converting the tin oxalate micro rod into the tin dioxide nano particle, thereby providing higher capacity and better cycle stability for lithium ion batteries and sodium ion batteries.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a Scanning Electron Microscope (SEM) image (a, c), a Transmission Electron Microscope (TEM) image (b, d) and an X-ray diffraction pattern (XRD) (e) of the tin dioxide particles prepared in example 1;
fig. 2 is a Scanning Electron Microscope (SEM) image (a, b) and a Transmission Electron Microscope (TEM) image (c, d) of the tin dioxide particle composite graphene prepared in example 1;
FIG. 3 is a graph (a, b, e) showing the cyclic stability test of the tin dioxide particle composite graphene lithium storage anode material prepared in example 1 at 100 mA g-1, 1000 mA g-1 and current densities of different multiplying powers, and a graph (c, d) showing the charge and discharge curves of the tin dioxide particle composite graphene lithium storage anode material at 1000 mA g-1;
FIG. 4 is a graph (a, b) showing the cyclic stability test of the tin dioxide particle composite graphene sodium storage anode material prepared in example 1 at current densities of 50 mA g-1 and 200 mA g-1 and a graph (c, d) showing the charge-discharge curve test at current densities of 50 mA g-1;
FIG. 5 is a graph of 1000 mA g of tin dioxide nanoparticle composite graphene synthesized by increasing oxalic acid amount in example 2 as a negative electrode of a lithium ion battery -1 Cycling stability test plot at current density.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
It should be noted that, in the embodiments of the present invention, all the expressions "first" and "second" are used to distinguish two entities with the same name but different entities or different parameters, and it is noted that the "first" and "second" are only used for convenience of expression, and should not be construed as limiting the embodiments of the present invention, and the following embodiments are not described one by one.
The terms of direction and position in the present invention, such as "up", "down", "front", "back", "left", "right", "inside", "outside", "top", "bottom", "side", etc., refer only to the direction or position of the drawing. Accordingly, directional and positional terms are used to illustrate and understand the invention and are not intended to limit the scope of the invention.
The invention provides a preparation method of a high-performance lithium and sodium storage material for synthesizing tin dioxide nano-particle composite graphene by oxalic acid assistance, which comprises the following steps:
s1: adding soluble tin salt and small molecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B to obtain a solution C;
s3: heating the solution C to 60-200 ℃ in a closed space for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nano particles;
s4: dispersing the tin dioxide nano-particles and graphene oxide in water, ball-milling, and removing liquid to obtain a tin dioxide nano-particle composite graphene high-performance lithium and sodium storage material;
the organic solvent is ethanol, glycol or glycerol.
In some embodiments of the invention, the soluble tin-containing compound is sodium stannate, potassium stannate, tin sulfate, stannous chloride, stannous acetate, or stannic chloride.
In some embodiments of the invention, the small molecule organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid, or L-aspartic acid.
In some embodiments of the invention, the solution C is sealed in a reaction kettle and placed in an oven at 60-200 ℃ for reaction, preferably at 100-190 ℃. In some embodiments of the invention, the reaction time is specifically 15-20 hours. In some embodiments of the present invention, the product of step S3 is washed 3 times with water and ethanol, respectively, and then dried in an oven at 80 ℃.
In some embodiments of the present invention, the product tin dioxide nanoparticles and graphene oxide are dispersed in water, transferred to a 50 ml zirconia ball milling tank, added with 300 zirconia balls with a diameter of 5mm, and ball milled for 6 hours under the condition of 1200 revolutions per minute of a motor of a swing ball mill.
In some embodiments of the invention, the graphene is prepared by an optimized Hummers method.
In some embodiments of the invention, the ratio of tin dioxide nanoparticles to graphene oxide is 4-8:1.
The preparation method of the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material prepared by the preparation method of the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material assisted by oxalic acid.
The negative electrode material containing the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material.
In some embodiments of the invention, the method of making the same comprises the steps of: weighing oxalic acid-assisted synthesized tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
A lithium ion battery comprising the negative electrode material as described above.
A sodium ion battery comprising the negative electrode material as described above.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation method of the high-performance lithium and sodium storage material for synthesizing the tin dioxide nanoparticle composite graphene by oxalic acid assistance comprises the following steps:
s1: 1mmoLSnCl is weighed in a reaction kettle 2 ·2H 2 5mL of ultrapure water is added into O and 1mmol of tartaric acid, ultrasonic mixing is carried out uniformly, 25mL of ethylene glycol is added, and the mixture is transferred to a magnetic stirrer at a certain temperature to be stirred for a period of time, so as to obtain solution A. 3mmol of oxalic acid was weighed in a beaker, 10mL of ultrapure water was added, and the mixture was mixed uniformly by ultrasonic to obtain a solution B.
