CN115092905B - Amorphous carbon material modified by carbon dots, and preparation method and application thereof - Google Patents
Amorphous carbon material modified by carbon dots, and preparation method and application thereof Download PDFInfo
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- CN115092905B CN115092905B CN202210872316.4A CN202210872316A CN115092905B CN 115092905 B CN115092905 B CN 115092905B CN 202210872316 A CN202210872316 A CN 202210872316A CN 115092905 B CN115092905 B CN 115092905B
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- Prior art keywords
- carbon
- amorphous carbon
- carbon material
- modified
- dots
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- 239000002194 amorphous carbon material Substances 0.000 title claims abstract description 86
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 96
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 77
- 229910003481 amorphous carbon Inorganic materials 0.000 claims abstract description 69
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 17
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 22
- 229910052786 argon Inorganic materials 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007833 carbon precursor Substances 0.000 claims description 13
- 229910021385 hard carbon Inorganic materials 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 230000020477 pH reduction Effects 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 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 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical group [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- 229910021538 borax Inorganic materials 0.000 claims description 4
- 229910052796 boron Inorganic materials 0.000 claims description 4
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 4
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002019 doping agent Substances 0.000 claims description 3
- 239000007773 negative electrode material Substances 0.000 claims description 3
- 229960004543 anhydrous citric acid Drugs 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 17
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 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 4
- 239000011734 sodium Substances 0.000 abstract description 4
- 229910052708 sodium Inorganic materials 0.000 abstract description 4
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 238000003860 storage Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 28
- 229910021384 soft carbon Inorganic materials 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 13
- 239000003575 carbonaceous material Substances 0.000 description 12
- 239000010426 asphalt Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 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 description 7
- 230000007547 defect Effects 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 229960001031 glucose Drugs 0.000 description 7
- 229910021389 graphene Inorganic materials 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 6
- 229960004106 citric acid Drugs 0.000 description 6
- 238000005087 graphitization Methods 0.000 description 6
- 229920002472 Starch Polymers 0.000 description 5
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 5
- 239000003830 anthracite Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000002096 quantum dot Substances 0.000 description 5
- 239000008107 starch Substances 0.000 description 5
- 235000019698 starch Nutrition 0.000 description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 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 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 229920005610 lignin Polymers 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 3
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229940032147 starch Drugs 0.000 description 2
- 229960004793 sucrose Drugs 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229940045136 urea Drugs 0.000 description 2
- 239000011782 vitamin Substances 0.000 description 2
- 229940088594 vitamin Drugs 0.000 description 2
- 229930003231 vitamin Natural products 0.000 description 2
- 235000013343 vitamin Nutrition 0.000 description 2
- 150000003722 vitamin derivatives Chemical class 0.000 description 2
- 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
- 239000002028 Biomass Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 239000006012 monoammonium phosphate Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
- 239000000467 phytic acid Substances 0.000 description 1
- 235000002949 phytic acid Nutrition 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/65—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing carbon
-
- 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
- H01M4/58—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
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an amorphous carbon material modified by carbon points, 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 carbon dot modification, which can utilize various methods such as hydrothermal method, calcination method, coprecipitation method and the like to grow carbon dots on the surface and inside of amorphous carbon in situ. The carbon dots grown on the surface of the amorphous carbon in situ can induce different SEI films in the sodium storage process, and the carbon dots grown in the amorphous carbon are beneficial to electron conduction and ion diffusion, so that the first coulomb efficiency and specific capacity of the sodium ion battery are effectively improved.
Description
Technical Field
The invention belongs to the technical field of amorphous carbon material preparation, and relates to an amorphous carbon material modified by carbon dots, and a preparation method and application thereof.
Background
In recent decades, methods for replacing fossil energy with green clean energy have been sought around the world. With the gradual maturity of lithium ion battery technology and the development of novel energy sources such as sodium ion batteries and solar batteries, the energy structure transformation steps into an acceleration stage. Lithium ion batteries have been widely used in life, almost replacing traditional lead acid batteries and other disposable batteries. However, the lithium resources are low in content and unevenly distributed on the earth, the price of lithium begins to surge along with the maturity of the lithium electric automobile technology, in addition, the content of the earth lithium is far from the requirement of replacing a complete gasoline automobile, and the development of sodium ion batteries is inevitable.
The sodium ion battery has a similar sodium storage principle as the lithium ion battery, namely, ions move between the anode and the cathode so as to realize charge and discharge. The anode materials studied at present mainly include alloys, metal compounds, carbon, organic species, polyanions, and the like. But most likely to be industrialized, the carbon material with low cost and stable performance is still adopted. At present, the carbon material is mainly from biomass carbon, and large-scale preparation is difficult to realize. But the performances of the asphalt-based carbon, coal-based carbon and the like with rich yield do not meet the requirements.
