CN117049517B - Modified hard carbon negative electrode material and preparation and application thereof - Google Patents
Modified hard carbon negative electrode material and preparation and application thereof Download PDFInfo
- Publication number
- CN117049517B CN117049517B CN202311314102.6A CN202311314102A CN117049517B CN 117049517 B CN117049517 B CN 117049517B CN 202311314102 A CN202311314102 A CN 202311314102A CN 117049517 B CN117049517 B CN 117049517B
- Authority
- CN
- China
- Prior art keywords
- carbon
- hard carbon
- carbon source
- negative electrode
- modified hard
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 145
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000007773 negative electrode material Substances 0.000 title claims description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 229
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 157
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 73
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 238000000151 deposition Methods 0.000 claims abstract description 45
- 239000010405 anode material Substances 0.000 claims abstract description 41
- 238000001816 cooling Methods 0.000 claims abstract description 17
- 230000031709 bromination Effects 0.000 claims abstract description 13
- 238000005893 bromination reaction Methods 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 50
- 239000010439 graphite Substances 0.000 claims description 50
- 230000008021 deposition Effects 0.000 claims description 38
- 238000003756 stirring Methods 0.000 claims description 30
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 23
- 229910052794 bromium Inorganic materials 0.000 claims description 23
- -1 bromine compound Chemical class 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 22
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 18
- 238000005406 washing Methods 0.000 claims description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 13
- 238000003763 carbonization Methods 0.000 claims description 13
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 12
- 150000003863 ammonium salts Chemical class 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 230000003647 oxidation Effects 0.000 claims description 9
- 238000007254 oxidation reaction Methods 0.000 claims description 9
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 7
- 229920001568 phenolic resin Polymers 0.000 claims description 7
- 239000005011 phenolic resin Substances 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 6
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 6
- XUXNAKZDHHEHPC-UHFFFAOYSA-M sodium bromate Chemical compound [Na+].[O-]Br(=O)=O XUXNAKZDHHEHPC-UHFFFAOYSA-M 0.000 claims description 6
- 235000019698 starch Nutrition 0.000 claims description 6
- 239000008107 starch Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- XWNSFEAWWGGSKJ-UHFFFAOYSA-N 4-acetyl-4-methylheptanedinitrile Chemical compound N#CCCC(C)(C(=O)C)CCC#N XWNSFEAWWGGSKJ-UHFFFAOYSA-N 0.000 claims description 3
- 229920001353 Dextrin Polymers 0.000 claims description 3
- 239000004375 Dextrin Substances 0.000 claims description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000005715 Fructose Substances 0.000 claims description 3
- 229930091371 Fructose Natural products 0.000 claims description 3
- 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 3
- 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 3
- 239000004153 Potassium bromate 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
- 229920001807 Urea-formaldehyde Polymers 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 3
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 235000019425 dextrin Nutrition 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 claims description 3
- 239000004005 microsphere Substances 0.000 claims description 3
- 229920005575 poly(amic acid) Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000019396 potassium bromate Nutrition 0.000 claims description 3
- 229940094037 potassium bromate Drugs 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 238000009740 moulding (composite fabrication) Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 26
- 239000007789 gas Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 22
- 239000011888 foil Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910003481 amorphous carbon Inorganic materials 0.000 description 20
- 239000010410 layer Substances 0.000 description 20
- 230000001590 oxidative effect Effects 0.000 description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000007800 oxidant agent Substances 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 14
- 239000013078 crystal Substances 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 239000011148 porous material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 8
- 230000007547 defect Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000004254 Ammonium phosphate Substances 0.000 description 7
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 7
- 235000019289 ammonium phosphates Nutrition 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000004020 conductor Substances 0.000 description 7
- 230000001276 controlling effect Effects 0.000 description 7
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 239000001768 carboxy methyl cellulose Substances 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 239000011331 needle coke Substances 0.000 description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002344 surface layer Substances 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
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000007580 dry-mixing Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 238000003466 welding Methods 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- 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 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000006260 foam 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
- 230000003993 interaction Effects 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- PBHYLKMSZFULFJ-UHFFFAOYSA-N [Co].[Ni].[Na] Chemical compound [Co].[Ni].[Na] PBHYLKMSZFULFJ-UHFFFAOYSA-N 0.000 description 1
- WFSRWJJESXWWSH-UHFFFAOYSA-N [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Fe+2].[Mn+2].[Ni+2].[Na+] WFSRWJJESXWWSH-UHFFFAOYSA-N 0.000 description 1
- XLCPLIJTRIGVDU-UHFFFAOYSA-N [O-2].[Mn+2].[Ni+2].[Na+] Chemical compound [O-2].[Mn+2].[Ni+2].[Na+] XLCPLIJTRIGVDU-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate 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
- 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
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 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
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a modified hard carbon anode material, and preparation and application thereof. The method comprises the steps of carrying out heat treatment on two carbon sources, cooling, forming and carbonizing to obtain a hard carbon material, carrying out bromination treatment, and depositing a surface carbon layer to obtain the modified hard carbon anode material. The modified hard carbon anode material obtained by the method can improve the initial coulomb efficiency and the electrochemical rate performance.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a modified hard carbon anode material, and preparation and application thereof.
