CN114512646A - Amorphous carbon material with multilayer gradient microstructure and preparation method and application thereof - Google Patents
Amorphous carbon material with multilayer gradient microstructure and preparation method and application thereof Download PDFInfo
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- CN114512646A CN114512646A CN202210079542.7A CN202210079542A CN114512646A CN 114512646 A CN114512646 A CN 114512646A CN 202210079542 A CN202210079542 A CN 202210079542A CN 114512646 A CN114512646 A CN 114512646A
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- Prior art keywords
- sodium
- metal
- amorphous carbon
- carbon material
- acid
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- 239000002194 amorphous carbon material Substances 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000003860 storage Methods 0.000 claims abstract description 37
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 34
- 229910052755 nonmetal Inorganic materials 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- GWBWGPRZOYDADH-UHFFFAOYSA-N [C].[Na] Chemical compound [C].[Na] GWBWGPRZOYDADH-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000007704 transition Effects 0.000 claims abstract description 11
- 239000007772 electrode material Substances 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 25
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002131 composite material Substances 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000011777 magnesium Substances 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- -1 polytetrafluoroethylene Polymers 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229960001031 glucose Drugs 0.000 claims description 11
- 150000002736 metal compounds Chemical class 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 239000002019 doping agent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- 239000008103 glucose Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 7
- 239000004094 surface-active agent Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 238000000197 pyrolysis Methods 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002671 adjuvant Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229920005610 lignin Polymers 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 229920001568 phenolic resin Polymers 0.000 claims description 4
- 239000005011 phenolic resin Substances 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- 229920001661 Chitosan Polymers 0.000 claims description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- 239000011280 coal tar Substances 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- 229960000355 copper sulfate Drugs 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 229940032296 ferric chloride Drugs 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- 229960002337 magnesium chloride Drugs 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229940068041 phytic acid Drugs 0.000 claims description 3
- 235000002949 phytic acid Nutrition 0.000 claims description 3
- 239000000467 phytic acid Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 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
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 2
- 239000004327 boric acid Substances 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 239000011295 pitch Substances 0.000 claims description 2
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- 239000011701 zinc Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 32
- 239000011734 sodium Substances 0.000 abstract description 14
- 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 abstract description 11
- 229910052708 sodium Inorganic materials 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 6
- 150000002500 ions Chemical class 0.000 abstract description 6
- 239000010410 layer Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 39
- 239000011572 manganese Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
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- 125000004437 phosphorous atom Chemical group 0.000 description 4
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
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- 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 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
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- 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
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Abstract
The invention relates to an amorphous carbon material with a multilayer gradient microstructure, and a preparation method and application thereof, and belongs to the technical field of amorphous carbon material preparation. The invention discloses an amorphous carbon material with a multilayer gradient microstructure, which comprises a non-metal doped disordered carbon sodium storage layer 50-99%, an ordered carbon transition layer 0.5-30% and a metal conducting layer 0.5-20% from inside to outside. The amorphous carbon material has the advantages of multiple sodium storage sites, fast ion diffusion and small interface impedance, can be widely used for preparing the electrode material of the sodium ion battery, and can simultaneously ensure the exertion of the capacity, the circulation and the multiplying power of the sodium ion battery based on the material at room temperature and low temperature.
Description
Technical Field
The invention belongs to the technical field of amorphous carbon material preparation, and relates to an amorphous carbon material with a multilayer gradient microstructure, and a preparation method and application thereof.
Background
The sodium ion battery is scientifically researched in the seventy-eight years of the last centuryThe widespread interest of researchers, but the rapid commercialization of lithium ion batteries in the nineties has led sodium ion batteries to be gradually ignored by researchers. In recent years, the application of lithium ion batteries in large-scale energy storage is bottleneck due to the problems of lithium resource scarcity, uneven distribution, difficulty in development and utilization and the like. Meanwhile, because the natural sodium resource is abundant, widely distributed and low in cost, the sodium ion battery has great potential in the field of large-scale energy storage, and the research hot tide is lifted again. The working principle of the sodium ion battery is similar to that of a rocking chair type lithium ion battery proposed by Armand et al in 1980, namely Na is utilized+Reversible storage between positive and negative electrode materials to realize charging and discharging.
