CN116040608A - Biomass-based hard carbon material and preparation method and application thereof - Google Patents
Biomass-based hard carbon material and preparation method and application thereof Download PDFInfo
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- CN116040608A CN116040608A CN202310063037.8A CN202310063037A CN116040608A CN 116040608 A CN116040608 A CN 116040608A CN 202310063037 A CN202310063037 A CN 202310063037A CN 116040608 A CN116040608 A CN 116040608A
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- biomass
- hard carbon
- shell
- based hard
- carbon material
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- 239000002028 Biomass Substances 0.000 title claims abstract description 95
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 76
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 45
- 239000002243 precursor Substances 0.000 claims abstract description 42
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000748 compression moulding Methods 0.000 claims abstract description 17
- 238000000746 purification Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 9
- 238000000465 moulding Methods 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims description 5
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 4
- 244000105624 Arachis hypogaea Species 0.000 claims description 4
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 4
- 235000018262 Arachis monticola Nutrition 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 240000007817 Olea europaea Species 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 4
- 150000003863 ammonium salts Chemical class 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 235000020232 peanut Nutrition 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 claims description 4
- 239000002023 wood Substances 0.000 claims description 4
- 244000144730 Amygdalus persica Species 0.000 claims description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- 244000060011 Cocos nucifera Species 0.000 claims description 3
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 3
- 240000009226 Corylus americana Species 0.000 claims description 3
- 235000001543 Corylus americana Nutrition 0.000 claims description 3
- 235000007466 Corylus avellana Nutrition 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 3
- 240000007049 Juglans regia Species 0.000 claims description 3
- 235000009496 Juglans regia Nutrition 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- 244000082204 Phyllostachys viridis Species 0.000 claims description 3
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 3
- 235000008331 Pinus X rigitaeda Nutrition 0.000 claims description 3
- 235000011613 Pinus brutia Nutrition 0.000 claims description 3
- 241000018646 Pinus brutia Species 0.000 claims description 3
- 240000006711 Pistacia vera Species 0.000 claims description 3
- 235000003447 Pistacia vera Nutrition 0.000 claims description 3
- 244000018633 Prunus armeniaca Species 0.000 claims description 3
- 235000009827 Prunus armeniaca Nutrition 0.000 claims description 3
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 3
- 244000269722 Thea sinensis Species 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000014571 nuts Nutrition 0.000 claims description 3
- 235000020233 pistachio Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000010902 straw Substances 0.000 claims description 3
- 235000020234 walnut Nutrition 0.000 claims description 3
- 239000011229 interlayer Substances 0.000 claims description 2
- 239000002019 doping agent Substances 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 14
- 239000007773 negative electrode material Substances 0.000 abstract description 9
- 238000001125 extrusion Methods 0.000 abstract description 5
- 230000035515 penetration Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- 238000012360 testing method Methods 0.000 description 16
- 239000002245 particle Substances 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 240000008042 Zea mays Species 0.000 description 3
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000005822 corn Nutrition 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012445 acidic reagent Substances 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 239000006012 monoammonium phosphate Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 239000004114 Ammonium polyphosphate Substances 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910016523 CuKa Inorganic materials 0.000 description 1
- 239000005696 Diammonium phosphate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 244000126002 Ziziphus vulgaris Species 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 description 1
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 1
- 229920001276 ammonium polyphosphate Polymers 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 description 1
- 239000004137 magnesium phosphate Substances 0.000 description 1
- 229910000157 magnesium phosphate Inorganic materials 0.000 description 1
- 229960002261 magnesium phosphate Drugs 0.000 description 1
- 235000010994 magnesium phosphates Nutrition 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Classifications
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- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a biomass-based hard carbon material, a preparation method and application thereof, and belongs to the technical field of negative electrode materials. The preparation method of the biomass-based hard carbon material provided by the invention comprises the following steps: mixing a biomass raw material and a doping source, and performing compression molding to obtain a first precursor; sequentially performing first sintering and purification on the first precursor to obtain a second precursor; performing second sintering on the second precursor to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900-1600 ℃. According to the invention, the biomass raw material and the doping source are subjected to compression molding, and in the compression molding process, the guide pipe and the screen pipe inside the biomass raw material are damaged due to extrusion, so that the penetration of doping elements is facilitated, the doping source and the carbonaceous material can be effectively combined by matching with the sintering process, and the prepared biomass-based hard carbon material is used as a secondary battery negative electrode material, and has high first reversible capacity and first coulombic efficiency.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to a biomass-based hard carbon material, and a preparation method and application thereof.