Background
Lithium Ion Batteries (LIBs) have become a major chemical source of power due to their advantages in energy density, power density, and cycle life. However, maldistribution of lithium resources can pose a risk to the lithium ion battery raw material supply chain, especially in terms of use for stationary energy storage. Sodium Ion Batteries (SIBs) are considered as important alternative secondary batteries to LIBs due to the abundance of sodium resources and the same rocking chair storage mechanism. But is large due to the difference between Li and Na. Sodium ions (0.102 nm) have a larger radius than lithium ions (0.076 nm), resulting in slow diffusion kinetics. Heretofore, efforts have been made to explore the cathode materials of SIBs, including layered transition metal oxides, prussian blue analogues and polyanionic compounds.
However, the study of the high-performance anode material is still in the beginning stage. Hard Carbon (HC) is a feasible embedded sodium ion negative electrode material, has the advantages of low cost, abundant resources, no toxicity, good conductivity, abundant microcrystalline structure, low embedded potential (0.1V) and the like, and is not only beneficial to absorbing more Na + And is favorable to Na + Is used for embedding and taking off. However, so far, the development and use of Hard Carbon (HC) has been due to low Initial Coulomb Efficiency (ICE) and low electrochemistryCapacity is limited.
Disclosure of Invention
The invention aims to solve the problems, and provides a modified hard carbon anode material, a preparation method and an application thereof, which can improve initial coulombic efficiency and electrochemical rate performance.
According to the technical proposal of the invention, the preparation method of the modified hard carbon anode material comprises the following steps,
s1: heating the mixture of the first carbon source and the second carbon source to obtain a mixed carbon source;
the first carbon source is selected from one or more of starch, dextrin, sucrose, fructose, glucose, phenolic resin, epoxy resin, urea-formaldehyde resin, polyvinylpyrrolidone and polyamic acid;
the second carbon source is graphitized carbon material subjected to oxidation treatment;
s2: performing rapid cooling treatment on the mixed carbon source obtained in the step S1 to obtain a formed mixed carbon source;
s3: carbonizing the formed mixed carbon source obtained in the step S2 under the condition of an inactive atmosphere to obtain a hard carbon material;
s4: brominating the hard carbon material obtained in the step S3 to obtain a modified hard carbon material;
s5: and (3) introducing carbon-containing gas into the modified hard carbon material under the heating condition, and carrying out carbon deposition to obtain the modified hard carbon material with the carbon deposition layer on the surface, namely the modified hard carbon negative electrode material.
Specifically, in the step S1, a first carbon source forms a polymer intermediate, a second carbon source forms a graphite intermediate, and the obtained mixed carbon source is a polymer intermediate embedded with the graphite intermediate;
in the step S2, the cooled polymer intermediate and the graphite intermediate are combined more tightly to form a formed mixed carbon source;
in the step S3, amorphous carbon (low in order degree and high in defect degree) is formed by carbonizing the polymer intermediate, and in the carbonizing process, the part of the amorphous carbon, which is close to the graphite intermediate, is induced to form graphitized carbon; the obtained hard carbon material is a material which takes amorphous carbon as a main body, graphite is embedded in the amorphous carbon, and the surface layer of the graphite is graphitized carbon-like;
in the step S4, a micropore structure (bromine vacancy) is formed on the surface layer (amorphous carbon) of the hard carbon material by bromination treatment, so as to obtain a modified hard carbon material;
in the step S5, carbon-containing gas is deposited on the surface of the modified hard carbon material to obtain a modified hard carbon negative electrode material; the deposition of the carbon-containing gas causes the coverage of large pores or defects, and the pores with consistent size are obtained by tightening, so that sodium ions in electrolyte consumed by the large pores or defects are reduced, thereby being capable of improving the intercalation amount of the sodium ions, containing more sodium ions and further improving ICE and capacity.