The key to the development of sodium ion batteries is to find suitable anode and cathode materials. The negative electrode materials mainly studied at present include carbon-based, titanium-based, organic, alloy and transition types. Among the reported negative electrode materials, the amorphous carbon material with large interlayer spacing and high disorder degree has become the most promising negative electrode material for sodium ion batteries due to the advantages of relatively low sodium storage potential, high sodium storage capacity, good cycle stability and the like. The double regulation and control of the carbon material bulk phase and the surface structure are the key points for improving the electrochemical performance of the carbon material bulk phase and the surface structure.
Disclosure of Invention
In view of the above, it is an object of the present invention to provide an amorphous carbon material having a multi-layered gradient microstructure; the second objective of the present invention is to provide a method for preparing an amorphous carbon material with a multi-layered gradient microstructure; the invention also aims to provide application of the amorphous carbon material with the multilayer gradient microstructure in preparation of the sodium-ion battery electrode material.
In order to achieve the purpose, the invention provides the following technical scheme:
1. an amorphous carbon material with a multilayer gradient microstructure, which comprises the following components in percentage by weight from inside to outside: 50-99% of a nonmetal-doped disordered carbon sodium storage layer, 0.5-30% of an ordered carbon transition layer and 0.5-20% of a metal conducting layer.
Preferably, the amorphous carbon material comprises the following components in percentage by weight from inside to outside: 90-99% of the nonmetal-doped disordered carbon sodium storage layer, 0.5-5% of the ordered carbon transition layer and 0.5-5% of the metal conducting layer.
2. The preparation method of the amorphous carbon material comprises the following steps:
(1) dissolving a carbon source in a solvent to form a solution with the concentration of 0.1-5 mol/L, adding a non-metal dopant, stirring to uniformly mix the non-metal dopant and the solution to form a mixed solution, and performing heat treatment to obtain a precursor of a non-metal doped disordered carbon sodium storage layer;
(2) dispersing the precursor of the non-metal doped disordered carbon sodium storage layer in a solvent, adding a carbon source again, stirring to uniformly mix the precursor and the carbon source, and performing heat treatment to obtain a composite precursor of the ordered carbon-coated non-metal doped disordered carbon sodium storage layer;
(3) dissolving the composite precursor in the step (2) in a solvent, adding a metal compound and an auxiliary agent, stirring to uniformly mix the metal compound and the auxiliary agent, and performing heat treatment to obtain a composite precursor with a metal conducting layer coated on the surface;
(4) and preheating the composite precursor with the surface coated with the metal conductive layer in a protective atmosphere, heating to a carbonization temperature for carbonization, naturally cooling, and taking out to obtain the amorphous carbon material with the multilayer gradient microstructure.
Preferably, the carbon source is any one or more of glucose, monohydrate glucose, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene, graphite, asphalt or coal tar;
the solvent is one or two of water, ethanol, isopropanol, N-Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or acetone;
the heat treatment mode comprises direct heating evaporation at 50-100 ℃, solvothermal at 100-200 ℃ and inert atmosphere pyrolysis at 200-800 ℃, wherein the inert atmosphere is any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas.
Preferably, in the step (1), the non-metal dopant is a non-metal-containing compound containing any one or more of boron (B), nitrogen (N), oxygen (O), fluorine (F), phosphorus (P) or sulfur (S);
the compound containing nonmetal comprises any one or more of boric acid, sodium borohydride, urea, melamine, chitosan, polytetrafluoroethylene, polyvinylidene fluoride, sodium polyacrylate, ammonium dihydrogen phosphate, phytic acid, thiourea or sodium dodecyl benzene sulfonate.
Preferably, In the step (3), the metal compound includes a compound containing any one or more of platinum (Pt), gold (Au), copper (Cu), magnesium (Mg), zinc (Zn), iron (Fe), manganese (Mn), indium (In), tin (Sn), antimony (Sb), or bismuth (Bi);
the metal compound comprises any one or more of platinum acid, chloroauric acid, copper sulfate, magnesium chloride, zinc hydroxide, ferric chloride, manganese carbonate, stannic chloride, manganese sulfate or bismuth oxide.
Preferably, the adjuvant in the step (3) comprises one or more of an oxidation reducing agent, an acid-base regulator or a surfactant;
the redox agent is one or more of ammonium persulfate, thioacetamide, potassium permanganate, formaldehyde, 15mol/L concentrated nitric acid and glucose, the acid-base regulator is one or more of concentrated hydrochloric acid with the concentration of 12mol/L, 25 wt.% ammonia water or sodium hydroxide, and the surfactant is sodium ethylene diamine tetracetate (Na)2EDTA), sodium dodecyl benzene sulfonate, cetyl trimethyl ammonium bromide, polyethyleneimine or polyvinylpyrrolidone.