It has therefore become an urgent need to find suitable carbon sources, simple preparation methods and efficient modification strategies.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide an amorphous carbon material modified with carbon dots; the second object of the present invention is to provide a method for producing an amorphous carbon material modified with carbon dots; the invention further aims to provide an application of the amorphous carbon material modified by carbon points in preparing a negative electrode material of a sodium ion battery.
In order to achieve the above purpose, the present invention provides the following technical solutions:
1. an amorphous carbon material modified by carbon dots, the amorphous carbon material comprising amorphous carbon and carbon dots, wherein the carbon dots account for 0.1-10% of the weight of the amorphous carbon, the diameter of the carbon dots is 3-50 nm, and the carbon dots are distributed on the surface and/or inside of the amorphous carbon.
2. The preparation method of the amorphous carbon material modified by carbon points comprises the following steps:
(1) Carrying out solvothermal treatment, roasting treatment or microwave radiation treatment on the activated carbon point carbon source and the acid-treated amorphous carbon source to enable carbon points to grow on the surface and/or the inside of the amorphous carbon precursor or the amorphous carbon in situ, so as to obtain the carbon point modified amorphous carbon precursor;
(2) And placing the carbon-point-modified amorphous carbon precursor in a protective atmosphere, heating to the point that the carbon source of the carbon points is completely carbonized, naturally cooling, and taking out to obtain the carbon-point-modified amorphous carbon material.
Preferably, the activation treatment is a pyrolysis treatment, an electrolysis treatment or an acid oxidation treatment of a carbon point carbon source;
the pyrolysis treatment is to heat a carbon point carbon source to pyrolysis temperature and continuously stir for 5-180 min;
the electrolysis treatment is to soak a carbon point carbon source as an electrode in the water electrolyte, generate defects by applying oxidation-reduction potential, or dissolve the carbon point carbon source in a solvent, insert two metal electrodes, electrify for 1-30 h under 2-50V voltage, and centrifugally collect;
the acid oxidation treatment is to dissolve carbon point carbon source in acid solution, then carry out water bath ultrasonic treatment for 12-200 h and then centrifuge.
Preferably, the amorphous carbon source is treated prior to the acid treatment in the following manner: pyrolyzing an amorphous carbon source in an inert atmosphere at 500-1600 ℃, and then crushing the amorphous carbon source to a particle size of 0.5-500 um to obtain an acid-treated amorphous carbon source;
the acid treatment is to add an amorphous carbon source into an acid solution, heat the amorphous carbon source, then carry out hydrothermal treatment, and wash and dry the amorphous carbon source after cooling;
the acid solution is any one or more of nitric acid, hydrochloric acid and sulfuric acid.
Preferably, the amorphous carbon source is any one or more of pitch, coal tar, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene or urea;
the carbon point carbon source is any one or more of animal hair, plant fiber, carbon fiber, graphene, graphite, anthracite, coke, carbon nanotube, urea, citric acid, glucose monohydrate, sucrose, starch, lignin, protein and vitamin;
the mass ratio of the amorphous carbon source to the carbon point carbon source is 1:0.1-1:10.
Preferably, the solvothermal treatment is specifically: dispersing an amorphous carbon source subjected to acid treatment in a solvent, adding a carbon point carbon source for dissolution, then placing the solution in a reaction kettle for sealing, preserving heat for 1-15 h at 100-250 ℃, cooling, washing and drying;
the solvent is any one or more of water, formamide, isopropanol, N-dimethylformamide, N-methylpyrrolidone and acetone.
Preferably, the roasting treatment is to heat the carbon point carbon source to melt, add the amorphous carbon source under stirring, and stir until uniformly mixed.
Preferably, the microwave radiation treatment specifically includes: dispersing amorphous carbon or an amorphous carbon source in a solvent, adding a carbon point carbon source for dissolution, and then placing the mixture in a microwave reactor for reaction, wherein the power in the microwave reactor is 200-1000W, the temperature is 60-200 ℃, and the reaction time is 20-120 min.
Preferably, in the step (2), the protective atmosphere is an atmosphere formed by any one or more of argon, nitrogen, ammonia gas or hydrogen-argon mixed gas, and the volume ratio of hydrogen to argon in the hydrogen-argon mixed gas is 5:95-10:90;
the carbonization specifically comprises the following steps: heating to 100-1600 ℃ at the speed of 0.5-10 ℃/min, and then preserving heat and pyrolyzing for 1-10 h.
3. The amorphous carbon material modified by carbon points is applied to the preparation of the negative electrode material of the sodium ion battery.
