CN117293312A - Hard carbon material, preparation method and application thereof, and sodium ion battery - Google Patents
Hard carbon material, preparation method and application thereof, and sodium ion battery Download PDFInfo
- Publication number
- CN117293312A CN117293312A CN202311579178.1A CN202311579178A CN117293312A CN 117293312 A CN117293312 A CN 117293312A CN 202311579178 A CN202311579178 A CN 202311579178A CN 117293312 A CN117293312 A CN 117293312A
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- CN
- China
- Prior art keywords
- hard carbon
- carbon material
- temperature
- sintering
- heating rate
- Prior art date
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- Granted
Links
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 137
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 132
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 56
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 63
- 238000005245 sintering Methods 0.000 claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 36
- 239000005539 carbonized material Substances 0.000 claims abstract description 35
- 239000002243 precursor Substances 0.000 claims abstract description 35
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- 239000000047 product Substances 0.000 claims description 45
- 238000000034 method Methods 0.000 claims description 25
- 238000012360 testing method Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 20
- 239000012298 atmosphere Substances 0.000 claims description 19
- 239000011148 porous material Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 16
- 239000012071 phase Substances 0.000 claims description 16
- 239000007790 solid phase Substances 0.000 claims description 16
- 230000003213 activating effect Effects 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 238000004321 preservation Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 238000012216 screening Methods 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 238000001069 Raman spectroscopy Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000001237 Raman spectrum Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003570 air Substances 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 229910052743 krypton Inorganic materials 0.000 claims description 5
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007773 negative electrode material Substances 0.000 claims description 5
- 229910052754 neon Inorganic materials 0.000 claims description 5
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052724 xenon Inorganic materials 0.000 claims description 5
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 241000196324 Embryophyta Species 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 230000002950 deficient Effects 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 238000000746 purification Methods 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 150000001720 carbohydrates Chemical class 0.000 claims description 3
- 235000014633 carbohydrates Nutrition 0.000 claims description 3
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 239000009719 polyimide resin Substances 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 235000011181 potassium carbonates Nutrition 0.000 claims description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 3
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 244000144725 Amygdalus communis Species 0.000 claims description 2
- 235000011437 Amygdalus communis Nutrition 0.000 claims description 2
- 244000144730 Amygdalus persica Species 0.000 claims description 2
- 235000017060 Arachis glabrata Nutrition 0.000 claims description 2
- 244000105624 Arachis hypogaea Species 0.000 claims description 2
- 235000010777 Arachis hypogaea Nutrition 0.000 claims description 2
- 235000018262 Arachis monticola Nutrition 0.000 claims description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 2
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 2
- 241001070941 Castanea Species 0.000 claims description 2
- 235000014036 Castanea Nutrition 0.000 claims description 2
- 244000060011 Cocos nucifera Species 0.000 claims description 2
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 2
- 240000009226 Corylus americana Species 0.000 claims description 2
- 235000001543 Corylus americana Nutrition 0.000 claims description 2
- 235000007466 Corylus avellana Nutrition 0.000 claims description 2
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 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 2
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 238000004566 IR spectroscopy Methods 0.000 claims description 2
- 240000007049 Juglans regia Species 0.000 claims description 2
- 235000009496 Juglans regia Nutrition 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000004640 Melamine resin Substances 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 244000082204 Phyllostachys viridis Species 0.000 claims description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 2
- 240000006711 Pistacia vera Species 0.000 claims description 2
- 235000003447 Pistacia vera Nutrition 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 235000006040 Prunus persica var persica Nutrition 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229920002472 Starch Polymers 0.000 claims description 2
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 2
- 244000126002 Ziziphus vulgaris Species 0.000 claims description 2
- 235000020224 almond Nutrition 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000011425 bamboo Substances 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000010902 jet-milling Methods 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 229920005610 lignin Polymers 0.000 claims description 2
- RCHKEJKUUXXBSM-UHFFFAOYSA-N n-benzyl-2-(3-formylindol-1-yl)acetamide Chemical compound C12=CC=CC=C2C(C=O)=CN1CC(=O)NCC1=CC=CC=C1 RCHKEJKUUXXBSM-UHFFFAOYSA-N 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920000368 omega-hydroxypoly(furan-2,5-diylmethylene) polymer Polymers 0.000 claims description 2
- 235000020232 peanut Nutrition 0.000 claims description 2
- 229920001568 phenolic resin Polymers 0.000 claims description 2
- 239000005011 phenolic resin Substances 0.000 claims description 2
- 235000020233 pistachio Nutrition 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 229920001225 polyester resin Polymers 0.000 claims description 2
- 239000004645 polyester resin Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920005672 polyolefin resin Polymers 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims description 2
- 229910001950 potassium oxide Inorganic materials 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 claims description 2
- 239000012264 purified product Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 235000020234 walnut Nutrition 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims description 2
- 239000013081 microcrystal Substances 0.000 claims 1
- 230000002441 reversible effect Effects 0.000 abstract description 8
- 230000000052 comparative effect Effects 0.000 description 36
- 238000001354 calcination Methods 0.000 description 19
- 238000001816 cooling Methods 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 230000032258 transport Effects 0.000 description 3
- 229920000936 Agarose Polymers 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000033228 biological regulation Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000208467 Macadamia Species 0.000 description 1
- 244000018633 Prunus armeniaca Species 0.000 description 1
- 235000009827 Prunus armeniaca Nutrition 0.000 description 1
- JETSKDPKURDVNI-UHFFFAOYSA-N [C].[Ca] Chemical compound [C].[Ca] JETSKDPKURDVNI-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- -1 nitrogen-bromine-calcium Chemical compound 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000006903 response to temperature Effects 0.000 description 1
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- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—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
-
- 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
-
- 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
- C01B32/20—Graphite
- C01B32/205—Preparation
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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Abstract
The invention provides a hard carbon material, a preparation method and application thereof, and a sodium ion battery. The preparation method comprises the following steps: sequentially carbonizing, crushing and purifying a carbon source to obtain a carbonized material precursor; sequentially sintering the carbonized material precursor at low temperature Duan Shaojie and high temperature, and performing post-treatment to obtain a hard carbon material; the low temperature Duan Shaojie adopts a first heating rate and a first sintering temperature, the high temperature section sintering adopts a second heating rate and a second sintering temperature, the first heating rate is higher than the second heating rate by more than 4.5 ℃/min, and the first sintering temperature is lower than the second sintering temperature by more than 200 ℃. The preparation method can obtain the hard carbon material with small domain size and low oxygen content, and the sodium ion battery based on the hard carbon material has higher reversible capacity, high first coulomb efficiency and good dynamic performance.