S2: dropwise adding the solution B into the solution A, magnetically stirring for 10 minutes, and uniformly mixing to obtain a solution C. And (3) sealing the solution C in the reaction kettle, and putting the solution C in a 180 ℃ oven for reaction for 20 hours. After the reaction is finished, the reaction kettle is quickly cooled to room temperature. And centrifuging all the solutions, cleaning the products with water and ethanol for 3 times, and then drying the products in an oven at 80 ℃ for 8 hours to obtain powdery products, namely the tin dioxide nano particles.
S3: mixing the product tin dioxide nano particles with graphene oxide according to a ratio of 4:1 into 30 ml of water, transferring the mixture to a 50 ml zirconia ball milling tank, adding 300 zirconia balls with the diameter of 5mm, ball milling the mixture for 6 hours under the condition that the motor revolution of a swinging ball mill is 1200 r/min, and stirring and evaporating the dispersion liquid in an oil bath at 80 ℃ to obtain the oxalic acid-assisted synthesized tin dioxide nano particle composite graphene high-performance lithium and sodium storage material.
In order to prove the high lithium and sodium storage performance of the oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphite, in the step S1 of the embodiment 1, 3mmol of oxalic acid is not added, and the oxalic acid-assisted-free tin dioxide nanoparticle composite graphene is comparatively synthesized.
Example 2
The preparation method of the high-performance lithium and sodium storage material for synthesizing the tin dioxide nanoparticle composite graphene by oxalic acid assistance comprises the following steps:
s1: 1mmoLSnCl is weighed in a reaction kettle 2 ·2H 2 5mL of ultrapure water is added into O and 1mmol of ascorbic acid, ultrasonic mixing is carried out uniformly, 25mL of glycerol is added, and the mixture is transferred to a magnetic stirrer at a certain temperature to be stirred for a period of time, so as to obtain solution A. 5mmol of oxalic acid was weighed in a beaker, 10mL of ultrapure water was added, and the mixture was mixed uniformly by ultrasonic to obtain a solution B.
S2: dropwise adding the solution B into the solution A, magnetically stirring for 10 minutes, and uniformly mixing to obtain a solution C. And (3) sealing the solution C in the reaction kettle, and putting the solution C in a 160 ℃ oven for reaction for 15 hours. After the reaction is finished, the reaction kettle is quickly cooled to room temperature. And centrifuging all the solutions, cleaning the products with water and ethanol for 3 times, and then drying the products in an oven at 80 ℃ for 8 hours to obtain powdery products, namely the tin dioxide nano particles.
S3: mixing the product tin dioxide nano particles with graphene oxide according to a ratio of 8:1 into 30 ml of water, transferring the mixture to a 50 ml zirconia ball milling tank, adding 300 zirconia balls with the diameter of 5mm, ball milling the mixture for 6 hours under the condition that the motor revolution of a swinging ball mill is 1200 r/min, and stirring and evaporating the dispersion liquid in an oil bath at 80 ℃ to obtain the oxalic acid-assisted synthesized tin dioxide nano particle composite graphene high-performance lithium and sodium storage material.
Microcosmic characterization
The following are microscopic characterizations of different means for oxalic acid-assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage materials:
FIG. 1 is SEM (a) and TEM (b) graphs of tin dioxide nanoparticles synthesized with the assistance of oxalic acid in example 1; SEM images (c) and TEM images (d) of tin dioxide particles synthesized without oxalic acid; x-ray diffraction patterns (XRD) contrast of oxalic acid-assisted synthesized tin dioxide nanoparticles and tin dioxide particles synthesized without oxalic acid. The comparison between SEM and TEM shows that the size of the tin dioxide nano particles synthesized by oxalic acid in the embodiment 1 is about 20-30 nm, the morphology is an aggregate of spherical particles, and the size is relatively uniform; the size of the tin dioxide particles prepared without oxalic acid is larger, the morphology is various, and the size is non-uniform. By XRD it can be seen that both materials synthesized in example 1 are tin dioxide.
Fig. 2 is SEM images (a) and TEM images (b) of tin dioxide nanoparticle composite graphene synthesized with the assistance of oxalic acid in example 1; the SEM image (c) and the TEM image (d) of the tin dioxide particle composite graphene synthesized by not adding oxalic acid can be compared, so that the effect of the tin dioxide nanoparticle composite graphene synthesized by the oxalic acid is better, and the tin dioxide nanoparticles are uniformly dispersed in the graphene.
The product morphology of example 2 is more similar to that of example 1.
Characterization of electrochemical Performance
FIG. 3 shows the use of oxalic acid-assisted synthesized tin dioxide nanoparticle composite graphene and oxalic acid-free synthesized tin dioxide nanoparticle composite graphene as a negative electrode of a lithium ion battery at 100 mA g in example 1 -1 Graph (a), 1000 mA g -1 Graph (b) and graph (e) for testing the cyclic stability at current densities of different multiplying power and 1000 mA g -1 And (c) and (d) are charge-discharge curve test diagrams under the current density. As can be seen by comparing the cycle stability performance graphs, the oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphene lithium storage anode material in the embodiment 1 is 100 mA g -1 At the current density of the current flow,after 50 circles, the capacity is 1378 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1000 mA g -1 At current density, after cycling to 500 circles, the capacity rises to 1739 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At different multiplying powers, at 2000 mA g -1 The capacity under the current condition is as high as 1037 mAh g -1 . Example 1 preparation of tin dioxide nanoparticles without oxalic acid composite graphene lithium storage anode material at 100 mA g -1 At a current density, the capacity after 50 cycles was 533 mA g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 1000 mA g -1 At current density, after circulation to 500 circles, the capacity is 365 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At different multiplying powers, at 2000 mA g -1 The capacity is only 500 mAh g under the current condition -1 . The oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material is good in cycling stability and high in capacity when used as a negative electrode of a lithium ion battery.