Preferably, in the step (3), the mass ratio of the metal compound to the composite precursor in the step (2) is 1:4 to 1: 200.
Preferably, the protective atmosphere in the step (4) is any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas;
the preheating solution is specifically as follows: heating to 100-800 ℃ at the speed of 0.5-10 ℃/min, and then carrying out thermal insulation pyrolysis for 0-10 h;
the carbonization temperature is 600-2800 ℃, the carbonization time is 0.5-10 h, and the temperature rise rate of carbonization is 0.5-10 ℃/min.
3. The amorphous carbon material is applied to the preparation of the sodium ion battery electrode material.
The invention has the beneficial effects that:
1. the invention discloses an amorphous carbon material with a multilayer gradient microstructure, which comprises, from inside to outside, a non-metal doped disordered carbon sodium storage layer 50-99%, an ordered carbon transition layer 0.5-30% and a metal conducting layer 0.5-20%. The non-metal doped disordered carbon sodium storage layer in the amorphous carbon material has the characteristics of high disorder degree, multiple sodium storage sites and fast ion diffusion, can provide enough space for sodium ion storage, is a main layer for sodium storage, and ensures the exertion of capacity; the arrangement of carbon atoms in the middle ordered carbon transition layer is relatively ordered, the content of defects and functional groups is less, the integral electronic conductance of the material can be improved, the charge transfer resistance can be reduced, the side reaction of an electrode and electrolyte can be reduced, the interface resistance can be reduced, and the polarization of the battery can be reduced; the metal conducting layer on the surface is used for coating a layer of metal or metal oxide with better conductivity on the surface of the carbon material with relatively poor conductivity, so that the electronic conductivity of the whole material can be further improved, the interface transfer impedance can be reduced, the content of organic functional groups on the surface of the carbon material can be further reduced, and the purposes of reducing the thickness of an electrode/electrolyte interface layer, reducing the interface impedance and reducing polarization at low temperature can be achieved. The amorphous carbon material has the advantages of multiple sodium storage sites, fast ion diffusion and small interface impedance, can be widely used for preparing the electrode material of the sodium ion battery, and can simultaneously ensure the exertion of the capacity, the circulation and the multiplying power of the sodium ion battery based on the material at room temperature and low temperature.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention. The objectives and other advantages of the invention may be realized and attained by the means of the instrumentalities and combinations particularly pointed out hereinafter.
Drawings
For the purposes of promoting a better understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description taken in conjunction with the accompanying drawings in which:
fig. 1 is an XRD comparison pattern of the N-doped gradient structure and the amorphous carbon material (GSCS) coated with metallic copper (Cu) prepared in example 1 and the comparative material (CS) prepared in comparative example 1;
fig. 2 is a comparison graph of electrochemical charge and discharge curves and cycle curves at room temperature of a button cell prepared using the N-doped gradient structure and the amorphous carbon material (GSCS) coated with metallic copper (Cu) prepared in example 1 and the comparative material (CS) prepared in comparative example 1;
fig. 3 is sem (a) and TEM (b and c) views of a P-doped gradient structure and an amorphous carbon material (GSCS) coated with metallic magnesium (Mg) prepared in example 2;
fig. 4 is a graph comparing electrochemical charge and discharge curves and cycle curves at-10 ℃ for a button cell prepared using the P-doped gradient structure and the amorphous carbon material (GSCS) coated with magnesium metal (Mg) prepared in example 2 and the comparative material (CS) prepared in comparative example 2;
fig. 5 is a Raman comparison graph of the F-doped gradient structure and the amorphous carbon material (GSCS) coated with manganese metal (Mn) on the surface prepared in example 3 and the comparative material (CS) prepared in comparative example 3;
fig. 6 is a graph comparing electrochemical charge and discharge curves and cycle curves at-20 ℃ for a coin cell prepared using the F-doped gradient structure and the amorphous carbon material (GSCS) coated with manganese metal (Mn) in the surface prepared in example 3 and the comparative material (CS) prepared in comparative example 3;
fig. 7 is a schematic structural diagram of an amorphous carbon material with a multi-layered gradient microstructure prepared according to the present invention, in which 1 is a metal conductive layer, 2 is an ordered carbon transition layer, and 3 is a non-metal doped disordered carbon sodium storage layer.