Description
Technical Field
The invention belongs to the technical field of carbon materials, and particularly relates to a hard carbon material, a preparation method and application thereof, and a sodium ion battery.
Background
In recent years, lithium electricity price has rapidly increased, and the problem of insufficient lithium ore resources faced in the field of large-scale application has been getting worse. Sodium Ion Batteries (SIBs) rely on sodium resources that are lower cost and more abundant than lithium batteries, and are widely recognized as the most competitive alternatives to lithium ion batteries. The graphite cathode materials commonly used in lithium ion batteries have very low sodium storage capacity and are not suitable for sodium ion battery systems. The hard carbon material has a long and highly reversible plateau region (< 0.1V), so that its performance in sodium ion batteries is relatively similar to that of graphite in lithium ion batteries, and is one of the preferred negative electrode materials for sodium ion batteries.
However, the application of the hard carbon material in the sodium ion full battery still has some challenges, wherein the main thing is that the hard carbon material has poor dynamic performance, is difficult to be compatible with high capacity and high rate performance, and has great hidden danger of sodium precipitation. Aiming at the problems, the CN115347185A is doped with N, br and Ca to exert the synergistic effect of three anions and cations co-doping, increase the interlayer spacing of the hard carbon, cause defect sites, improve the embedding capacity and the adsorption capacity of the hard carbon material and improve the multiplying power performance of the material; meanwhile, by introducing calcium-carbon ionic bonds and combining three ions, the multiplying power performance of the material is further improved, so that the nitrogen-bromine-calcium co-doped hard carbon material has good charge-discharge cycling stability under a large multiplying power. However, doping of the hetero atoms can have a certain improvement effect on the rate performance, but the doping process is complex, the efficiency is lower, and meanwhile, the cost of doping auxiliary materials is increased, so that the hard carbon material loses the cost advantage of the hard carbon material. And the sodium storage capacity provided by the heteroatom defect is poor in reversibility and poor in cycle performance. CN114524433a utilizes the characteristic that agarose can form gel state, so that agarose and template agent form a highly dispersed integral structure, then the use amount of different template agents is regulated to realize the optimal regulation of pore diameter and number of pores, and further the specific surface area and defect sites of porous carbon are regulated, so that unnecessary specific surface area and defect sites are reduced, and the hierarchical porous structure hard carbon material is obtained. Although the construction of the pore structure of the hard carbon material can improve the sodium storage capacity, the pore diameter suitable for sodium ion storage has stricter requirements, and the oversized pore structure has poor dynamic performance and poor reversibility, so that the multiplying power performance and the cycle performance of the pore structure are poor, and therefore, the means for constructing the multistage pore structure is not suitable for the hard carbon material for sodium ion storage.
Therefore, providing a hard carbon material for sodium ion batteries with good rate capability and fast dynamic process is one of the problems to be solved in the field.
Disclosure of Invention
In order to solve all or part of the technical problems, the invention provides the following technical scheme:
one of the objects of the present invention is to provide a hard carbon material in which the domain size of graphite crystallites isL a Less than 50 and nm, and the oxygen element content delta is less than 10 percent;
wherein,L a is obtained by carrying out Raman spectrum test on the hard carbon material,L a =(2.4*10 -10 )λ nm 4 (I G /I D )，I G is a Raman shift of 1500cm in Raman spectrum -1 ～1650cm -1 Peak intensity of G peak appearing in the range of (I) D Is a Raman shift of 1300cm in Raman spectrum -1 ～1400cm -1 Peak intensity of D peak appearing in range lambda nm A wavelength of light emitted by the raman light source;
delta is by converting the hard carbon material to CO 2 And then measured by infrared spectroscopy.
The storage of sodium ions from the outside of the hard carbon material to the inside of the pore structure of the hard carbon material needs to undergo the transportation of crystal domains, and in the range of the crystal domain size La of the hard carbon material provided by the invention, the transportation of sodium ions can be accelerated, so that the carbon material has a rapid sodium ion transmission dynamic process; oxygen element plays a role in blocking sodium ion transmission, and the small-domain hard carbon material with the oxygen element content within the range further increases the sodium ion transmission efficiency.
In some embodiments, delta < 2%,L a < 11.5 nm. When the small-domain hard carbon material with the domain size and the oxygen element characteristics is used as a negative electrode material of the sodium ion battery, the assembled sodium ion battery has higher reversible capacity, first coulomb efficiency and quick dynamic process.
In some embodiments, dQ/dV is greater than 0.53V in a discharge curve obtained by performing a constant current charge-discharge test on the hard carbon material. The hard carbon material provided by the invention has higher platform voltage passing constant-current charge and discharge tests.
The second object of the present invention is to provide a method for producing a hard carbon material, the method comprising:
sequentially carbonizing, crushing and purifying a carbon source to obtain a carbonized material precursor;
sequentially sintering the carbonized material precursor at low temperature Duan Shaojie and high temperature, and performing post-treatment to obtain a hard carbon material;
the low temperature Duan Shaojie adopts a first heating rate and a first sintering temperature, the high temperature section sintering adopts a second heating rate and a second sintering temperature, the first heating rate is higher than the second heating rate by more than 4.5 ℃/min, and the first sintering temperature is lower than the second sintering temperature by more than 200 ℃.