Further, the mass ratio of the first carbon source to the second carbon source is 100: 0.1-30, wherein too little second carbon source does not induce the amorphous carbon to form graphitization-like effect, and too much second carbon source affects the performance of the hard carbon.
Further, the graphitized carbon material subjected to the oxidation treatment is obtained by treating graphitized carbon material with an oxidant, wherein the oxidant is one or more selected from nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate and sodium persulfate;
the graphitized carbon material is selected from one or more of graphite, graphite carbon microspheres, aphanitic graphite, crystalline graphite, bulk graphite and graphene.
Further, the consumption of the oxidant is 0.5-2 times of the mass of the graphitized carbon material, the temperature of the oxidant treatment is 40-90 ℃, and the time is 30 min-8 h.
Specifically, the preparation method of the second carbon source (graphitized carbon material after oxidation treatment) may be as follows: and (3) placing the graphitized carbon material into a solution containing an oxidant (the concentration of the oxidant can be 0.2-38wt%) for reaction at 40-90 ℃ for 30 min-8 h, and then washing and drying to obtain the second carbon source.
Further, the graphitized carbon material is obtained by high-temperature graphitization of needle coke, petroleum coke, square coke and the like, and the graphitized carbon material has the length of 0.01-100 mu m and the width of 0.001-50 mu m.
Further, in the step S1, the heat treatment is performed under a stirring condition, the stirring speed is 60 rpm to 480rpm, and the stirring time is 10min to 5h; the heat treatment temperature is 120-400 ℃, and the heating rate is 2-20 ℃/min.
In step S2, the rapid cooling treatment is performed to reduce the temperature to below 15 ℃ within a cooling time of 2-4 hours, so as to obtain any block, flake, sphere and other shaped mixed carbon sources.
Further, the inert atmosphere is selected from one or more of nitrogen, helium, neon and argon.
Further, in the step S3, the carbonization treatment time is 30 min-8 h; the carbonization treatment temperature is 1000-1800 ℃.
Further, in the step S4, the specific operation of the bromination treatment is as follows: 4-1) dissolving a bromine compound in an ammonium salt solution to obtain a bromine mixture with a bromine compound concentration of 0.1-1wt%, wherein the bromine compound is selected from sodium bromide, potassium bromide, lithium bromide, sodium bromate, potassium bromate, hypobromous acid or ammonium bromide; 4-2) mixing the bromine mixture and the hard carbon material according to the mass ratio of 100:1-50, and reacting for 20 min-4 h at the temperature of 70-110 ℃; 4-3) washing the first product obtained in the step 4-2); 4-4) drying the second product obtained in the step 4-3) to obtain the modified hard carbon material.
Further, the concentration of ammonium salt in the ammonium salt solution is 2-13wt% and the solvent is water; the ammonium salt is selected from one or more of ammonium phosphate, ammonium oxalate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium carbonate and ammonium chloride for activating the bromine compound such that the bromide ions and corresponding cations are adsorbed into micropores of the surface of the hard carbon material.
Further, in the step S5, the heating condition is 400 to 1000 ℃; the carbon-containing gas is selected from one or more of methane, ethane, propane, acetylene, propyne, butyne and ethylene; the carbon deposition time is 5 min-60 min.
The second aspect of the invention provides the modified hard carbon anode material prepared by the preparation method.
Further, the modified hard carbon anode material meets the following conditions:
(1) An ordered graphite structure exists inside and is combined with amorphous carbon;
(2) Specific surface area (BET) of 0.3-12 m 2 /g；
(3) The pore volume is 0.001-0.018 m 3 /g；
(4) The particle diameter D50 is 1.2-35 mu m;
(5) The carbon content is more than or equal to 80wt%, the oxygen content is less than or equal to 10wt%, and the carbon content is more than or equal to 8.1.
The sodium ion secondary battery of the third aspect of the invention comprises a negative electrode plate, wherein the negative electrode plate comprises a negative electrode current collector and a negative electrode material layer, and the negative electrode material layer contains the modified hard carbon negative electrode material.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) In step S1 of the present application, the first carbon source molecule forms a polymer intermediate in a molten state rich in hydroxyl groups while stirring and heating, and since the second carbon source is a graphite intermediate having a surface rich in hydroxyl groups, the graphite intermediate is embedded in the polymer intermediate, and the polymer intermediate in which the graphite intermediate is embedded is a mixed carbon source.