Background
The hard carbon material has the advantages of rich raw material reserves and low cost, and has good application prospect when being used as a negative electrode material; however, the hard carbon negative electrode also faces the problems of low first-week coulombic efficiency, insufficient long-cycle stability, poor rate performance and the like in practical application, and in recent years, many researchers are devoted to the research on the performance optimization of the hard carbon negative electrode.
Biomass raw materials are rich in sources and low in cost, so that the biomass raw materials become one of the carbonaceous raw materials with the most application prospect. The performance improvement direction of the hard carbon material at present mainly comprises structure regulation, morphology design, interface structure, electrolyte optimization and the like, and element doping is one of methods for improving the hard carbon performance. In the prior art, the element doping mode is generally to directly stir and mix the biomass raw material and the doping source, and then sinter the mixture to prepare the biomass-based hard carbon material containing the doping element. However, the doping element is difficult to effectively dope by adopting the method, and the first reversible capacity and the first coulomb efficiency are low when the biomass-based hard carbon material containing the doping element is used as a negative electrode material.
Disclosure of Invention
The invention aims to provide a biomass-based hard carbon material, a preparation method and application thereof, and the method provided by the invention can be used for effectively doping elements, so that the prepared biomass-based hard carbon material has higher first reversible capacity and first coulombic efficiency when being used as a secondary battery negative electrode material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the preparation method of the biomass-based hard carbon material comprises the following steps:
mixing a biomass raw material and a doping source, and performing compression molding to obtain a first precursor;
sequentially performing first sintering and purification on the first precursor to obtain a second precursor;
performing second sintering on the second precursor to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900-1600 ℃.
Preferably, the pressure of the compression molding is 2-10 MPa; the time of the compression molding is 1-15 s.
Preferably, the biomass raw material comprises one or more of olive shell, hawaii shell, apricot shell, walnut shell, rice hull, peach shell, oil tea shell, pistachio shell, pine nut shell, peanut shell, coconut shell, jujube shell, hazelnut shell, cotton seed shell, li Ke, wood, corncob, bamboo and straw.
Preferably, the doping source comprises one or more of ammonium salt, phosphate, sulfate, sulfite, thiosulfate, urea, melamine, red phosphorus, sulfur and thiourea.
Preferably, the mass ratio of the biomass raw material to the doping source is 1:0.01 to 0.15.
Preferably, the temperature of the first sintering is 350-900 ℃; the time of the first sintering is 2-10 h.
Preferably, the purification comprises water washing and/or acid washing.
Preferably, the heat preservation time of the second sintering is 1-9.5 h.
The invention also provides the biomass-based hard carbon material prepared by the preparation method, which comprises a carbonaceous material and doping elements doped on the surface of the carbonaceous material and in the pore canal, wherein the specific surface area of the biomass-based hard carbon material is 1.5-25 m 2 And/g, wherein the interlayer spacing of the 002 surface of the biomass-based hard carbon material is 0.36-0.42 nm.
The invention also provides application of the biomass-based hard carbon material in the secondary battery anode material.