The invention has the beneficial effects that: the invention discloses an amorphous carbon material modified by carbon dots, which is characterized in that carbon dots with the weight percentage of 0.1-10% and the diameter of 5-50 nm are distributed on the surface and/or inside of amorphous carbon. The carbon dots are mainly crystalline carbon with good crystallinity, different graphitization degrees are utilized to have a certain influence on the formation of the SEI film, the inorganic salt and organic matter content of the SEI film can be improved by growing on the surface of amorphous carbon, through regulating and controlling the proportion, the inorganic salt can enable sodium ions to quickly pass through the SEI film, the ion impedance and the interfacial charge transfer impedance are reduced, the organic component content is increased, the mechanical property of the SEI film can be improved, the damage of volume expansion to the SEI film is prevented, the continuous dissolution of inorganic components in electrolyte is slowed down, and the cycle performance is improved; in addition, the growth of carbon dots with higher graphitization degree on the surface of the amorphous carbon reduces the specific surface area and surface defects, so that the first coulombic efficiency of the sodium ion battery is effectively improved. The carbon dots grown inside the amorphous carbon facilitate the transport of ions inside the bulk phase while increasing the electron conductivity, which greatly improves ion diffusion compared to unmodified amorphous carbon materials. The amorphous carbon material modified by carbon dots has the advantages of small specific surface area, few surface defects, faster ion diffusion rate, small charge transfer interface impedance and good ion conductivity of the SEI film, can be widely applied to preparing the electrode material of the sodium ion battery, ensures the increase of the initial coulombic efficiency of the material, and effectively improves the specific capacity and the rate capability.
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 objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the specification.
Drawings
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in the following preferred detail with reference to the accompanying drawings, in which:
FIG. 1 is an XRD contrast pattern of the carbon dot modified amorphous carbon material (nitrogen doped carbon dot modified pitch-based amorphous carbon material (CDMP)) prepared in example 1 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 1;
FIG. 2 is a graph comparing electrochemical charge and discharge curves (a) and cycle performance (b) at room temperature of button cells prepared from carbon-dot modified amorphous carbon material (nitrogen-doped carbon-dot modified pitch-based amorphous carbon material (CDMP)) prepared by the method of example 1 and pure pitch-based amorphous carbon (PP) prepared in comparative example 1;
FIG. 3 is a TEM image of carbon dot modified amorphous carbon material (CDMC) (a, b) and pure hard carbon material (HC) (c) prepared in example 2;
FIG. 4 is a graph showing the comparison of electrochemical charge and discharge curves at room temperature for button cells prepared from carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and pure hard carbon material (HC) prepared in comparative example 2;
FIG. 5 is a Raman comparison graph of the graphene quantum dot modified amorphous carbon material (GDMC) prepared in example 3 and the Soft Carbon (SC) prepared in comparative example 3 without modification of graphene quantum dots;
FIG. 6 is a graph of cycle performance (a) and rate performance (b) at room temperature of the graphene quantum dot modified amorphous carbon material (GDMC) of example 3 and the Soft Carbon (SC) prepared in comparative example 3 without graphene quantum dot modification;
FIG. 7 is a SEM comparative view of soft carbon modified with Carbon Dots (CDSC) (a) prepared by the calcination method of example 4 and pure pitch-based amorphous carbon (PP) (b) prepared in comparative example 4;
fig. 8 is a charge-discharge curve of soft carbon modified with Carbon Dots (CDSC) in example 4 and pure pitch-based amorphous carbon (PP) prepared in comparative example 4.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention. It should be noted that the illustrations provided in the following embodiments merely illustrate the basic idea of the present invention by way of illustration, and the following embodiments and features in the embodiments may be combined with each other without conflict.
Example 1
An amorphous carbon material modified by carbon dots (nitrogen-doped carbon dot modified pitch-based amorphous carbon material), the specific preparation method comprising the steps of:
(1) And (3) placing 2g of asphalt serving as an amorphous carbon source into a high-temperature tube furnace for annealing treatment under an argon protective atmosphere, wherein the air flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is increased to 800 ℃, the temperature is kept for 2 hours, and the product is obtained after the asphalt is naturally cooled to room temperature, so that the pure asphalt-based amorphous carbon material is obtained.
(2) The pure asphalt-based amorphous carbon material is placed in a planetary ball mill for crushing treatment (ball milling is carried out for 2 hours at the rotating speed of 600 rpm) until the particle size is 0.5-500 um, amorphous carbon powder obtained by ball milling is placed in 3.5mol/L nitric acid solution for stirring for 30min, hydrothermal treatment is carried out for 1.5 hours at the temperature of 160 ℃, after the amorphous carbon material is naturally cooled to normal temperature, the product is taken out, filtered and washed for 3 times by 1000mL deionized water, and dried overnight in a blast drying oven at the temperature of 60 ℃ to obtain the amorphous carbon material subjected to hydrothermal acidification treatment.