(2) In the step S2, in the process of rapidly cooling to less than 15 ℃, the hydrogen bond interaction between the polymer intermediate and the graphite intermediate is enhanced, the combination of the polymer intermediate and the graphite intermediate is enhanced, and further the formation of a graphitized-like structure is facilitated, wherein the more tightly combined graphite intermediate and the polymer intermediate are the formed mixed carbon source.
(3) In the step S3, in the thermal pyrolysis carbonization process, the polymer intermediate forms amorphous carbon, the graphite intermediate is embedded in the amorphous carbon to form an interpolation layer, and because the amorphous carbon and the graphite intermediate have structural similarity and strong affinity and the amorphous carbon and the graphite intermediate are tightly anchored, the part of the amorphous carbon adjacent to the graphite intermediate can be induced by graphite to form graphitized carbon in situ under the high temperature condition, and the graphitization is more convenient and simpler than the graphitization carried out at the traditional temperature.
(4) For the point that amorphous carbon adjacent to a graphite intermediate is induced to form graphitized carbon-like carbon during high-temperature carbonization, the modified hard carbon negative electrode material is facilitated to form a lower specific surface area and a lower defect degree (the (002) crystal plane peak near 23 degrees in an XRD pattern shifts to a high angle, the increase of the order degree of the material is reflected to increase, the defect degree is reduced, the increase of the order degree is the appearance of the increase of the graphitization degree), and meanwhile, a large interlayer distance is kept, fewer defects and fewer irreversible sodium ion absorption sites are formed, so that the modified hard carbon negative electrode material is facilitated to contain more sodium ions which can be embedded and extracted, and further the ICE of the modified hard carbon negative electrode material is facilitated to be improved and the capacity is increased.
(5) In the step S4, after the ammonium ions, the bromide ions of the bromine compounds and the corresponding cations are diffused in the ammonium salt solution, the ammonium ions and the bromide ions are adsorbed on the surface of the modified hard carbon material (amorphous carbon surface), and the movement of the ions in the ammonium salt solution is accelerated due to the fact that the ammonium ions and the bromide ions are heated, so that the amount of the ions adsorbed on the surface of the modified hard carbon material (amorphous carbon surface) is increased; and then washing out ions adsorbed on the surface of the modified hard carbon material to form vacancy sites, so that the micropore ratio of the surface of the modified hard carbon material is improved, the pore size is more consistent, the vacancy sites are used as sodium ion migration channels, and when the sodium ions are embedded into or removed from the modified hard carbon negative electrode material, the adsorption and migration of the sodium ions on the surface of the amorphous carbon are improved, and the sodium ions are promoted to cross the non-crystal boundary surface, thereby being beneficial to improving the sodium ion diffusion capacity of the modified hard carbon negative electrode material and improving the electrical property of the modified hard carbon negative electrode material.
(6) In step S5, an amorphous carbon layer with less residual oxygen atoms and defects is formed on the surface of the modified hard carbon material, wherein the carbon layer can reduce Na + Diffusion resistance on the surface of the modified hard carbon anode material.
Drawings
Fig. 1 is an XRD (x-ray diffraction) pattern of the modified hard carbon negative electrode material obtained in example 4, comparative example 1, example 1.
Fig. 2 is a raman diagram of the modified hard carbon negative electrode materials obtained in comparative example 1, example 4, and example 1.
Fig. 3 is a TEM (transmission electron microscope) image of the modified hard carbon anode material obtained in example 1.