FIG. 4 shows the use of oxalic acid-assisted synthesized tin dioxide nanoparticle composite graphene and oxalic acid-free synthesized tin dioxide nanoparticle composite graphene as a negative electrode of a sodium ion battery at 50 mA g in example 1 -1 Graph (a) and 200 mA g -1 Graph (b) cycle stability test at 50 mA g -1 And (c) and (d) are charge-discharge curve test diagrams under the current density. As can be seen by comparing the cycling stability performance graphs, the oxalic acid-assisted synthesis of the tin dioxide nanoparticle composite graphene sodium storage anode material of the embodiment 1 is in a range of 50 mA g -1 At current density, the first discharge capacity was 1151.8 mAh g -1 The capacity after being circulated to 60 circles is 485 mAh g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 200 mA g -1 At current density, the first discharge capacity was 1216.2 mAh g -1 The capacity after 100 circles is 337 mAh g -1 . Example 1 preparation of tin dioxide nanoparticles without oxalic acid composite graphene sodium storage negative electrode material at 50 mA g -1 At current density, the first discharge capacity was 571.5 mAh g -1 The capacity after being circulated to 60 circles is 293 mA g -1 The method comprises the steps of carrying out a first treatment on the surface of the At 200 mA g -1 At current density, the first discharge capacity was 646.7 mAh g -1 The capacity after being circulated to 100 circles is 254 mA g -1 . Illustrating high-performance lithium and sodium storage material for synthesizing tin dioxide nano particle composite graphene by oxalic acid assistanceThe cycling stability of the cathode of the sodium ion battery is also good, and the capacity is also high.
FIG. 5 is a graph of 1000 mA g of tin dioxide nanoparticle composite graphene synthesized by increasing oxalic acid amount in example 2 as a negative electrode of a lithium ion battery -1 Cycling stability test plot at current density. As can be seen, after 500 cycles, the capacity increased to 1307 mAh g -1 . The invention also discloses a method for preparing the tin dioxide nano particles with good performance by fine tuning experiments.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The preparation method of the high-performance lithium and sodium storage material for synthesizing the tin dioxide nanoparticle composite graphene by oxalic acid is characterized by comprising the following steps of:
s1: adding soluble tin salt and small molecular organic acid into ultrapure water, uniformly mixing, adding an organic solvent, and uniformly stirring to obtain a solution A; adding oxalic acid into ultrapure water to obtain a solution B;
s2: dropwise adding the solution B into the solution A, and stirring to uniformly mix the solution B to obtain a solution C;
s3: heating the solution C to 60-200 ℃ in a closed space for reaction, cooling to room temperature after the reaction is finished, centrifuging, washing and drying to obtain tin dioxide nano particles;
s4: dispersing the tin dioxide nano-particles and graphene oxide in water, ball-milling, and removing liquid to obtain a tin dioxide nano-particle composite graphene high-performance lithium and sodium storage material;
the organic solvent is ethanol, glycol or glycerol;
the small molecule organic acid is salicylic acid, DL-malic acid, ascorbic acid, malonic acid, citric acid or L-aspartic acid.
2. The method for preparing the oxalic acid-assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, which is disclosed in claim 1, is characterized by comprising the following steps: the soluble tin-containing compound is sodium stannate, potassium stannate, tin sulfate, stannous chloride, stannous acetate or stannic chloride.
3. The method for preparing the oxalic acid-assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, which is disclosed in claim 1, is characterized by comprising the following steps: the graphene is prepared by an optimized Hummers method.
4. The method for preparing the oxalic acid-assisted synthesis of tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, which is disclosed in claim 1, is characterized by comprising the following steps: the ratio of the tin dioxide nano particles to the graphene oxide is 4-8:1.
5. The method for preparing the oxalic acid-assisted synthesis tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material according to any one of claims 1-4.
6. A negative electrode material containing the tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material according to claim 5.
7. The anode material according to claim 6, characterized in that the preparation method thereof comprises the steps of: weighing oxalic acid-assisted synthesized tin dioxide nanoparticle composite graphene high-performance lithium and sodium storage material, acetylene black and sodium alginate, uniformly mixing, adding a solvent, stirring into paste, and coating on a current collector.
8. A lithium ion battery comprising the negative electrode material of claim 6.
9. A sodium ion battery comprising the negative electrode material of claim 6.
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