(3) And (3) uniformly dispersing the amorphous carbon material subjected to the hydrothermal acidification in 40mL of formamide solvent, adding 2g of urea as a carbon point carbon source, stirring and uniformly mixing, sealing in a reaction kettle, performing hydrothermal treatment at 200 ℃ for 5 hours, taking out a product, performing suction filtration and washing 3 times by using 1000mL of deionized water and ethanol after the product is naturally cooled to normal temperature, and drying in a blast drying oven at 60 ℃ for overnight to obtain the amorphous carbon precursor modified by the carbon point.
(4) And (3) placing the carbon-point-modified amorphous carbon precursor in a high-temperature tube furnace for annealing treatment under an argon protection atmosphere (the air flow rate is 50mL/min, the heating rate is 5 ℃/min, the heating is up to 800 ℃ and the heat preservation is carried out for 1 h), and taking out after the amorphous carbon precursor is naturally cooled to room temperature, thus obtaining the carbon-point-modified amorphous carbon material (nitrogen-doped carbon-point-modified asphalt-based amorphous carbon material (CDMP)).
Comparative example 1
The pure pitch was treated only by step (1) of example 1 to obtain pure pitch-based amorphous carbon (PP).
Performance testing
Fig. 1 is an XRD comparison pattern of the amorphous carbon material modified with carbon dots (nitrogen doped carbon dot modified pitch-based amorphous carbon material (CDMP)) prepared in example 1 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 1. As can be seen from fig. 1, both CDMP and PP have two distinct characteristic peaks corresponding to the (002) and (100) crystal planes of the disordered carbon material, respectively, but because the carbon dot size is only nano-scale and the content is small, no distinct graphite characteristic peak is detected.
The carbon-point-modified amorphous carbon material prepared in example 1 (nitrogen-doped carbon-point-modified pitch-based amorphous carbon material (CDMP)) and the pure pitch-based amorphous carbon (PP) prepared in comparative example 1 were used to prepare sodium ion batteries to test their properties, as follows:
(1) The amorphous carbon material modified by carbon dots (nitrogen doped carbon dot modified pitch-based amorphous carbon material (CDMP)) prepared in example 1 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 1 were respectively mixed and milled with sodium alginate in a mass ratio of 9:1, and deionized water was added to conduct wet milling until the slurry was able to pass through a 200 mesh stainless steel screen;
(2) Coating the two slurries ground in the step (1) on copper foil by using a wet film coater respectively, controlling the thickness to be 200 mu m, and then transferring to a vacuum oven at 120 ℃ for drying for 12 hours;
(3) Cutting the two pole pieces in the step (2) into small pieces with the diameter of 12mm, transferring the small pieces into a glove box filled with argon, and assembling a button cell by adding 150 mu L of electrolyte in 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 type of the button cell used is CR2032, the diaphragm is a glass fiber diaphragm, and the electrolyte is 1M NaPF) 6 Ethylene carbonate and dimethyl carbonate (1:1)).
(4) After the assembly was completed, the two button cells were removed from the glove box and allowed to stand at room temperature for 8 hours, and then electrochemical performance test was performed on the LAND cell test system.
Fig. 2 is a graph comparing electrochemical charge and discharge curves (a) and cycle properties (b) at room temperature of button cells prepared from carbon-dot modified amorphous carbon material (nitrogen-doped carbon-dot modified pitch-based amorphous carbon material (CDMP)) prepared by the method of example 1 and pure pitch-based amorphous carbon (PP) prepared in comparative example 1. As can be seen from fig. 2, the amorphous carbon material modified by carbon dots (nitrogen doped carbon dot modified pitch-based amorphous carbon material (CDMP)) prepared in example 1 exhibited higher gram specific capacity and first coulombic efficiency in the constant current charge and discharge test compared to the pure pitch-based amorphous carbon (PP) prepared in comparative example 1. The gram specific capacities of the carbon dot modified amorphous carbon material prepared in example 1 (nitrogen doped carbon dot modified pitch based amorphous carbon material (CDMP)) and the pure pitch based amorphous carbon (PP) prepared in comparative example 1 were 409.0mAh/g and 199.7mAh/g, respectively, with first coulombic efficiencies of 76.10% and 65.82%, respectively, at a current density of 30 mA/g. The whole disorder of the microstructure is favorable for the storage of sodium ions, but is also unfavorable for the first coulomb efficiency and the ion and electron transmission, so that the ordered distribution of the nanometer scale inside and on the surface of disordered carbon is very significant for improving the reaction kinetics.