The preparation method can regulate and control the domain size and the oxygen content of the carbon material at the same time, and improve the dynamic performance of the hard carbon material, so that the sodium ion battery based on the hard carbon material has high capacity and high multiplying power. According to the invention, the growth of the hard carbon material in La and Lc directions is different in response to temperature, la has a relatively high growth speed in a low-temperature section, and Lc has a relatively high growth speed in a high-temperature section, so that La and Lc can be regulated and controlled by rapidly heating in the low-temperature section and slowly heating in the high-temperature section, and a small-crystal domain hard carbon material with relatively small La is obtained; meanwhile, the temperature regulation mode can obtain the hard carbon material with low oxygen content, so that the sodium ion transmission dynamics of the hard carbon material is further improved.
Further, the first sintering temperature is 800-1000 ℃, and the second sintering temperature is 1200-1400 ℃.
Further, the first heating rate is 5-20 ℃/min, and the second heating rate is 0.5-10 ℃/min. Further, the first temperature rising rate is preferably 8-15 ℃/min. The second heating rate is preferably 3-5 ℃/min.
Further, when the high-temperature section sintering is performed, the heat preservation time at the second sintering temperature is 0.5-24h. The holding time of the second sintering temperature is preferably 2-5h. That is, the preparation method is to raise the temperature to the first sintering temperature at the first temperature raising rate, change the temperature raising rate to the second temperature raising rate after reaching the first sintering temperature, raise the temperature to the second sintering temperature at the second temperature raising rate, and then keep the temperature.
The two-stage sintering treatment adopted in the invention, in particular to the sintering temperature, the heating speed and the heat preservation time adopted in the high-temperature stage sintering, has great influence on the control of the oxygen content, and the hard carbon material with low oxygen content can be obtained in the sintering temperature, the heating speed and the heat preservation time adopted in the high-temperature stage sintering.
Further, the low temperature Duan Shaojie and high temperature sintering are performed in an inert atmosphere. The inert atmosphere comprises any one or a combination of at least two of nitrogen, argon, neon, helium, xenon and krypton.
In some embodiments, the carbon source comprises one or more of a plant-based carbon source, a carbohydrate carbon source, a resin-based carbon source, and a polymer-based carbon source.
Further, the plant carbon source comprises one or more of coconut shell, almond shell, pistachio shell, macadamia shell, jujube core shell, chestnut shell, hazelnut shell, peanut shell, walnut shell, peach core shell, cotton, wood, bamboo, straw and lignin.
Further, the carbohydrate carbon source comprises one or more of glucose, sucrose, maltose, lactose, fructose, starch, cellulose.
Further, the resin-based carbon source includes one or more combinations of phenolic resin, epoxy resin, urea resin, melamine resin, polyimide resin, polyester resin, aldehyde resin, polyolefin resin, polyacrylic resin.
Further, the polymer-based carbon source comprises one or a combination of more of polyfurfuryl alcohol, polyaniline, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, natural rubber and polyacrylonitrile.
In some embodiments, the carbonization treatment comprises: heating the carbon source at 400-800 deg.c for 0.5-24 hr. Preferably, the carbon source is heated at a temperature of 500 ℃ to 600 ℃ for 1 to 5 hours.
In some embodiments, the carbonization treatment is performed in an inert atmosphere or an oxygen-deficient atmosphere.
Further, the inert atmosphere comprises one or more of nitrogen, argon, neon, helium, xenon, krypton.
Further, the oxygen-deficient atmosphere is a gas atmosphere with an oxygen content of less than or equal to 1 wt%.
In some embodiments, the comminution process comprises: the carbonized product was crushed to a median particle size of 1 μm to 15 μm and sieved using a 30 mesh sieve. If the particle size is small, an excessively large specific surface area results in low initial efficiency of the battery, and if the particle size is large, it also results in reduced battery performance.
Further, the crushing treatment comprises one or a combination of more of ball milling, air flow crushing, mechanical crushing and extrusion crushing. The pulverizing treatment is performed, for example, using one or a combination of at least two of a ball mill, a jet mill, a mechanical pulverizer, and a roll mill.
In some embodiments, the preparation method specifically includes: sequentially carbonizing, crushing, activating and purifying the carbon source to obtain a carbonized material precursor; wherein the activation treatment comprises solid phase pore-forming and/or gas phase pore-forming.
Further, the solid phase pore-forming comprises: and uniformly mixing the crushed product with the solid phase pore-forming agent under the inert atmosphere condition, and carrying out high-temperature treatment.
And further, after the solid phase pore forming is completed, washing the activation treatment product to pH of 4-8, and drying.
Further, the solid phase pore-forming agent comprises one or a combination of more of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate.
Further, the mass ratio of the crushing treatment product to the solid phase pore-forming agent is 1:2-2:1.
Further, in the solid phase pore-forming, the temperature of the high-temperature treatment is 500-800 ℃, and the time of the high-temperature treatment is 10-120 min.
Further, the gas phase pore forming includes: and under the inert atmosphere condition, heating the crushed product to a third temperature, then preserving heat, introducing a gas-phase pore-forming agent in the heat preservation process, and stopping introducing the gas-phase pore-forming agent after the heat preservation is finished.
Further, the gas phase pore former comprises one or more of water vapor, carbon dioxide, oxygen and air.
Further, in the gas phase pore forming, the third temperature is 700 ℃ to 1000 ℃.
Further, in the gas phase pore forming, the heat preservation time is 0.5h-10h.
Further, the inert atmosphere adopted by the solid phase pore-forming and the gas phase pore-forming independently comprises one or a combination of more of nitrogen, argon, neon, helium, xenon and krypton.