The invention provides a preparation method of a biomass-based hard carbon material, which comprises the following steps: mixing a biomass raw material and a doping source, and performing compression molding to obtain a first precursor; sequentially performing first sintering and purification on the first precursor to obtain a second precursor; performing second sintering on the second precursor to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900-1600 ℃. According to the invention, the biomass raw material and the doping source are subjected to compression molding, and in the compression molding process, the guide pipe and the screen pipe inside the biomass raw material are damaged due to extrusion, so that the penetration of doping elements is facilitated, the doping source and the biomass raw material can be effectively combined by matching with the sintering process, and the prepared biomass-based hard carbon material is used as a secondary battery negative electrode material, and has high first reversible capacity and first coulombic efficiency. The example result shows that the biomass-based hard carbon material prepared by the invention is used as a negative electrode material, and the first reversible capacity is larger than 315mAh/g; in addition, in the ion battery test system, the initial coulombic efficiency is greater than 88%. Meanwhile, the biomass-based hard carbon material is prepared by using low-cost raw materials, and the preparation process and equipment are mature, so that the biomass-based hard carbon material is suitable for large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the drawings that are needed in the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an EDS analysis chart of a biomass-based hard carbon material prepared in example 1 of the present invention;
fig. 2 is a graph showing the first charge and discharge of the biomass-based hard carbon material prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a biomass-based hard carbon material, which comprises the following steps:
mixing a biomass raw material and a doping source, and performing compression molding to obtain a first precursor;
sequentially performing first sintering and purification on the first precursor to obtain a second precursor;
performing second sintering on the second precursor to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900-1600 ℃.
In the present invention, each of the preparation raw materials used is a commercially available product well known to those skilled in the art unless specified otherwise.
The method comprises the steps of mixing a biomass raw material with a doping source, and performing compression molding to obtain a first precursor. In the present invention, the biomass raw material preferably includes one or more of olive shell, hawaii shell, apricot shell, walnut shell, rice hull, peach shell, oil tea shell, pistachio shell, pine nut shell, peanut shell, coconut shell, date shell, hazelnut shell, cotton seed shell, li Ke, wood, corncob, bamboo and straw.
In the present invention, the doping source preferably includes one or more of ammonium salt, phosphate, sulfate, sulfite, thiosulfate, urea, melamine, red phosphorus, sulfur and thiourea. In the present invention, the ammonium salt is preferably one or more of ammonium chloride, ammonium carbonate, ammonium bicarbonate, ammonium acetate, ammonium oxalate, diammonium phosphate, monoammonium phosphate, ammonium polyphosphate and ammonium sulfate; the phosphate is preferably calcium phosphate and/or magnesium phosphate; the sulfate is preferably one or more of calcium sulfate, zinc sulfate and magnesium sulfate; the sulfite is preferably sodium sulfite and the thiosulfate is preferably sodium thiosulfate.
In the invention, the mass ratio of the biomass raw material to the doping source is preferably 1:0.01 to 0.15, more preferably 1:0.04 to 0.1, more preferably 1:0.05 to 0.06.
In the present invention, the press forming means is preferably one or more of screw extrusion, mechanical punching and hydraulic punching. In the present invention, the pressure of the press molding is preferably 2 to 10MPa, more preferably 2.5 to 5MPa, still more preferably 3.5 to 4MPa; the time for the press molding is preferably 1 to 15 seconds, more preferably 2 to 7 seconds, and still more preferably 3 to 5 seconds. In the compression molding process, the guide pipe and the screen pipe inside the biomass raw material are damaged due to extrusion, so that the infiltration of doping elements is facilitated.
Before the biomass raw material and the doping source are mixed, the method preferably further comprises the steps of crushing the biomass raw material to obtain biomass raw material particles; the average particle diameter of the biomass raw material particles is preferably not more than 600. Mu.m, more preferably 100 to 500. Mu.m, still more preferably 200 to 300. Mu.m. The crushing mode is not particularly limited in the present invention, and the required particle size may be achieved.
The mixing mode of the biomass raw material and the doping source is not particularly limited, and a mode well known to a person skilled in the art can be adopted.