Example 2
An amorphous carbon material modified by carbon dots (boron doped carbon dot modified hard carbon), the preparation method comprises the following steps:
(1) And (3) placing 2g of glucose serving as an amorphous carbon source into a high-temperature tube furnace for annealing treatment under an argon protective atmosphere, wherein the air flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 1200 ℃, the temperature is kept for 2 hours, and the amorphous carbon material is obtained after the glucose is naturally cooled to room temperature.
(2) And (3) placing the amorphous carbon material into a planetary ball mill for crushing treatment (the rotating speed is 600rpm for ball milling for 2 hours) until the particle size is 0.5-500 um, then placing hard carbon powder obtained by ball milling into 3.5mol/L nitric acid solution for stirring for 30 minutes, carrying out hydrothermal reaction for 1.5 hours at 160 ℃, taking out the product after the product is naturally cooled to normal temperature, carrying out suction filtration and washing on the product by using 1000mL of deionized water for 3 times, and drying overnight in a blast drying oven at 60 ℃ to obtain the amorphous carbon material subjected to hydrothermal acidification treatment.
(3) And (3) uniformly dispersing the amorphous carbon material subjected to the hydrothermal acidification in 40mL of formamide solvent, adding 2g of anhydrous citric acid as a carbon point carbon source, adding 1g of boric acid and sodium borate as boron atom doping agents, stirring until the boric acid and the sodium borate are completely dissolved, carrying out hydrothermal reaction for 5 hours at 200 ℃, taking out the amorphous carbon material after the amorphous carbon material is naturally cooled to normal temperature, carrying out suction filtration and washing for 3 times by 1000mL of deionized water and ethanol, and drying overnight in a blast drying oven at 60 ℃ to obtain the amorphous carbon precursor modified by carbon points.
(4) And (3) placing the precursor in a high-temperature tube furnace for annealing treatment under the protection of argon (the air flow rate is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 1200 ℃ and the heat is preserved for 1 h), and taking out the precursor after the precursor is naturally cooled to room temperature to obtain the product, thus obtaining the amorphous carbon material (CDMC) modified by carbon points.
Comparative example 2
Glucose was subjected to only step (1) of example 2 to obtain pure hard carbon material (HC).
Performance testing
FIG. 3 is a TEM image of carbon dot modified amorphous carbon material (CDMC) (a, b) and pure hard carbon material (c) prepared in example 2. It can be seen from FIG. 3 that the carbon dots are combined with hard carbon, the carbon dots are distributed in a dispersed manner and are not agglomerated, the particle size distribution of the carbon dots is about 10-20 nm, obvious lattice fringes can be seen, and the interplanar spacing is 0.22nm, which is consistent with common carbon dots; the pure hard carbon material has a well-aligned, curved carbon layer. The difference in microstructure causes a difference in performance.
The electrochemical charge-discharge curves at room temperature of the button cell prepared from the carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and the pure hard carbon material (HC) prepared in comparative example 2 are shown in fig. 4, except that the ester electrolyte was replaced with NaPF6 dimethyl ether, and the electrode and the sodium ion cell prepared from the carbon dot modified amorphous carbon material (CDMC) prepared in example 2 and the pure hard carbon material (HC) prepared in comparative example 2 were prepared according to the method for testing the product properties in example 1 described above. As can be seen from the results of fig. 4: at a current density of 30mA/g, the amorphous carbon material (CDMC) modified by carbon dots shows similar first discharge capacity compared with the pure hard carbon material (HC), and the first discharge capacity is more than 450mAh/g, and the platform capacities almost coincide, which shows that the modification of the carbon dots hardly affects the intercalation of sodium ions; however, amorphous carbon materials (CDMC) modified by carbon dots exhibit higher average voltages and slightly higher capacities at the ramp section, indicating that carbon dots may have some effect on the adsorption capacity of sodium ions. This may be related to the surface heterogeneity, reactive groups and boundary effects that the carbon sites themselves have, but the higher average voltage is detrimental to the full cell energy density. Furthermore, the first coulombic efficiency of the carbon-point-modified hard carbon is improved to some extent, which may be related to surface defects and reduction of specific surface area.
Example 3
The preparation method of the amorphous carbon material modified by carbon dots (graphene quantum dot modified soft carbon) comprises the following steps:
(1) And (3) placing 2g of anthracite as an amorphous carbon source in a high-temperature tube furnace for annealing treatment under an argon protective atmosphere (the air flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 800 ℃ and the heat is preserved for 2 hours), and taking out after the anthracite is naturally cooled to room temperature, so as to obtain the pure asphalt-based amorphous carbon material.