In some embodiments, the purification process comprises: and uniformly mixing the crushed product with acid, stirring for 0.5-24h, and carrying out solid-liquid separation after stirring.
Further, the purification treatment specifically includes: mixing the crushed product, acid and water according to the mass ratio of 1:1:1-1:1:10, stirring, washing the purified product obtained by solid-liquid separation to pH of 4-8, and drying.
Further, the acid includes one or more of hydrochloric acid, hydrofluoric acid, nitric acid, phosphoric acid, and sulfuric acid.
Further, the concentration of the acid is 35-98 wt%.
In some embodiments, the post-processing includes: and carrying out VC mixing and screening on the products sintered in the high-temperature section to obtain the hard carbon material.
Further, the screening adopts a screen mesh number of 200-400 meshes. Preferably, the screen mesh number is 325 mesh.
It is a further object of the present invention to provide a hard carbon material obtained by the method according to any one of the above.
In some embodiments, the hard carbon material has a median particle size of 5 to 9 μm. The specific surface area of the hard carbon material is 3-30 m 2 And/g. The hard carbon material has an oxygen element content of less than 10wt%, preferably less than 2wt%. The hard carbon material has a domain size La of less than 50 nm, preferably less than 11.5 nm.
The fourth object of the present invention is to provide an application of the hard carbon material in preparing a carbon negative electrode material for sodium ion batteries or sodium ion batteries.
It is a fifth object of the present invention to provide a sodium ion battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, the negative electrode comprising the hard carbon material of any one of the above.
The sixth object of the present invention is to provide a method for controlling the domain size and oxygen content of a hard carbon material, comprising:
sequentially carbonizing, crushing and purifying a carbon source to obtain a carbonized material precursor;
sequentially sintering the carbonized material precursor at low temperature Duan Shaojie and high temperature, and performing post-treatment to obtain a hard carbon material;
the low temperature Duan Shaojie adopts a first heating rate and a first sintering temperature, the high temperature section sintering adopts a second heating rate and a second sintering temperature, the first heating rate is higher than the second heating rate by more than 4.5 ℃/min, and the first sintering temperature is lower than the second sintering temperature by more than 200 ℃.
Further technical solutions of the "method for controlling domain size and oxygen content of hard carbon material" described in the sixth aspect of the present invention are described in detail in the second aspect of the present invention, and are not described herein.
Compared with the prior art, the invention has at least the following beneficial effects: the invention provides a hard carbon material with small crystal domain (La size) to shorten the transmission distance of sodium ions in the hard carbon material and further combine the characteristic of low oxygen content to improve the transmission dynamics of sodium ions; the invention provides a high-temperature sintering method combining fast and slow heating modes, which can regulate and control the domain size and oxygen content of a hard carbon material at the same time, so as to prepare the hard carbon material with low oxygen content and small domain; the sodium ion battery based on the hard carbon material has higher reversible capacity, high first coulombic efficiency and good dynamic performance.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required to be used in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments described in the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a diagram showing the structure of graphite crystallites in a hard carbon material prepared in example 1 of the present invention;
FIG. 2 is an XRD pattern of the hard carbon material prepared in example 1 and comparative example 1 according to the present invention;
FIG. 3 is an SEM image of a hard carbon material prepared according to example 1 of the present invention;
FIG. 4 is a graph showing the first charge-discharge curves of the hard carbon materials prepared in example 1 and comparative example 1 according to the present invention;
FIG. 5 is a graph showing the sub-discharge curve dQ/dV of the hard carbon material prepared in example 1 and comparative example 1;
fig. 6 is a ratio reversible capacity comparison chart of batteries based on the corresponding hard carbon materials prepared in example 1 and comparative example 1 according to the present invention.
Detailed Description
The following detailed description of the present invention is provided in connection with specific embodiments so that those skilled in the art may better understand and practice the present invention. Specific functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed embodiment.
Example 1
Under the nitrogen atmosphere, the apricot shells are placed in a box-type furnace to be carbonized for 1h at 600 ℃, and after carbonization, carbonized products are cooled to room temperature; coarse crushing the carbonized product, and crushing the carbonized product by adopting air current until the median particle diameter is about 5.0 mu m to obtain a crushed product; then VC mixing the crushed product and sodium hydroxide according to the mass ratio of 1:1, heating to 700 ℃ in an activating furnace under nitrogen atmosphere, preserving heat for 30min to perform activating treatment, and cooling after the activating treatment is completed to obtain an activated product; mixing the activated product, concentrated hydrochloric acid (with the acid concentration of 37%) and pure water according to the mass ratio of 1:1:3, stirring for 3 hours, centrifuging to remove filtrate, washing the precipitate with pure water to PH=4-7, centrifuging and drying to obtain a carbonized material precursor;
placing the carbonized material precursor in a box furnace, firstly raising the temperature to 1000 ℃ at the heating rate of 15 ℃/min, then raising the temperature to 1400 ℃ at the heating rate of 3 ℃/min, and then preserving the heat for 2 hours to perform calcination treatment; and (5) cooling and VC mixing after the calcination is finished, and screening by adopting a 325-mesh screen to obtain the hard carbon material.
The median particle diameter, specific surface area, oxygen content and domain size characteristics of the hard carbon material obtained in this example are shown in table 1. Fig. 1 is a diagram showing the structure of crystallites of graphite in the hard carbon material prepared in this example. Fig. 2 shows the XRD pattern of the hard carbon material prepared in this example. Fig. 3 is an SEM image of the hard carbon material prepared in this example.