Detailed Description
The embodiments of the present invention are described below with reference to specific embodiments, and other advantages and effects of the present invention will be easily understood by those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and of being practiced or of being carried out in various ways, and its several details are capable of modification in various respects, all without departing from the spirit and scope of the present invention. It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present invention in a schematic way, and the features in the following embodiments and examples may be combined with each other without conflict.
Example 1
An amorphous carbon material with a multi-layer gradient microstructure (an amorphous carbon material with an N-doped gradient structure and a surface coated with metal copper (Cu)) is prepared by the following steps:
(1) dissolving 22g of glucose as a carbon source in 60mL of deionized water to form a solution with the concentration of 2mol/L, adding 1g of nonmetal dopant urea, stirring and dispersing in a beaker for 30min until the solution is clear and transparent, carrying out hydrothermal reaction for 24h at 180 ℃, after naturally cooling to normal temperature, taking out a product, carrying out suction filtration and washing for 3 times by using 1000mL of deionized water, and drying in a forced air drying oven at 60 ℃ overnight to obtain a precursor of the nitrogen atom (N) doped disordered carbon sodium storage layer;
(2) adding 60 wt.% of solid-content polytetrafluoroethylene concentrated dispersion liquid (the added carbon source is polytetrafluoroethylene, the mass of the added carbon source is equal to that of the glucose in the step (1)) into the nitrogen atom (N) doped disordered carbon sodium storage layer precursor, stirring to uniformly mix the polytetrafluoroethylene concentrated dispersion liquid and the carbon source, transferring the mixture into a 100mL polytetrafluoroethylene reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 24 hours, and naturally cooling to normal temperature to obtain a composite precursor of the ordered carbon-coated nitrogen (N) atom doped disordered carbon sodium storage layer;
(3) dissolving the composite precursor in deionized water, and adding 0.2g of CuSO4·5H2O and an auxiliary agent (wherein the auxiliary agent comprises 5g of surfactant sodium dodecyl benzene sulfonate, 2g of acid-base regulator sodium hydroxide and 1g of reducing agent formaldehyde), stirring for 15min at 80 ℃ to uniformly mix, heating at 100 ℃ to evaporate a solvent, and drying to obtain a composite precursor with a metal conducting layer (nano Cu particles) coated on the surface;
(4) and (2) placing the composite precursor with the surface coated with the metal conductive layer (nano Cu particles) in a high-temperature tube furnace for annealing treatment under the protection of argon, wherein the flow rate is 50mL/min, the heating rate is 5 ℃/min, heating to 1200 ℃, keeping the temperature for 3h, naturally cooling to room temperature, and taking out to obtain a product, thereby obtaining the amorphous carbon material (GSCS) with the N-doped gradient structure and the surface coated with metal copper (Cu)) with the multilayer gradient microstructure.
Comparative example 1
The precursor of the nitrogen atom (N) -doped disordered sodium-storage layer prepared in step (1) of example 1 was subjected to the treatment in example (4), to obtain a comparative material (CS) having no gradient structure.
Fig. 1 is an XRD comparison pattern of the N-doped gradient structure and the amorphous carbon material (GSCS) coated with metallic copper (Cu) prepared in example 1 and the comparative material (CS) prepared in comparative example 1. As can be seen from fig. 1, GSCS and CS both have two distinct characteristic peaks corresponding to the (002) crystal plane and the (100) crystal plane of the disordered carbon material, respectively. GSCS does not exhibit a distinct diffraction peak for metallic Cu due to its low content and nano-size.