(2) And (3) placing the amorphous carbon material into a planetary ball mill for crushing treatment (the rotating speed is 600rpm, the ball milling is carried out for 2 hours) until the particle size is 0.5-500 um, then placing amorphous carbon powder obtained by ball milling into a nitric acid solution with the concentration of 3.5mol/L, stirring for 30 minutes, carrying out hydrothermal treatment at 160 ℃ for 1.5 hours, taking out the product, carrying out suction filtration and washing 3 times by using 1000mL deionized water after the product is naturally cooled to normal temperature, and drying overnight in a blast drying oven with the temperature of 60 ℃ to obtain the amorphous carbon material subjected to hydrothermal acidification treatment.
(3) And (3) uniformly dispersing the amorphous carbon material subjected to the hydrothermal acidification in 40mL of deionized water solvent, adding 1g of starch serving as a carbon point carbon source, stirring at 60 ℃ for 15min, rapidly pouring into a 100mL of polytetrafluoroethylene high-pressure reaction kettle after complete dissolution, carrying out hydrothermal treatment at 190 ℃ for 2h, taking out a product after the product is naturally cooled to normal temperature, carrying out suction filtration and washing 3 times by using 1000mL of deionized water and ethanol, and drying overnight in a blast drying oven at 60 ℃ to obtain the amorphous carbon precursor modified by the graphene quantum dots.
(4) And (3) placing the precursor in a high-temperature tube furnace for annealing treatment under an argon protective atmosphere (the air flow rate is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 800 ℃ and the heat is preserved for 1 h), and taking out the precursor after the precursor is naturally cooled to room temperature to obtain the product, thus obtaining the graphene quantum dot modified amorphous carbon material (GDMC).
Comparative example 3
And (3) treating the anthracite only by the step (1) in the embodiment 3 to obtain Soft Carbon (SC) which is not modified by the graphene quantum dots.
Performance testing
Fig. 5 is a Raman comparison graph of the amorphous carbon material (GDMC) modified with graphene quantum dots prepared in example 3 and the Soft Carbon (SC) not modified with graphene quantum dots prepared in comparative example 3. As can be seen from FIG. 5, both materials exhibited broader D and G peaks, indicating that both carbon materials contained more defective SP at the same time 3 SP with high carbon and graphitization degree 2 And (3) carbon. Through careful analysis, it was found that the amorphous carbon material (GDMC) modified with graphene quantum dots prepared in example 3 was compared with the comparative material (SC) prepared in comparative example 3 D /I G Slightly smaller, indicating a higher order, probably due to the more highly crystalline graphene quantum dots contained in the amorphous carbon phase.
The amorphous carbon material (GDMC) modified with graphene quantum dots in example 3 and the Soft Carbon (SC) not modified with graphene quantum dots prepared in comparative example 3 were prepared into an electrode and a sodium ion battery according to the performance test method of the product prepared in example 1 above, and then were prepared at 10C (1c=300 mAh g -1 ) Electrochemical tests were performed at large current densities and rate performance tests at different current densities. Fig. 6 is a graph of cycle performance (a) and rate performance (b) at room temperature of the amorphous carbon material (GDMC) modified with graphene quantum dots in example 3 and the Soft Carbon (SC) not modified with graphene quantum dots prepared in comparative example 3. As can be seen from fig. 6, at a high current density of 10C, the capacity of both is only about 1/3 of the theoretical specific capacity, which means that the rate performance is poor, and that the soft carbon prepared in example 4 has a poor ion diffusion rate, and in addition, there is a possibility that the soft carbon has a certain relationship with the poor ion diffusion rate of the ester electrolyte. Through the rate performance test, the soft carbon modified by the graphene quantum dots has higher specific capacity under the current density of 30, 50, 300, 600, 1500 and 3000mA/g respectively. The specific capacity of the soft carbon modified by the graphene quantum dots (amorphous carbon material (GDMC) modified by the graphene quantum dots) is improved to a certain extent, and the graphene quantum dots cannot store sodium due to the smaller interlayer spacing, so that the ionic diffusion rate and the electronic conductivity of the graphene quantum dots are improved.
Example 4
An amorphous carbon material modified by carbon dots (a carbon dot modified soft carbon is prepared by a roasting method), and the specific preparation method comprises the following steps:
(1) 2g of citric acid was used as a carbon source of carbon dots, ground to have no granular feel, placed in a beaker, heated at 250 ℃ for 15min, and vigorously stirred with a glass rod to obtain citric acid in a molten state as an amorphous carbon material, and a large amount of carbon dots were formed in the process.