The sodium ion button half cell is prepared by adopting the hard carbon material, and the preparation of the button cell pole piece is prepared by adopting a method known in the art:
the hard carbon material, the conductive agent (SP) and the binder (LA 133) are mixed according to the mass ratio of 91:3:6Mixing to obtain a mixture, regulating the solid content of the mixture to 50% with deionized water, uniformly mixing to obtain a uniform mixture, coating the uniform mixture on a copper foil current collector, vacuum drying, and rolling to obtain the final product with an areal density of 5.5+ -0.5 mg/cm 2 Is a negative electrode plate;
and (3) manufacturing a button cell: naPF with sodium sheet as counter electrode, 1mol/L 6 DIGLYME (100 Vol%) as electrolyte, glass fiber as separator, and 2032 button cell casing was used for assembly to obtain button half cell.
The battery performance of the button half cell was tested and the test results are shown in table 2.
Example 2
Under argon atmosphere, placing cellulose into a box furnace, carbonizing at 500 ℃ for 24 hours, and cooling carbonized products to room temperature after carbonization; mechanically crushing the carbonized product to a median particle diameter of about 7.0 mu m to obtain a crushed product; then VC mixing the crushed product and potassium hydroxide according to the mass ratio of 1:2, heating to 800 ℃ in an activating furnace under nitrogen atmosphere, preserving heat for 1h to perform activating treatment, and cooling after the activating treatment is completed to obtain an activated product; mixing an activated product, concentrated nitric acid (with the acid concentration of 69%) and pure water according to the mass ratio of 1:1:3, stirring for 3 hours, centrifuging to remove filtrate, washing precipitate with pure water to PH=4-7, centrifuging and drying to obtain a carbonized material precursor;
placing the carbonized material precursor in a box furnace, firstly raising the temperature to 800 ℃ at the heating rate of 5 ℃/min, then raising the temperature to 1300 ℃ at the heating rate of 0.5 ℃/min, and then preserving the heat for 5 hours to perform calcination treatment; and (5) cooling and VC mixing after the calcination is finished, and screening by adopting a 325-mesh screen to obtain the hard carbon material. The median particle diameter, specific surface area, oxygen content and domain size characteristics of the hard carbon material obtained in this example are shown in table 1.
The hard carbon material in example 1 was replaced with the hard carbon material in this example, and a sodium ion button half cell was assembled in the same manner as in example 1, and the cell performance was as shown in table 2.
Example 3
Under argon atmosphere, placing polyimide resin into a box-type furnace, carbonizing for 5 hours at 800 ℃, and cooling carbonized products to room temperature after carbonization; then carrying out jet milling on the carbonized product until the median particle diameter is about 6.0 mu m to obtain a milled product; cooling the crushed product, transferring the crushed product into an activation furnace, heating to 900 ℃, introducing steam under nitrogen atmosphere, preserving heat for 2 hours, stopping introducing steam and cooling to obtain a carbonized material precursor;
placing the carbonized material precursor in a box furnace, firstly raising the temperature to 900 ℃ at the heating rate of 20 ℃/min, then raising the temperature to 1200 ℃ at the heating rate of 10 ℃/min, and then preserving the heat for 1h to perform calcination treatment; and (5) cooling and VC mixing after the calcination is finished, and screening by adopting a 325-mesh screen to obtain the hard carbon material. The median particle diameter, specific surface area, oxygen content and domain size characteristics of the hard carbon material obtained in this example are shown in table 1.
The hard carbon material in example 1 was replaced with the hard carbon material in this example, and a sodium ion button half cell was assembled in the same manner as in example 1, and the cell performance was as shown in table 2.
Example 4
Under vacuum condition, placing polyvinylidene fluoride into a box furnace, carbonizing at 700 ℃ for 8 hours, and cooling carbonized products to room temperature after carbonization; coarse crushing the carbonized product, and crushing the carbonized product by adopting air current until the median particle diameter is about 5.0 mu m to obtain a crushed product; then, carrying out VC mixing on the crushed product and sodium oxide according to the mass ratio of 2:1, heating to 750 ℃ in an activating furnace under the nitrogen atmosphere, preserving heat for 2 hours to carry out activating treatment, cooling after the activating treatment is finished, washing with pure water until PH=4-8, centrifuging and drying to obtain a carbonized material precursor;
placing the carbonized material precursor in a box furnace, firstly raising the temperature to 1000 ℃ at the heating rate of 10 ℃/min, then raising the temperature to 1250 ℃ at the heating rate of 5 ℃/min, and then preserving the heat for 5 hours to perform calcination treatment; and (5) cooling and VC mixing after the calcination is finished, and screening by adopting a 325-mesh screen to obtain the hard carbon material. The median particle diameter, specific surface area, oxygen content and domain size characteristics of the hard carbon material obtained in this example are shown in table 1.
The hard carbon material in example 1 was replaced with the hard carbon material in this example, and a sodium ion button half cell was assembled in the same manner as in example 1, and the cell performance was as shown in table 2.
Example 5
Under the nitrogen atmosphere, placing sucrose into a box furnace, carbonizing for 3 hours at 550 ℃, and cooling carbonized products to room temperature after carbonization; coarse crushing the carbonized product, and crushing the carbonized product by adopting air current until the median particle diameter is about 8.0 mu m to obtain a crushed product; then VC mixing the crushed product and potassium carbonate according to the mass ratio of 2:1, heating to 750 ℃ in an activating furnace under nitrogen atmosphere, preserving heat for 1h to perform activating treatment, cooling after the activating treatment is finished, washing with pure water to PH=4-8, centrifuging and drying to obtain a carbonized material precursor;
placing the carbonized material precursor in a box furnace, firstly raising the temperature to 900 ℃ at the heating rate of 15 ℃/min, then raising the temperature to 1300 ℃ at the heating rate of 2 ℃/min, and then preserving the heat for 1h to perform calcination treatment; and (5) cooling and VC mixing after the calcination is finished, and screening by adopting a 325-mesh screen to obtain the hard carbon material. The median particle diameter, specific surface area, oxygen content and domain size characteristics of the hard carbon material obtained in this example are shown in table 1.