Performance testing
The N-doped gradient structure and the amorphous carbon material (GSCS) coated with metallic copper (Cu) prepared in example 1 and the comparative material (CS) prepared in comparative example 1 were used to prepare a sodium ion battery to test the performance thereof, and the specific procedures were as follows:
(1) mixing and grinding the N-doped gradient structure prepared in example 1, the amorphous carbon material (GSCS) with the surface coated with the metal copper (Cu) and the comparative material (CS) prepared in comparative example 1 with sodium alginate according to a mass ratio of 9:1, and adding deionized water for wet grinding until slurry can pass through a 200-mesh stainless steel screen;
(2) respectively coating the two kinds of slurry ground in the step (1) on copper foil by using a wet film coater, controlling the thickness to be 200 mu m, and then transferring the copper foil to a vacuum oven at 120 ℃ for drying for 12 h;
(3) cutting the two pole pieces in the step (2) into 12mM small round pieces are transferred into a glove box filled with argon, and the button cell assembly is carried out by adding 150 mu L of electrolyte according to the sequence of a negative electrode shell, an elastic piece, a gasket, a metal sodium piece, a diaphragm, a current collector and a positive electrode shell (the model of the used button cell is CR2032, the diaphragm is a glass fiber diaphragm, and the electrolyte is 1M NaPF6Ethylene glycol dimethyl ether electrolyte);
(4) after the assembly, the two button cells were removed from the glove box, left to stand at room temperature for 8 hours, and then subjected to electrochemical performance testing on a LAND cell testing system.
Fig. 2 is a comparison graph of electrochemical charge and discharge curves at room temperature of button cells prepared using the N-doped gradient structure and the amorphous carbon material (GSCS) coated with metallic copper (Cu) prepared in example 1 and the comparative material (CS) prepared in comparative example 1. As can be seen from fig. 2, the amorphous carbon material (GSCS) having the N-doped gradient structure and the surface-coated metallic copper (Cu) exhibited higher krf capacity and first coulombic efficiency in the constant current charge and discharge test, compared to the comparative material (CS) prepared in comparative example 1. The specific gram capacities of the N-doped gradient structure prepared in example 1 and the amorphous carbon material (GSCS) coated with metallic copper (Cu) in the surface thereof and the comparative material (CS) prepared in comparative example 1 were 278.1mAh/g and 233.6mAh/g, respectively, and the first coulombic efficiencies were 89.2% and 84.2%, respectively, at a current density of 150 mA/g. The overall disordering of the microstructure is beneficial to the storage of sodium ions, and the structural characteristic of the external ordered and internal disordered structure can reduce the defect concentration of the material while ensuring the sodium storage capacity, so that the irreversible reaction between the material and the electrolyte is reduced, and the first coulomb efficiency of the material is improved.
Example 2
An amorphous carbon material with a multilayer gradient microstructure (an amorphous carbon material with a P-doped gradient structure and surface coated with magnesium (Mg)) is prepared by the following steps:
(1) dissolving 20g of sucrose as a carbon source in 60mL of deionized water to form a solution with the concentration of 1mol/L, adding 1g of nonmetallic dopant ammonium dihydrogen phosphate, and pyrolyzing the mixture in an argon atmosphere at 700 ℃ to obtain a phosphorus atom (P) doped disordered carbon sodium storage layer precursor;
(2) dispersing the precursor of the phosphorus atom (P) doped disordered carbon sodium storage layer into a mixed solution formed by deionized water and ethanol in a volume ratio of 1:1, adding asphalt which is 1% of the mass fraction of the sucrose and serves as a carbon source, stirring the mixture until the solution is uniformly mixed, evaporating the solvent from the mixed solution at 80 ℃, naturally cooling the mixture to the normal temperature, taking out the product, performing suction filtration and washing on the product for 3 times by using 1000mL of deionized water, and drying the product in a 60 ℃ forced air drying oven for 12 hours to obtain a composite precursor of the ordered carbon-coated phosphorus (P) atom doped disordered carbon sodium storage layer;
(3) dispersing the composite precursor in deionized water, adding 0.5g MgCl2And an adjuvant (wherein the adjuvant is sodium ethylene diamine tetracetate (Na) serving as a surfactant2EDTA)2g), stirring at 60 ℃ for reaction for 1h, filtering, washing to neutrality, and drying to obtain a compound precursor with the surface coated with the Mg-EDTA compound;
(4) and heating the compound precursor coated with the Mg-EDTA compound on the surface to 500 ℃ at the speed of 2 ℃/min in a mixed gas formed by 10% of hydrogen and 90% of argon, preserving the heat for 1h at the temperature of 500 ℃, then heating to 1000 ℃ at the speed of 5 ℃/min, preserving the heat for 2h at the temperature of 1000 ℃, and taking out after naturally cooling to obtain the amorphous carbon material (the amorphous carbon material with a P-doped gradient structure and the surface coated with metal magnesium (Mg)) with a multilayer gradient microstructure (GSCS).