Fig. 4 is an SEM (scanning electron microscope) image of the modified hard carbon anode material obtained in example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
The invention provides a modified hard carbon anode material, which is prepared by the following steps:
(1) According to the mass ratio of 100: placing 0.1-30 of a first carbon source and a second carbon source to obtain a matched mixture, and performing heat treatment to obtain a mixed carbon source;
the heat treatment is carried out under the stirring condition, the stirring rotating speed is 60-480 rpm, and the stirring time is 10 min-5 h; the heat treatment temperature is 120-400 ℃, and the heating rate is 2-20 ℃/min;
wherein the first carbon source is selected from at least one of starch, dextrin, sucrose, fructose, glucose, phenolic resin, epoxy resin, urea-formaldehyde resin, polyvinylpyrrolidone, polyamic acid, etc.;
wherein the graphitized carbon material subjected to the second carbon source oxidation treatment is at least one of graphite obtained by high-temperature graphitization of needle coke, petroleum coke, square coke and the like, graphite carbon microspheres, aphanitic graphite, crystalline graphite, blocky graphite, graphene and the like;
the oxidation treatment is to put graphitized carbon material into a solution containing 0.2-38wt% of oxidant (nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate and sodium persulfate) (the amount of the oxidant is 0.5-2 times of the mass of graphitized carbon material), react in a reaction kettle at 40-90 ℃ for 30 min-8 h, and finally, fully wash with deionized water and dry; in addition, some volatile molecules, such as water, CO, generated during the formation of the polymer intermediate 2 CO along with being rich in hydroxyl groupsThe graphite intermediate body surface layer escapes to reduce the generation of pores, and the pores need to be timely pumped out;
(2) Carrying out rapid cooling treatment on the mixed carbon source to obtain a formed mixed carbon source in any of a block shape, a sheet shape and a spherical shape, wherein the rapid cooling treatment is that the temperature is reduced to below 15 ℃ within the cooling time of 2-4 hours;
(3) Carbonizing the formed mixed carbon source under the condition of inactive atmosphere, crushing, demagnetizing and screening to obtain a hard carbon material;
wherein the inactive atmosphere is selected from at least one of argon, helium and nitrogen;
wherein the carbonization treatment time is 30 min-8 h; the carbonization treatment temperature is 1000-1800 ℃.
(4) Brominating the hard carbon material to obtain a modified hard carbon material;
the specific operation steps of the bromination treatment are as follows: 4-1) dissolving a bromine compound in an ammonium salt solution to obtain a bromine mixture with the concentration of the bromine compound of 0.1-1wt%, wherein the bromine compound is selected from sodium bromide, potassium bromide, lithium bromide, sodium bromate, potassium bromate, hypobromous acid or ammonium bromide; 4-2) mixing the bromine mixture and the hard carbon material according to the mass ratio of 100:1-50, and reacting for 20 min-4 h at the temperature of 70-110 ℃; 4-3) washing the first product obtained in the step 4-2); 4-4) drying the second product obtained in the step 4-3) to obtain the modified hard carbon material. The ammonium salt solution is an aqueous solution containing 2 to 13wt% of an ammonium salt.
(5) Introducing carbon-containing gas into the modified hard carbon material under the heating condition, and performing carbon deposition to obtain the modified hard carbon negative electrode material; wherein the heating condition is 400-1000 ℃, and the heating rate is 5-20 ℃/min; the carbon-containing gas is one or more selected from methane, ethane, propane, acetylene, propyne, butyne and ethylene, and the carbon deposition time is 5 min-60 min.
The modified hard carbon anode material meets the following conditions:
(1) An ordered graphite structure exists inside and is combined with amorphous carbon;
(2) Specific surface area (BE)T) is 0.3-12 m 2 /g；
(3) The pore volume is 0.001-0.018 m 3 /g；
(4) The particle diameter D50 is 1.2-35 mu m;
(5) The modified hard carbon anode material comprises at least one element of carbon, oxygen and hydrogen, wherein the carbon content is more than or equal to 80wt%, the oxygen content is less than or equal to 10wt%, and the carbon content is more than or equal to 8.1.
(6) As shown in FIG. 2, in the Raman diagram of the modified hard carbon anode material, the wave number is 1340-1350 cm −1 Where (D band, disordered carbon or defective graphite tape), the presence of which reflects the degree of defects in the carbon layer structure, the peak intensity here being denoted SD; and the wave number is 1580-1590 cm -1 The (G band, crystalline graphite ribbon) at which the degree of order in the long-range carbon layer is reflected, where the peak intensity is noted as SG, satisfies 0.32.ltoreq.SD/(SD+SG). Ltoreq.1.88. The raman diagram of the modified hard carbon anode material can be measured by the following test conditions: during testing, the laser wavelength of the Raman spectrometer is set to be 532nm, and the wave number range of the test is 1000-2000 cm -1 。
(7) As shown in fig. 1, in the XRD pattern of the modified hard carbon negative electrode material, the (002) crystal face peak intensity S (002) corresponding to the carbon material in the vicinity of 23 to 24 ° and the (100) crystal face peak intensity S (100) corresponding to the carbon material in the vicinity of 43 to 44 °, there are (002) crystal face peaks or (100) crystal face peaks which are non-sharp crystal face peaks (broad peaks), and S (002) > S (100). The XRD pattern of the modified hard carbon negative electrode material can be measured by the following test conditions: the X-ray diffraction analysis ray source adopts Cu-K alpha radiation, the wavelength is 1.5406A, the tube voltage is 20-50 kV, the tube current is 15-60 mA, the stepping scanning mode is adopted, and the angle range is 0-90 degrees.