After the first precursor is obtained, the first precursor is subjected to first sintering and purification in sequence to obtain a second precursor. In the present invention, the temperature of the first sintering is preferably 350 to 900 ℃, more preferably 500 to 650 ℃, still more preferably 550 to 600 ℃; the holding time of the first sintering is preferably 2 to 10 hours, more preferably 2 to 4 hours, and still more preferably 2.5 to 3 hours. In the present invention, the first sintering is preferably performed in a protective atmosphere; the shielding gas for providing the shielding atmosphere is preferably one of nitrogen, helium, neon and argon, more preferably nitrogen.
In the present invention, the purification preferably includes washing with water and/or acid, more preferably washing with acid and washing with water sequentially. In the present invention, the acid reagent used for the acid washing preferably includes one or more of hydrofluoric acid, sulfurous acid, phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid, aqueous citric acid, aqueous acetic acid and aqueous oxalic acid, more preferably hydrochloric acid or aqueous citric acid; the concentration of the acid reagent is preferably 0.2 to 2mol/L, more preferably 0.5 to 1.5mol/L, and even more preferably 1mol/L. In the invention, deionized water is preferably used for the water washing; the water washing is preferably to be neutral. In the present invention, the purification has the effect of removing calcium, magnesium and magnetic substances (e.g., iron, cobalt, nickel) from the biomass feedstock.
In the present invention, the first sintering and purifying preferably further comprises: and carrying out particle shaping on the material obtained after the first sintering. In the present invention, the particle shaping preferably includes sequentially pulverizing and classifying. In the present invention, the equipment used for the pulverization is preferably one or two of a jaw crusher, a roller crusher, a twin roller crusher, a hammer crusher, an impact crusher, a vertical crusher, and a pneumatic pulverizer, more preferably a pneumatic pulverizer; the apparatus used for the classification is preferably a classifier. In the present invention, the pulverization is preferably performed so that the material particle size D50 is 3 to 20. Mu.m, more preferably 4 to 15. Mu.m, still more preferably 5 to 10. Mu.m; the classification is preferably carried out so that the particle size D10 of the material is not less than 3. Mu.m, more preferably 3.2 to 5.5. Mu.m, still more preferably 3.3 to 4.5. Mu.m.
In the present invention, the purification preferably further comprises drying the purified material. In the present invention, the drying temperature is preferably 80 to 120 ℃, more preferably 85 to 105 ℃, and even more preferably 95 to 100 ℃. The drying method of the present invention is not particularly limited, and may be any method known to those skilled in the art.
After a second precursor is obtained, the second precursor is subjected to second sintering to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900 to 1600 ℃, preferably 1150 to 1450 ℃, and more preferably 1250 to 1300 ℃. In the present invention, the holding time of the second sintering is preferably 1 to 9.5 hours, more preferably 1.5 to 4.5 hours, and still more preferably 3 to 3.5 hours. In the present invention, the second sintering is preferably performed in a protective atmosphere; the shielding gas for providing the shielding atmosphere is preferably one of nitrogen, helium, neon and argon, more preferably nitrogen. The invention also provides the biomass-based hard carbon material prepared by the preparation method, which comprises a carbonaceous material and doping elements doped on the surface and in pore channels of the carbonaceous material, wherein the specific surface area of the biomass-based hard carbon material is 1.5-25 m 2 Preferably 4.7 to 6.8m 2 Preferably 5.9 to 6.3m 2 /g; the biomass-based hard carbon materialThe layer spacing of the 002 face of (C) is 0.36 to 0.42nm, preferably 0.37 to 0.39nm; the biomass-based hard carbon material preferably has a median particle diameter D50 of 3 to 20 μm, more preferably 7.2 to 9.8 μm, and still more preferably 7.9 to 8.9 μm.
The invention also provides application of the biomass-based hard carbon material in the secondary battery anode material.
In the present invention, the secondary battery preferably includes a lithium ion secondary battery, a sodium ion secondary battery, a potassium ion secondary battery, a super capacitor, or a nickel hydrogen battery, more preferably a lithium ion secondary battery or a sodium ion secondary battery.