(2) And 2g of asphalt is added into the molten citric acid obtained in the step 1, and the mixture is vigorously stirred, so that the asphalt and the citric acid are uniformly mixed, and the carbon point modified amorphous carbon precursor is obtained.
(3) And (3) placing the carbon-point-modified amorphous carbon precursor obtained in the step (2) in a high-temperature tube furnace for annealing treatment under an argon protective atmosphere (the air flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is increased to 800 ℃ and the heat is preserved for 2 hours), and taking out the carbon-point-modified amorphous carbon precursor after the carbon-point-modified amorphous carbon precursor is naturally cooled to the room temperature to obtain a product, thus obtaining the carbon-point-modified soft carbon (CDSC) prepared by a roasting method.
Comparative example 4
The pure pitch was treated only by step (1) of example 1 to obtain pure pitch-based amorphous carbon (PP).
Performance testing
FIG. 7 is a SEM comparison of soft carbon (CDSC) (a) modified with carbon dots prepared by the calcination method in example 4 and pure pitch-based amorphous carbon (PP) (b) prepared in comparative example 4. As can be seen from fig. 7, the soft carbon (CDSC) surface modified with carbon dots prepared by the firing method of example 4 is more rough and has more uniform protrusions than the pure pitch-based amorphous carbon (PP) of comparative example 4, which may be caused by uniform bonding of carbon dots with pitch.
The soft carbon modified with Carbon Dots (CDSC) of example 4 and the pure pitch-based amorphous carbon (PP) prepared in comparative example 4 were prepared into an electrode and a sodium ion battery according to the method of the performance test of example 1, and then were prepared at 0.1C (1c=300 mAh g -1 ) Electrochemical tests were performed at current densities of (c) and charge and discharge curves are shown in fig. 8. At a current density of 0.1C, it is inclinedThe slope capacity and the first effect are improved obviously. Combining the previous examples, it is speculated that the reason for the increased ramp capacity may be that the distribution of carbon sites over the amorphous carbon increases ion diffusion capacity and electron conductivity, and the first effect of carbon sites on the soft carbon may be that the high graphitization degree of carbon sites reduces open pores and defects on the surface of the amorphous carbon.
Also, the amorphous carbon source in the above embodiments may be any one or more of pitch, coal tar, glucose monohydrate, sucrose, starch, lignin, cellulose, charcoal, phenolic resin, sodium polyacrylate, polytetrafluoroethylene, or urea; the carbon source can be any one or more of animal hair, plant fiber, carbon fiber, graphene, graphite, anthracite, coke, carbon nanotube, urea, citric acid, glucose monohydrate, sucrose, starch, lignin, protein and vitamin; the solvent can be any one or more of water, formamide, isopropanol, N-dimethylformamide, N-methylpyrrolidone and acetone; the heat treatment mode can be solvothermal at 100-250 ℃, inert atmosphere pyrolysis at 500-1500 ℃ and heating evaporation at 40-100 ℃, wherein the inert atmosphere is any one or more of argon, nitrogen, ammonia or hydrogen-argon mixed gas (the volume ratio of hydrogen and argon in the hydrogen-argon mixed gas is 5:95-10:90). The carbon quantum dot dopant can be a nonmetallic compound (such as boric acid, sodium borohydride, urea, melamine, chitosan, polytetrafluoroethylene, polyvinylidene fluoride, sodium polyacrylate, monoammonium phosphate, phytic acid, thiourea or sodium dodecyl benzene sulfonate) containing any one or more elements of boron, nitrogen, oxygen, fluorine, phosphorus or sulfur, the carbon quantum dot can be graphite carbon dots, amorphous carbon dots or the coexisting carbon dots modify amorphous carbon, and the formed amorphous carbon material modified by the carbon dots has the advantages of high electronic conductivity, fast ion diffusion, small interface impedance and the like, and can be widely used for preparing the electrode material of the sodium ion battery.