The modified hard carbon negative electrode material can be used for preparing a negative electrode plate and a sodium ion secondary battery, and the specific process is as follows:
(1) Primary mixing: placing the modified hard carbon anode material and the conductive material into a stirring tank of a stirrer, and dry-mixing and stirring for 5-30 min at the rotating speed of 200-1500 r/min to obtain a mixture;
wherein the modified hard carbon anode material, the conductive material and the bonding substance respectively account for 85-99.6wt%, 0.2-7wt% and 0.2-8.0wt% in percentage by mass;
the conductive material is at least one of conductive carbon black, acetylene black, graphite, graphene, carbon micro-wires, carbon nano-wires, carbon micro-tubes and carbon nano-tubes;
(2) Secondary mixing: adding a binding substance and deionized water into a container, adding water until the content of solid substances in a stirring tank is 40-60% (preferably 45-55%), adjusting the viscosity to be 1.0-6 Pa.s (preferably 2.5-4 Pa.s), obtaining mixed hard carbon slurry, coating the mixed hard carbon slurry on a negative current collector, drying at 80-105 ℃, rolling and cutting to obtain a hard carbon negative electrode plate;
wherein the bonding substance is polyacrylonitrile, polyvinylidene fluoride, polyvinyl alcohol, carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium carboxymethyl cellulose, polymethacrylate, polyacrylic acid, lithium polyacrylate, polyacrylamide styrene-butadiene rubber, sodium alginate and the like;
the negative current collector is one or more of aluminum foil, porous aluminum foil, foam nickel/aluminum foil, galvanized aluminum foil, nickel-plated aluminum foil, carbon-coated aluminum foil, nickel foil and titanium foil. Preferably aluminum foil, nickel-plated aluminum foil and carbon-coated aluminum foil; the thickness is 2-50 mu m;
the compacted density of the cut hard carbon negative plate is 0.80-1.80 g/cm 3 The thickness is 35-500 μm, preferably 0.90-1.55 g/cm 3 The thickness is 80-380 mu m;
(3) And (3) manufacturing a battery: sequentially stacking and winding the positive plate, the isolating film and the hard carbon negative plate to obtain a bare cell and an ultrasonic welding tab, putting the bare cell into a battery shell, drying at 150-180 ℃ to remove moisture, injecting electrolyte into the battery shell, and packaging to obtain the sodium ion secondary battery;
wherein the positive electrode sheet includes a positive electrode current collector and a positive electrode active material,
the positive electrode current collector and the negative electrode current collector are independently selected from one or more of aluminum foil, porous aluminum foil, foam nickel/aluminum foil, galvanized aluminum foil, nickel-plated aluminum foil, carbon-coated aluminum foil, nickel foil and titanium foil; preferably aluminum foil, nickel-plated aluminum foil and carbon-coated aluminum foil; the thickness is 2-50 mu m;
the positive electrode active material is at least one of sodium nickel manganese oxide, sodium nickel cobalt aluminate, sodium vanadium fluorophosphate, sodium iron manganese fluorophosphate and sodium nickel iron manganese oxide;
the isolating film is at least one polymer membrane of polyethylene, polypropylene, polysulfonyl, polyacrylonitrile, polyvinyl alcohol, polyarylethersulfone, polyvinylidene fluoride and polymalonic acid.