For further explanation of the present invention, the biomass-based hard carbon materials provided by the present invention are described in detail below with reference to the accompanying drawings and examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Weighing 3kg of corn stalks, crushing the corn stalks to an average grain size of 300 mu m, and uniformly mixing the corn stalks with 150g of red phosphorus to obtain a mixture; pressing and forming the mixture for 5s under the pressure condition of 5MPa by adopting mechanical stamping to obtain 3.1kg of a first precursor;
the first precursor is subjected to first sintering for 3 hours in a nitrogen atmosphere at 500 ℃ and cooled to room temperature to obtain 1.1kg of sintered material;
crushing the sintered material by a jaw crusher until the material granularity D50 is 8.2 mu m, crushing by a jet mill, classifying to obtain the material granularity D10 of 3.3 mu m, pickling the obtained material by a citric acid aqueous solution with the concentration of 1mol/L, and drying at 100 ℃ to obtain 1.05kg of a second precursor;
and (3) carrying out second sintering on the second precursor in nitrogen atmosphere at 1300 ℃ for 1.5h, and cooling to room temperature to obtain 0.94kg of biomass-based hard carbon material.
Example 2
Weighing 5kg of peanut shells, crushing to an average particle size of 500 mu m, and uniformly mixing with 500g of monoammonium phosphate to obtain a mixture; the mixture is pressed and molded for 7s under the pressure condition of 3.5MPa by adopting screw extrusion, so as to obtain 5.5kg of first precursor;
the first precursor is subjected to first sintering for 2.5 hours in a nitrogen atmosphere at 550 ℃ and cooled to room temperature to obtain 1.6kg of sintered materials;
crushing the sintered material by a jaw crusher until the material granularity D50 is 10.3 mu m, crushing by a jet mill, classifying to obtain the material granularity D10 of 4.1 mu m, pickling the obtained material by hydrochloric acid with the concentration of 1mol/L, washing by deionized water until the filtrate is neutral, and drying at 100 ℃ to obtain 1.5kg of a second precursor;
and (3) carrying out second sintering on the second precursor in nitrogen atmosphere at 1450 ℃ for 3 hours, and cooling to room temperature to obtain 1.3kg of biomass-based hard carbon material.
Example 3
Weighing 5kg of olive shells, crushing to an average particle size of 100 mu m, and uniformly mixing with 200g of sulfur to obtain a mixture; pressing and molding the mixture for 5s under the pressure of 2.5MPa by adopting mechanical backlog to obtain 5.2kg of a first precursor;
the first precursor is subjected to heat preservation in a nitrogen atmosphere at 650 ℃ for first sintering for 2 hours, and cooled to room temperature to obtain 1.4kg of sintered materials;
crushing the sintered material by adopting a jaw crusher until the material granularity D50 is 7.8 mu m, crushing by adopting a jet mill, classifying to obtain the material granularity D10 of 3.2 mu m, washing the obtained material by adopting deionized water until the filtrate is neutral, and drying at 95 ℃ to obtain 1.35kg of a second precursor;
and (3) carrying out second sintering on the second precursor in nitrogen atmosphere at 1250 ℃ for 3.5 hours, and cooling to room temperature to obtain 1.16kg of biomass-based hard carbon material.
Example 4
Weighing 5kg of wood, crushing to an average particle size of 600 mu m, and uniformly mixing with 300g of melamine to obtain a mixture; pressing and forming the mixture for 2s under the pressure of 4MPa by adopting mechanical backlog to obtain 6.3kg of first precursor;
the first precursor is subjected to first sintering for 4 hours in a nitrogen atmosphere at 600 ℃ and cooled to room temperature to obtain 1.6kg of sintered materials;
crushing the sintered material by adopting a jaw crusher until the material granularity D50 is 9.4 mu m, crushing by adopting a jet mill, classifying to obtain the material granularity D10 of 3.7 mu m, washing the obtained material by adopting deionized water until the filtrate is neutral, and drying at 95 ℃ to obtain 1.55kg of a second precursor;
and (3) carrying out second sintering on the second precursor in nitrogen atmosphere at 1150 ℃ for 4.5 hours, and cooling to room temperature to obtain 1.33kg of biomass-based hard carbon material.