Comparative example 2
The precursor of the phosphorus atom (P) -doped disordered carbon sodium storage layer prepared in the step (1) of example 2 was directly treated by the method of the step (4), so as to obtain a comparative material (CS).
Fig. 3 is sem (a) and TEM (b and c) images of an amorphous carbon material (GSCS) having a P-doped gradient structure and surface-coated metallic magnesium (Mg) prepared in example 2. As can be seen from fig. 3, the SEM image shows that the amorphous carbon material (GSCS) having the P-doped gradient structure and the surface coated with magnesium metal (Mg) prepared in example 2 has a spherical structure, and the TEM image shows that the amorphous carbon material (GSCS) having the P-doped gradient structure and the surface coated with magnesium metal (Mg) prepared in example 2 has an obvious gradient structure, the surface carbon layers have a long length and are arranged in order, and the internal carbon layers have a short length and are arranged in order.
Performance testing
The amorphous carbon material (GSCS) having a P-doped gradient structure and coated with magnesium metal (Mg) prepared in example 2 and the comparative material (CS) prepared in comparative example 2 were prepared into an electrode and a sodium ion battery according to the method for testing the performance of example 1, and then subjected to electrochemical testing at-10 c, with the results shown in fig. 4. As can be seen from the results of the performance test of fig. 4: under the current density of 30mA/g, the comparative material (CS) shows large capacity attenuation, the specific capacity of the comparative material (CS) is only 86.7mAh/g after 10 circles of operation, and the capacity retention rate is 37.1 percent of that of the comparative material at normal temperature; however, the specific capacity of the amorphous carbon material (GSCS) with the P-doped gradient structure and the surface coated with the magnesium metal (Mg) is 274.6mAh/g after 10 circles of operation, and the capacity retention rate is 98.7%.
Example 3
An amorphous carbon material with a multi-layer gradient microstructure (an amorphous carbon material with an F-doped gradient structure and a surface coated with metal manganese (Mn)) is prepared by the following steps:
(1) adding 50mL of polytetrafluoroethylene with the mass fraction of 5 wt.% into 100mL of lignin aqueous solution (with the mass fraction of 5 wt.%) as a nonmetal dopant, and stirring and dispersing until the solution is clear and transparent;
(2) continuously adding 300mL of olive oil and 1 wt.% of phenolic resin aqueous solution, stirring for 2h at 85 ℃, centrifuging to remove redundant olive oil, and washing for 6 times by using n-hexane to obtain a phosphorus atom (P) doped disordered sodium carbonate layer precursor;
(3) dissolving the composite precursor in deionized water, and adding 0.02g of MnSO4Stirring and reacting for 24h at room temperature with an auxiliary agent (wherein the auxiliary agent is 1.5 hexadecyl trimethyl ammonium bromide (CTAB)), filtering, washing for 6 times, and drying to obtain a composite precursor with the surface coated with the Mn-CTAB composite;
(4) heating the composite precursor with the surface coated with the Mn-CTAB composite to 350 ℃ at the speed of 1 ℃/min under the nitrogen atmosphere, preserving heat for 5h at 350 ℃, then heating to 1300 ℃ at the speed of 10 ℃/min, preserving heat for 1h at 1300 ℃, and taking out after naturally cooling to obtain the target product, namely the amorphous carbon material (GSCS) with the multilayer gradient microstructure, wherein the amorphous carbon material has an F-doped gradient structure and the surface coated with metal manganese (Mn).
Comparative example 3
The precursor of the disordered carbon sodium storage layer doped with the fluorine atoms (F) prepared in the step (2) of example 3 is directly processed by the method of the step (4), so as to obtain the comparative material (CS).
Fig. 5 shows Raman comparison graphs of the amorphous carbon material (GSCS) having the F-doped gradient structure and the surface-coated metal manganese (Mn) prepared in example 3 and the comparative material (CS) prepared in comparative example 3. As can be seen in FIG. 5, both materials exhibit broader D and G peaks, indicating that both carbon materials contain a more defective SP at the same time3Carbon and SP with high degree of graphitization2Carbon. Through careful analysis, it was found that I of the amorphous carbon material (GSCS) having an F-doped gradient structure and surface-coated metal manganese (Mn) prepared in example 3 was compared to that of the comparative material (CS) prepared in comparative example 3D/IGSlightly smaller, indicating a higher degree of order, probably due to the manganese atoms being able to catalyze the graphitization of the carbon material.