The hard carbon material in example 1 was replaced with the hard carbon material in this example, and a sodium ion button half cell was assembled in the same manner as in example 1, and the cell performance was as shown in table 2.
Comparative example 1
Comparative example 1 was different from example 1 only in that the carbonized material precursor was placed in a box furnace, heated to 1400 c at a heating rate of 0.5 c/min, and then heat-preserved for 2 hours to perform calcination treatment, and otherwise the same procedure as example 1 was performed to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as example 1.
Fig. 2 shows the XRD pattern of the hard carbon material prepared in this comparative example 1. Fig. 4 is a graph showing the first charge-discharge curves of the hard carbon materials prepared in example 1 and comparative example 1. FIG. 5 is a graph showing the sub-discharge curve dQ/dV of the hard carbon material prepared in example 1 and comparative example 1. Fig. 6 is a ratio reversible capacity comparison chart of the batteries based on the corresponding hard carbon materials prepared in example 1 and comparative example 1. As can be seen by comparison, the hard carbon material prepared by the embodiment of the invention shows better electrochemical comprehensive performance.
Comparative example 2
Comparative example 2 differs from example 2 only in that comparative example 2 was not subjected to the activation treatment step, resulting in a carbonized material precursor; the carbonized material precursor was placed in a box furnace, heated to 1100 ℃ at a heating rate of 1 ℃/min, and the rest was carried out in the same manner as in example 2 to obtain a hard carbon material, and a sodium ion button half cell was assembled by using the hard carbon material in the same manner as in example 1.
Comparative example 3
Comparative example 3 differs from example 3 only in that the carbonized product was jet-pulverized to a median particle diameter of about 15.0 μm; the carbonized material precursor was placed in a box furnace, heated to 1600 ℃ at a heating rate of 20 ℃/min, then heat-preserved for 1 hour to perform calcination treatment, and the rest was performed in the same manner as in example 3 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as in example 1.
Comparative example 4
Comparative example 4 differs from example 4 only in that comparative example 4 was not subjected to an activation step, resulting in a carbonized material precursor; the carbonized material precursor was placed in a box furnace, heated to 1250 ℃ at a heating rate of 2 ℃/min, then heat-preserved for 5 hours to perform calcination treatment, and the rest was performed in the same manner as in example 4 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as in example 1.
Comparative example 5
Comparative example 5 differs from example 5 only in that comparative example 5 was not subjected to an activation step to obtain a carbonized material precursor; the carbonized material precursor was placed in a box furnace, heated to 900 ℃ at a heating rate of 5 ℃/min, then heat-preserved for 1 hour to perform calcination treatment, and the rest was performed in the same manner as in example 5 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as in example 1.
Comparative example 6
Comparative example 6 was different from example 1 only in that a carbonized material precursor was placed in a box furnace, heated to 1400 c at a heating rate of 15 c/min, then heat-preserved for 2 hours to perform calcination treatment, and the rest was performed in the same manner as example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as example 1.
Comparative example 7
Comparative example 7 was different from example 1 only in that a carbonized material precursor was placed in a box furnace, heated to 1400 c at a heating rate of 3 c/min, then heat-preserved for 2 hours to perform calcination treatment, and the rest was performed in the same manner as example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as example 1.
Comparative example 8
Comparative example 8 was different from example 1 only in that a carbonized material precursor was placed in a box furnace, heated to 1000 c at a heating rate of 3 c/min, heated to 1400 c at a heating rate of 15 c/min, and then heat-preserved for 2 hours to perform a calcination treatment, and the rest was conducted in the same manner as in example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled in the same manner as in example 1 using the hard carbon material.
Comparative example 9
Comparative example 9 was different from example 1 only in that the activation treatment was not performed, and the rest was performed in the same manner as in example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as in example 1.
Comparative example 10
Comparative example 10 was different from example 1 only in that a carbonized material precursor was placed in a box furnace, heated to 900 c at a heating rate of 15 c/min, then heat-preserved for 2 hours to perform calcination treatment, and the rest was performed in the same manner as example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as example 1.
Comparative example 11
Comparative example 11 was different from example 1 only in that a carbonized material precursor was placed in a box furnace, heated to 2500 c at a heating rate of 10 c/min, then heat-preserved for 2 hours to perform calcination treatment, and the rest was performed in the same manner as example 1 to obtain a hard carbon material, and a sodium ion button half cell was assembled using the hard carbon material in the same manner as example 1.
The hard carbon materials and the sodium ion button half cells obtained in the above examples and comparative examples were subjected to the related performance tests under the following conditions, and the test results are shown in table 1 and table 2, respectively:
(1) And testing the oxygen content of the carbon material. The content of oxygen element is tested by adopting an inert gas melting infrared method, a sample is heated and melted under the protection of helium, oxygen is reduced by carbon at high temperature to generate a large amount of CO, and the CO is oxidized into CO by using a glowing CuO reagent 2 And (5) entering an infrared absorption cell for detection. Each sample was tested in 5 groups and averaged to obtain the oxygen content of the sample, and the measured value was mass percent.
(2) XRD data are obtained by testing with a Panalytical X' Pert PRO MPD tester, using K alpha rays (wavelength lambda= 0.1541 nm) of a Cu target as a light source, and in the range of 2 Theta 10 DEG to 90 deg.