Comparative example 1
Biomass-based hard carbon materials were prepared by the method of reference example 1, except that the press molding process was omitted.
Comparative example 2
Biomass-based hard carbon material was prepared by the method of reference example 1, except that a doping source (red phosphorus) was not added.
Comparative example 3
Biomass-based hard carbon material was prepared by the method of reference example 1, except that the purification treatment (acid washing) was not performed after the first sintering.
Comparative example 4
Biomass-based hard carbon material was prepared according to the method of example 1, except that the temperature of the second sintering was 850 ℃.
Test example 1
The biomass-based hard carbon material prepared in example 1 was subjected to EDS analysis by JSM-7160 scanning electron microscopy spectrometer of japan electronics company, and the EDS result is shown in fig. 1, and it is clear from fig. 1 that the biomass-based hard carbon material prepared in example 1 was subjected to effective phosphorus doping.
Test example 2
The biomass-based hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 4 were tested for median particle size using a dandong Baite laser particle sizer BT-9300ST, and the results are shown in Table 1.
Test example 3
The specific surface areas of the biomass-based hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 4 were measured using Kang Da NOVA4000e in U.S. a, and the results are shown in table 1.
Test example 4
XRD detection was performed on the biomass-based hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 4, with the wavelength of CuKa rays set to 0.15418nm, and the d002 face layer spacing was calculated according to formula I, and the results are shown in Table 1.
d002 Formula I =λ/(2sinθ);
where λ is the wavelength of the X-ray (cuka=0.15418); θ is the diffraction angle.
Table 1 performance parameters of the biomass-based hard carbon materials prepared in examples 1 to 4 and comparative examples 1 to 4
As is clear from table 1, the doping element cannot be doped into the carbonaceous material bulk phase effectively without performing the press molding process, resulting in significantly lower 002-face carbon layer spacing, which proves that the present invention can effectively increase 002-face carbon layer spacing by employing the press molding process.
Test example 5
The biomass-based hard carbon materials obtained in examples 1 to 4 and comparative examples 1 to 4, conductive carbon black and a binder are mixed in pure water according to a mass ratio of 96:1:3, and uniformly stirred to obtain homogenate, wherein the solid content of the homogenate is 48%, the homogenate is coated on a copper foil current collector, and the copper foil current collector is subjected to vacuum baking at 105 ℃ for 6 hours, and after compression molding, a negative electrode plate is prepared through punching. The button half cell is assembled in a glove box filled with argon, the counter electrode is a metal lithium sheet, the diaphragm used is PE, and the electrolyte is NaPF of 1mol/L 6 Solutions (solvent is a 1:1 EC to DMC mixture by volume). The button half cell is subjected to charge and discharge test (the test equipment is LAND battery test system of blue electric electronic Co., ltd.) and the test flow is carried out0.2C DC to 0V,0.05C DC to 0V,0V CV 50. Mu.A, 0.01C DC to 0V,0V CV 20. Mu.A, rest 10min,0.2C CC to 2V. The first reversible capacity and first coulombic efficiency of the biomass-based hard carbon materials in the examples and comparative examples were measured, and the results are shown in fig. 2 and table 2.
The button cell test equipment is LAND cell test system of Wuhan city blue electric electronic Co.
Table 2 data for electrochemical performance test of anode materials in examples 1 to 4 and comparative examples 1 to 4
| Biomass-based hard carbon material source | First reversible capacity (mAh/g) | First coulombic efficiency (%) |
| Example 1 | 317 | 91.5 |
| Example 2 | 322 | 89.9 |
| Example 3 | 325 | 90.6 |
| Example 4 | 321 | 90.1 |
| Comparative example 1 | 297 | 87.7 |
| Comparative example 2 | 285 | 83.7 |
| Comparative example 3 | 277 | 85.6 |
| Comparative example 4 | 259 | 78.3 |
Fig. 2 is a graph of the first charge and discharge of the biomass-based hard carbon material prepared in example 1 of the present invention, and as can be seen from fig. 2, the hard carbon negative electrode material prepared in example 1 has a higher platform capacity.