Performance testing
The amorphous carbon material (GSCS) having the F-doped gradient structure and the surface coated with manganese metal (Mn) of example 3 and the comparative material (CS) prepared in comparative example 3 were prepared into an electrode and a sodium ion battery according to the performance test method of example 1, and then subjected to an electrochemical test at-20 c, and the test results are shown in fig. 6. The results of the performance test were: at 30mA g-1Under the current density of the material, the first charging specific capacity of the CS is only 27.8mAh/g, and the first charging specific capacity of the CS is only 13.5mAh/g after 10 cycles of circulation, which shows that the material has serious capacity attenuation due to the slow intrinsic ion diffusion rate under the low-temperature condition, and the retention rate is only 11.9% under the normal-temperature condition. However, due to the disordered internal structure of the GSCS, the increased order degree of the middle layer and the surface conducting layer, the relatively high specific capacity can still be maintained at the temperature of-20 ℃, and the first-turn charging specific capacity is 216.9mA h g-1206.4 mA hr g at turn 10-1The retention rate was 78.0% at room temperature.
Similarly, the carbon source in the above embodiment may be any one or more of glucose, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene, graphite, pitch or coal tar, the solvent may be any one or two of water, ethanol, isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone, the heat treatment may be direct evaporation at 50 to 100 ℃, solvothermal at 100 to 200 ℃ or pyrolysis in an inert atmosphere at 200 to 800 ℃, the inert gas may be any one or more of argon, nitrogen, ammonia or argon mixture, and the nonmetal dopant may be a nonmetal-containing compound (e.g., a compound containing one or more of boron, nitrogen, oxygen, fluorine, phosphorus or sulfur) containing nonmetal, Sodium borohydride, urea, melamine, chitosan, polytetrafluoroethylene, polyvinylidene fluoride, sodium polyacrylate, ammonium dihydrogen phosphate, phytic acid, thiourea or sodium dodecyl benzene sulfonate), the metal compound can be any one or more compounds containing any one or more elements of platinum, gold, copper, magnesium, zinc, iron, manganese, indium, tin, antimony or bismuth (such as platinum auric acid, chloroauric acid, copper sulfate, magnesium chloride, zinc hydroxide, ferric chloride, manganese carbonate, tin tetrachloride, manganese sulfate or bismuth oxide), the auxiliary agent comprises an oxidation reducing agent (such as any one or more of ammonium persulfate, thioacetamide, potassium permanganate, formaldehyde, 15mol/L concentrated nitric acid and glucose), an acid-base regulator (such as any one or more of 12mol/L concentrated hydrochloric acid, 25 wt.% ammonia water or sodium hydroxide) or a surfactant (such as sodium ethylene diamine tetracetate, sodium chloride, Any one or more of sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, polyethyleneimine or polyvinylpyrrolidone) and protective gas can be any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas, and the formed amorphous carbon material with the multilayer gradient microstructure has the advantages of multiple sodium storage sites, fast ion diffusion, small interface impedance and the like, and can be widely used for preparing sodium ion battery electrode materials.
In summary, the invention discloses an amorphous carbon material with a multilayer gradient microstructure (a structural schematic diagram is shown in fig. 7, wherein 1 is a metal conducting layer, 2 is an ordered carbon transition layer, and 3 is a non-metal doped disordered carbon sodium storage layer), the amorphous carbon material comprises, from inside to outside, 50-99% of the non-metal doped disordered carbon sodium storage layer, 0.5-30% of the ordered carbon transition layer, and 0.5-20% of the metal conducting layer, and has the advantages of multiple sodium storage sites, fast ion diffusion, small interface impedance and the like, so that the amorphous carbon material can be widely used for preparing an electrode material of a sodium ion battery, and can simultaneously ensure the exertion of capacity, cycle and multiplying power of the sodium ion battery based on the material at room temperature and low temperature.
Finally, the above embodiments are only intended to illustrate the technical solutions of the present invention and not to limit the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it will be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions, and all of them should be covered by the claims of the present invention.
Claims (10)
1. An amorphous carbon material having a multi-layered gradient microstructure, comprising, in weight percent, from the inside out: 50-99% of a nonmetal-doped disordered carbon sodium storage layer, 0.5-30% of an ordered carbon transition layer and 0.5-20% of a metal conducting layer.