In summary, the invention discloses an amorphous carbon material modified by carbon dots, wherein carbon dots with the weight percentage of 0.1-10% and the diameter of 5-50 nm are distributed on the surface and/or inside of amorphous carbon. The carbon dots are mainly crystalline carbon with good crystallinity, different graphitization degrees are utilized to have a certain influence on the formation of the SEI film, the inorganic salt and organic matter content of the SEI film can be improved by growing on the surface of amorphous carbon, through regulating and controlling the proportion, the inorganic salt can enable sodium ions to quickly pass through the SEI film, the ion impedance and the interfacial charge transfer impedance are reduced, the organic component content is increased, the mechanical property of the SEI film can be improved, the damage of volume expansion to the SEI film is prevented, the continuous dissolution of inorganic components in electrolyte is slowed down, and the cycle performance is improved; in addition, the growth of carbon dots with higher graphitization degree on the surface of the amorphous carbon reduces the specific surface area and surface defects, so that the first coulombic efficiency of the sodium ion battery is effectively improved. The carbon dots grown inside the amorphous carbon facilitate the transport of ions inside the bulk phase while increasing the electron conductivity, which greatly improves ion diffusion compared to unmodified amorphous carbon materials. The amorphous carbon material modified by carbon dots has the advantages of small specific surface area, few surface defects, high ion diffusion rate, small charge transfer interface impedance and good ion conductivity of the SEI film, can be widely applied to preparing the electrode material of the sodium ion battery, ensures the increase of the initial coulombic efficiency of the material, and effectively improves the specific capacity and the multiplying power performance.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the present invention, which is intended to be covered by the claims of the present invention.
Claims (3)
1. The preparation method of the amorphous carbon material modified by the carbon dots is characterized by comprising the following steps of:
(1) 2g of glucose is taken as an amorphous carbon source to be placed in a high-temperature tube furnace for annealing treatment under the protection of argon, the air flow is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 1200 ℃ and kept for 2 hours, and the amorphous carbon material is obtained after the glucose is naturally cooled to room temperature;
(2) Placing the amorphous carbon material into a planetary ball mill for crushing treatment until the particle size is 0.5-500 um, then placing hard carbon powder obtained by ball milling into 3.5mol/L nitric acid solution, stirring for 30min, carrying out hydrothermal treatment for 1.5h under the reaction condition of 160 ℃, taking out the product after the product is naturally cooled to normal temperature, carrying out suction filtration and washing 3 times by using 1000mL deionized water, and drying overnight in a blast drying oven at 60 ℃ to obtain the amorphous carbon material subjected to hydrothermal acidification treatment;
(3) Uniformly dispersing the amorphous carbon material subjected to hydrothermal acidification in 40mL of formamide solvent, adding 2g of anhydrous citric acid as a carbon point carbon source, adding 1g of boric acid and sodium borate as boron atom doping agents, stirring until the boric acid and the sodium borate are completely dissolved, carrying out hydrothermal reaction for 5 hours at 200 ℃, taking out 1000mL of deionized water and ethanol after the amorphous carbon material is naturally cooled to normal temperature, carrying out suction filtration and washing for 3 times, and drying overnight in a blast drying oven at 60 ℃ to obtain an amorphous carbon precursor modified by carbon points;
(4) And (3) placing the precursor in a high-temperature tube furnace for annealing treatment under the protection of argon, wherein the air flow rate in the treatment process is 50mL/min, the heating rate is 5 ℃/min, the temperature is raised to 1200 ℃ and the heat is preserved for 1h, and taking out the product after the product is naturally cooled to room temperature, thus obtaining the amorphous carbon material modified by carbon points.
2. The amorphous carbon material modified by carbon dots prepared by the preparation method according to claim 1.
3. The use of the amorphous carbon material modified by carbon dots according to claim 2 for preparing a negative electrode material of a sodium ion battery.
Priority Applications (1)
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| CN108832107A (en) * | 2018-06-22 | 2018-11-16 | 江南大学 | Graphene quantum dot-biology base absorbent charcoal composite material and preparation method thereof |
| CN112271402A (en) * | 2020-11-13 | 2021-01-26 | 四川轻化工大学 | Method for preparing carbon-point modified lithium-sulfur battery diaphragm by taking cellulose acetate as carbon source |
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| CN114506836A (en) * | 2022-01-24 | 2022-05-17 | 西南大学 | Hard carbon material with two-stage adsorption characteristics and preparation method and application thereof |
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| CN108832107A (en) * | 2018-06-22 | 2018-11-16 | 江南大学 | Graphene quantum dot-biology base absorbent charcoal composite material and preparation method thereof |
| CN112271402A (en) * | 2020-11-13 | 2021-01-26 | 四川轻化工大学 | Method for preparing carbon-point modified lithium-sulfur battery diaphragm by taking cellulose acetate as carbon source |
| CN113206246A (en) * | 2021-04-27 | 2021-08-03 | 天津理工大学 | Biomass hard carbon negative electrode material of sodium ion battery and preparation method thereof |
| CN114057180A (en) * | 2021-11-22 | 2022-02-18 | 北京化工大学 | Preparation method and application of carbon quantum dot modified PTCDA-based carbon material |
| CN114506836A (en) * | 2022-01-24 | 2022-05-17 | 西南大学 | Hard carbon material with two-stage adsorption characteristics and preparation method and application thereof |
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