(3) Raman testing of carbon materials. In order to analyze the internal structural information of the carbon cathode, a high-energy argon ion beam is adopted to cut the carbon cathode material, so that a section sample can be obtained. The Raman spectrum is tested by a Raman tester under the conditions of He-Ne laser (wavelength 532 nm), filter 10%, hole 500 μm, slit 100 μm, grating 1800 gr/mm, exposure time 60 s, cumulative times 2 times, microscope objective 50X Lwd, test range. Peak D->Nearby, G peak is atNearby. Randomly selecting 5 points on the surface of the carbon material to test Raman I G /I D Peak intensity ratio (i.e. the ratio of G peak intensity to D peak intensity), I is taken G /I D Average value according to the formulaL a (nm)=(2.4*10 -10 )λ nm 4 (I G /I D ) The domain size can be calculatedL a 。
(4) Nitrogen adsorption test was performed at 77K using a microphone specific surface area tester (model ASAP 2460) to obtain specific surface area and pore volume, wherein the specific surface area was calculated by BET formula (unit is m 2 The pore volume Vpore is the total pore volume of single point adsorption (in cm. Mu.m/g).
(5) Specific capacity and first time efficiency test conditions: testing on a Land battery testing system at room temperature, firstly discharging the constant current of 0.1C to 1mV, and stopping discharging; after standing, the mixture was charged at 0.1C, the cut-off voltage was 2V, and the test results are shown in Table 2. The specific capacity (mAh/g) is the first discharge capacity divided by the weight of the carbon negative electrode material (namely the hard carbon material) contained in the negative electrode plate, the nominal specific capacity is 300mAh/g, and the first efficiency is the ratio of the first charge capacity to the first discharge capacity.
(6) And (3) multiplying power performance test: and (3) performing constant-current charge and discharge tests on the battery subjected to the first week test at 0.1C/0.1C, 0.5C/0.5C, 1C/1C and 2C/2C at normal temperature, and dividing the 2C charge capacity by the 0.1C gram capacity to obtain the rate discharge retention rate.
Table 1 hard carbon material related characteristics in examples, comparative examples
Table 2 battery-related properties in examples, comparative examples
Referring to tables 1 and 2, the reversible specific capacity of the batteries in examples 1-5 is 298.3-335.2mAh/g, the initial coulomb efficiency is 85.2% -94.0%, the 2C capacity retention rate is 71.5% -75.7%, the electrochemical performance is better, and it can be found that the direct linear relation between the voltage level and the rate performance is better, and the higher the voltage level is, the better the rate performance is. This is because oxygen plays an obstacle role in sodium ion transport, so that the lower the oxygen content, the faster the sodium ion transport, while the smaller the domain size La represents the transport distance of sodium ions, the shorter the transport distance, which means the faster the whole transport process. Therefore, the sodium ion battery prepared from the hard carbon material provided by the invention has the characteristics of high reversible capacity, high first coulomb efficiency, good dynamic performance and the like.
Furthermore, as can be seen from the combination of tables 1 and 2, the correlation between the first coulombic efficiency of the battery and the content of oxygen element in the hard carbon material is large, because most oxygen element defects have strong binding energy with sodium ions, i.e. after capturing sodium ions, sodium ions are difficult to remove again, so that the coulombic efficiency is low. In addition, because sodium ions are transported in the hard carbon material from interlayer to closed cell structure, the hard carbon material with low oxygen content and small domain size (La) has better rate capability and rapid dynamic process.
The various aspects, embodiments, features and examples of the invention are to be considered in all respects as illustrative and not intended to limit the invention, the scope of which is defined solely by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
In addition, the inventors have conducted experiments with other materials, process operations, and process conditions as described in this specification with reference to the foregoing examples, and have all obtained desirable results.
While the invention has been described with reference to an illustrative embodiment, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims. Moreover, unless specifically stated any use of the terms first, second, etc. do not denote any order or importance, but rather the terms first, second, etc. are used to distinguish one element from another.
Claims (20)
1. A hard carbon material is characterized in that the domain size of graphite microcrystals in the hard carbon materialL a Less than 50 and nm, and the oxygen element content delta is less than 10 percent;
wherein,L a is obtained by carrying out Raman spectrum test on the hard carbon material,L a =(2.4*10 -10 )λ nm 4 (I G /I D )，I G is a Raman shift of 1500cm in Raman spectrum -1 ～1650cm -1 Peak intensity of G peak appearing in the range of (I) D Is a Raman shift of 1300cm in Raman spectrum -1 ～1400cm -1 Peak intensity of D peak appearing in range lambda nm A wavelength of light emitted by the raman light source;
delta is by converting the hard carbon material to CO 2 And then measured by infrared spectroscopy.
2. The hard carbon material according to claim 1, wherein: delta is less than 2 percent,L a ＜11.5 nm。
3. the hard carbon material according to claim 2, wherein: and performing constant-current charge and discharge test on the hard carbon material, wherein the test condition is 0.1C/0.1C constant-current charge and discharge, the test voltage range is 0.001V-2V, and dQ/dV is more than 0.53V in a discharge curve obtained by the constant-current charge and discharge test.
4. A method for preparing a hard carbon material, comprising:
sequentially carbonizing, crushing and purifying a carbon source to obtain a carbonized material precursor;
sequentially sintering the carbonized material precursor at low temperature Duan Shaojie and high temperature, and performing post-treatment to obtain a hard carbon material;
the low temperature Duan Shaojie adopts a first heating rate and a first sintering temperature, the high temperature section sintering adopts a second heating rate and a second sintering temperature, the first heating rate is higher than the second heating rate by more than 4.5 ℃/min, and the first sintering temperature is lower than the second sintering temperature by more than 200 ℃.
5. The method of manufacturing according to claim 4, wherein: the first sintering temperature is 800-1000 ℃, and the second sintering temperature is 1200-1400 ℃;
and/or the first heating speed is 5-20 ℃/min, and the second heating speed is 0.5-10 ℃/min;
and/or, when the high-temperature section sintering is carried out, the heat preservation time at the second sintering temperature is 0.5-24h.
6. The method of manufacturing according to claim 5, wherein: the first heating rate is 8-15 ℃/min; and/or the second heating rate is 2-5 ℃/min; and/or, the low temperature Duan Shaojie and high temperature section sintering is performed in an inert atmosphere; and/or the heat preservation time of the second sintering temperature is 2-5h.