2. The amorphous carbon material of claim 1, comprising, in weight percent, from the inside out: 90-99% of the nonmetal-doped disordered carbon sodium storage layer, 0.5-5% of the ordered carbon transition layer and 0.5-5% of the metal conducting layer.
3. The method for preparing an amorphous carbon material as claimed in any one of claims 1 to 2, wherein the method comprises the steps of:
(1) dissolving a carbon source in a solvent to form a solution with the concentration of 0.1-5 mol/L, adding a non-metal dopant, stirring to uniformly mix the non-metal dopant and the solution to form a mixed solution, and performing heat treatment to obtain a precursor of a non-metal doped disordered carbon sodium storage layer;
(2) dispersing the precursor of the non-metal doped disordered carbon sodium storage layer in a solvent, adding a carbon source again, stirring to uniformly mix the precursor and the carbon source, and performing heat treatment to obtain a composite precursor of the ordered carbon-coated non-metal doped disordered carbon sodium storage layer;
(3) dissolving the composite precursor in the step (2) in a solvent, adding a metal compound and an auxiliary agent, stirring to uniformly mix the metal compound and the auxiliary agent, and performing heat treatment to obtain a composite precursor with a metal conducting layer coated on the surface;
(4) and preheating the composite precursor with the surface coated with the metal conductive layer in a protective atmosphere, heating to a carbonization temperature for carbonization, naturally cooling, and taking out to obtain the amorphous carbon material with the multilayer gradient microstructure.
4. The preparation method according to claim 3, wherein the carbon source is any one or more of glucose, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene, graphite, pitch or coal tar;
the solvent is any one or two of water, ethanol, isopropanol, N-dimethylformamide, N-methylpyrrolidone or acetone;
the heat treatment mode comprises direct heating evaporation at 50-100 ℃, solvothermal at 100-200 ℃ and inert atmosphere pyrolysis at 200-800 ℃, wherein the inert atmosphere is any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas.
5. The preparation method according to claim 3, wherein in the step (1), the nonmetal dopant is a nonmetal-containing compound containing any one or more of boron, nitrogen, oxygen, fluorine, phosphorus or sulfur;
the compound containing nonmetal comprises any one or more of boric acid, sodium borohydride, urea, melamine, chitosan, polytetrafluoroethylene, polyvinylidene fluoride, sodium polyacrylate, ammonium dihydrogen phosphate, phytic acid, thiourea or sodium dodecyl benzene sulfonate.
6. The method according to claim 3, wherein in the step (3), the metal compound comprises a compound containing any one or more of platinum, gold, copper, magnesium, zinc, iron, manganese, indium, tin, antimony, and bismuth;
the metal compound comprises any one or more of platinum acid, chloroauric acid, copper sulfate, magnesium chloride, zinc hydroxide, ferric chloride, manganese carbonate, stannic chloride, manganese sulfate or bismuth oxide.
7. The amorphous carbon material as claimed in claim 3, wherein the adjuvant in step (3) comprises one or more of an oxidation reducing agent, an acid-base modifier or a surfactant;
the oxidation reducing agent is one or more of ammonium persulfate, thioacetamide, potassium permanganate, formaldehyde, 15mol/L concentrated nitric acid and glucose, the acid-base regulator is one or more of concentrated hydrochloric acid with the concentration of 12mol/L, 25 wt.% ammonia water or sodium hydroxide, and the surfactant is one or more of sodium ethylene diamine tetracetate, sodium dodecyl benzene sulfonate, hexadecyl trimethyl ammonium bromide, polyethyleneimine or polyvinylpyrrolidone.
8. The preparation method according to claim 3, wherein in the step (3), the mass ratio of the metal compound to the composite precursor in the step (2) is 1:4 to 1: 200.
9. The preparation method according to claim 3, wherein the protective atmosphere in the step (4) is any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas;
the preheating solution specifically comprises the following steps: heating to 100-800 ℃ at the speed of 0.5-10 ℃/min, and then carrying out thermal insulation pyrolysis for 0-10 h;
the carbonization temperature is 600-2800 ℃, the carbonization time is 0.5-10 h, and the temperature rise rate of carbonization is 0.5-10 ℃/min.
10. Use of the amorphous carbon material of any one of claims 1 to 2 for the preparation of an electrode material for a sodium ion battery.
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