From the results in table 2, comparative example 1 and comparative example 1 revealed that the first reversible capacity of the prepared biomass-based hard carbon material was only 297mAh/g, and the first coulombic efficiency was 87.7% without compression molding. From the test results, the first reversible capacity and the first coulombic efficiency of the biomass-based hard carbon material can be effectively improved by adopting the compression molding process.
As can be seen from comparison of example 1 and comparative example 2, the biomass-based hard carbon material prepared without any doping source treatment had a capacity of only 285mAh/g and a first coulombic efficiency of 83.7%. From the test results, the element doping of the carbon raw material can effectively improve the first reversible capacity and the first coulombic efficiency of the biomass-based hard carbon material.
As is clear from comparison between example 1 and comparative example 3, the prepared biomass-based hard carbon material has a high content of impurities such as magnetic foreign matters without purification treatment, the reversible capacity and the first effect of the prepared biomass-based hard carbon material are obviously reduced, the reversible capacity is 277mAh/g, and the first coulomb efficiency is 85.6%. From the test results, the first reversible capacity and the first coulombic efficiency of the biomass-based hard carbon material can be effectively improved by purifying the biomass raw material.
Comparing example 1 with comparative example 4, it is seen that the second sintering temperature is too high, and the capacity of the prepared biomass-based hard carbon material is only 259mAh/g, and the initial coulombic efficiency is 78.3%. From the above test results, it is known that the first reversible capacity and the first coulombic efficiency of the biomass-based hard carbon material can be effectively improved by controlling the temperature of the second sintering within the range of the present invention.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, it should be understood that other embodiments may be devised in accordance with the present embodiments without departing from the spirit and scope of the invention.
Claims (10)
1. The preparation method of the biomass-based hard carbon material comprises the following steps:
mixing a biomass raw material and a doping source, and performing compression molding to obtain a first precursor;
sequentially performing first sintering and purification on the first precursor to obtain a second precursor;
performing second sintering on the second precursor to obtain a biomass-based hard carbon material; the temperature of the second sintering is 900-1600 ℃.
2. The method according to claim 1, wherein the pressure of the press molding is 2 to 10MPa; the time of the compression molding is 1-15 s.
3. The method of claim 1, wherein the biomass feedstock comprises one or more of olive shell, hawaii shell, apricot shell, walnut shell, rice hull, peach shell, oil tea shell, pistachio shell, pine nut shell, peanut shell, coconut shell, date shell, hazelnut shell, cotton seed shell, li Ke, wood, corncob, bamboo, and straw.
4. The method of claim 1, wherein the doping source comprises one or more of ammonium salt, phosphate, sulfate, sulfite, thiosulfate, urea, melamine, red phosphorus, sulfur, and thiourea.
5. The method of claim 1, 3 or 4, wherein the mass ratio of biomass feedstock to dopant source is 1:0.01 to 0.15.
6. The method of claim 1, wherein the first sintering temperature is 350-900 ℃; the heat preservation time of the first sintering is 2-10 h.
7. The method of claim 1, wherein the purifying comprises water washing and/or acid washing.
8. The method according to claim 1, wherein the second sintering is performed for a holding time of 1 to 9.5 hours.
9. The biomass-based hard carbon material prepared by the preparation method of any one of claims 1 to 8, which comprises a carbonaceous material and doping elements doped on the surface and in pore channels of the carbonaceous material, wherein the specific surface area of the biomass-based hard carbon material is 1.5 to 25m 2 And/g, wherein the interlayer spacing of the 002 surface of the biomass-based hard carbon material is 0.36-0.42 nm.
10. The use of the biomass-based hard carbon material according to claim 9 in a secondary battery anode material.
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