7. The method of manufacturing according to claim 4, wherein: the carbon source comprises one or a combination of a plurality of plant carbon sources, sugar carbon sources, resin carbon sources and polymer carbon sources;
and/or, the carbonization treatment comprises: heating the carbon source at 400-800 ℃ for 0.5-24h;
and/or the carbonization treatment is performed in an inert atmosphere or an oxygen-deficient atmosphere.
8. The method of manufacturing according to claim 7, wherein: the plant carbon source comprises one or more of coconut shell, almond shell, pistachio shell, hawaii shell, jujube core shell, chestnut shell, hazelnut shell, peanut shell, walnut shell, peach core shell, cotton, wood, bamboo, straw and lignin;
and/or the carbohydrate carbon source comprises one or more of glucose, sucrose, maltose, lactose, fructose, starch, cellulose;
and/or the resin-based carbon source comprises one or more of phenolic resin, epoxy resin, urea resin, melamine resin, polyimide resin, polyester resin, aldehyde resin, polyolefin resin, polyacrylic resin;
and/or the polymer carbon source comprises one or a combination of more of polyfurfuryl alcohol, polyaniline, polyethylene glycol, polyethylene oxide, polyvinylidene fluoride, natural rubber and polyacrylonitrile;
and/or, the carbonization treatment comprises: heating the carbon source at 500-600 ℃ for 1-5h;
and/or the inert atmosphere comprises one or more of nitrogen, argon, neon, helium, xenon, krypton;
and/or the oxygen-deficient atmosphere is a gas atmosphere with the oxygen content less than or equal to 1 wt%.
9. The method according to claim 4, wherein the pulverization treatment comprises: crushing the carbonized product to a median particle size of 1-15 mu m, and screening by a 30-mesh screen;
and/or the crushing treatment comprises one or a combination of more of ball milling crushing, jet milling, mechanical crushing and extrusion crushing.
10. The preparation method according to claim 4, which comprises the following steps: sequentially carbonizing, crushing, activating and purifying the carbon source to obtain a carbonized material precursor; wherein the activation treatment comprises solid phase pore-forming and/or gas phase pore-forming.
11. The method of claim 10, wherein the solid phase pore-forming comprises: uniformly mixing the crushed product with a solid phase pore-forming agent under the condition of inert atmosphere, and carrying out high-temperature treatment;
and/or, the gas phase pore forming comprises: and under the inert atmosphere condition, heating the crushed product to a third temperature, then preserving heat, introducing a gas-phase pore-forming agent in the heat preservation process, and stopping introducing the gas-phase pore-forming agent after the heat preservation is finished.
12. The method of manufacturing according to claim 11, wherein: washing the activation treatment product to pH of 4-8 after the solid phase pore-forming is completed, and drying;
and/or the solid phase pore-forming agent comprises one or a combination of more of sodium hydroxide, potassium hydroxide, sodium oxide, potassium oxide, sodium carbonate, sodium bicarbonate, potassium carbonate and potassium bicarbonate;
and/or the mass ratio of the crushing treatment product to the solid phase pore-forming agent is 1:2-2:1;
and/or, in the solid phase pore-forming, the temperature of the high-temperature treatment is 500-800 ℃, and the time of the high-temperature treatment is 10-120 min;
and/or the gas phase pore former comprises one or more of water vapor, carbon dioxide, oxygen, air;
and/or, in the gas phase pore-forming, the third temperature is 700 ℃ -1000 ℃;
and/or, in the gas phase pore forming, the heat preservation time is 0.5h-10h;
and/or the inert atmosphere adopted by the solid phase pore-forming and the gas phase pore-forming independently comprises one or a combination of more of nitrogen, argon, neon, helium, xenon and krypton.
13. The method of claim 4, wherein the purification treatment comprises: and uniformly mixing the crushed product with acid, stirring for 0.5-24h, and carrying out solid-liquid separation after stirring.
14. The method according to claim 13, wherein the purification treatment specifically comprises: mixing the crushed product, acid and water according to the mass ratio of 1:1:1-1:1:10, stirring, washing the purified product obtained by solid-liquid separation to pH of 4-8, and drying;
and/or the acid comprises a combination of one or more of hydrochloric acid, hydrofluoric acid, nitric acid, phosphoric acid, and sulfuric acid;
and/or the concentration of the acid is 35-98 wt%.
15. The method of claim 4, wherein the post-treatment comprises: and carrying out VC mixing and screening on the products sintered in the high-temperature section to obtain the hard carbon material.
16. The method of manufacturing according to claim 15, wherein: the number of the screen meshes adopted by the screening is 200-400 meshes.
17. The hard carbon material obtained by the preparation method according to any one of claims 4 to 16.
18. Use of the hard carbon material of any one of claims 1, 2, 3, 17 in the preparation of a carbon negative electrode material for sodium ion batteries or sodium ion batteries.
19. A sodium ion battery, includes positive pole, negative pole, electrolyte and diaphragm, its characterized in that: the negative electrode comprising the hard carbon material of any one of claims 1, 2, 3, 17.
20. A method for adjusting and controlling the domain size and the oxygen content of a hard carbon material, comprising the steps of:
sequentially carbonizing, crushing and purifying a carbon source to obtain a carbonized material precursor;
sequentially sintering the carbonized material precursor at low temperature Duan Shaojie and high temperature, and performing post-treatment to obtain a hard carbon material;
the low temperature Duan Shaojie adopts a first heating rate and a first sintering temperature, the high temperature section sintering adopts a second heating rate and a second sintering temperature, the first heating rate is higher than the second heating rate by more than 4.5 ℃/min, and the first sintering temperature is lower than the second sintering temperature by more than 200 ℃.
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