Example 1:
1. preparation of modified hard carbon anode material:
(1) Placing a first carbon source (phenolic resin, available from Allatin, CAS number: 9003-35-4, the same applies hereinafter) and a second carbon source (graphene with the length of 2.0-35 μm and the width of 0.3-16 μm), carrying out graphene oxidation treatment, namely placing 100g of graphene into 1L of solution containing 13.6wt% of oxidant (sulfuric acid), reacting at 60 ℃ in a reaction kettle, stirring for 2h, and finally fully washing and drying with deionized water to obtain the second carbon source), stirring for 2h at 350 ℃ (placing the second carbon source in the reaction kettle according to the mass ratio of 50:0.5), and carrying out heating rate of 3 ℃/min, wherein the obtained product is the mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) The mixed carbon source is sent to a heating furnace, then inactive gas argon is introduced to remove air in the heating furnace, the temperature of the heating furnace is controlled at 1300 ℃, carbonization is carried out for 4 hours, and hard carbon materials are obtained through crushing, demagnetizing and screening;
(4) Brominating a hard carbon material: adding a bromine mixture (containing 0.3wt% of sodium bromate in 3.8wt% of ammonium phosphate aqueous solution) into a hard carbon material according to the mass ratio of 100:25, then conveying the hard carbon material into a reaction kettle, performing hydrothermal bromination treatment at 80 ℃ for 1h, washing with water, and drying to obtain a modified hard carbon material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 5 ℃/min, introducing carbon-containing gas acetylene, and depositing for 25min to obtain the modified hard carbon anode material with the surface carbon deposition layer.
2. Application:
(1) Primary mixing: placing the modified hard carbon anode material and the conductive material (90% of conductive carbon black and 10% of carbon nano tubes) in a stirring tank of a stirrer, and dry-mixing and stirring for 60min at a rotating speed of 1500r/min to obtain a mixture;
(2) Secondary mixing: adding bonding substance (33% sodium carboxymethylcellulose+33% sodium polyacrylate+33% styrene-butadiene rubber) and deionized water into container (95.5wt%, 1.5wt% and 3.0wt% of modified hard carbon anode material, conductive material and bonding substance) until the content of solid substance in stirring tank is 52%, regulating viscosity to 3Pa.s to obtain mixed hard carbon slurry, coating the mixed hard carbon slurry on carbon coated aluminum foil/aluminum foil of anode current collector, drying at 95deg.C, and compacting density of 0.92 g/cm after rolling 3 A hard carbon negative plate with the thickness of 125 mu m;
(3) And (3) manufacturing a battery: sequentially stacking and winding a positive plate (nickel iron sodium manganate with 97.8wt% of positive active substance), a polypropylene isolating film and a hard carbon negative plate to obtain a bare cell, ultrasonically welding a tab, putting the bare cell into a battery shell, drying at 180 ℃ to remove water, injecting electrolyte into the battery shell, and packaging to obtain the sodium ion secondary battery.
Example 2:
the difference from example 1 is the preparation of a modified hard carbon anode material:
(1) Placing a first carbon source (phenolic resin) and a second carbon source (graphene with the length of 2.0-35 mu m and the width of 0.3-16 mu m, carrying out graphene oxidation treatment, namely placing 150g of graphene into 1L of solution containing 13.6wt% of oxidant (sulfuric acid), reacting at 60 ℃ in a reaction kettle, stirring for 2 hours, finally fully washing with deionized water, drying to obtain the second carbon source), stirring at 350 ℃ for 2 hours (placing the second carbon source in the reaction kettle according to the mass ratio of 50:1.5), and heating at the rate of 3 ℃/min to obtain a product which is a mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) The mixed carbon source is sent to a heating furnace, then inactive gas argon is introduced to remove air in the heating furnace, the temperature of the heating furnace is controlled at 1400 ℃, carbonization is carried out for 4 hours, and hard carbon materials are obtained through crushing, demagnetizing and screening;
(4) Brominating a hard carbon material: adding a bromine mixture (containing 3.8wt% of sodium bromate in an ammonium phosphate aqueous solution with the mass of 0.5wt% into the hard carbon negative electrode material) into the hard carbon negative electrode material according to the mass ratio of 100:25, and carrying out hydrothermal bromination treatment for 1h at 80 ℃ in a reaction kettle, washing with water and drying to obtain a modified hard carbon negative electrode material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 5 ℃/min, introducing carbon-containing gas acetylene, and depositing for 25min to obtain the modified hard carbon anode material with the surface carbon deposition layer.
Example 3:
the difference from example 1 is the preparation of a modified hard carbon anode material:
(1) Placing a first carbon source (phenolic resin) and a second carbon source (graphene with the length of 2.0-35 mu m and the width of 0.3-16 mu m, carrying out graphene oxidation treatment, namely placing 200g of graphene into 1L of solution containing 13.6wt% of oxidant (sulfuric acid), reacting at 60 ℃ in a reaction kettle, stirring for 2 hours, finally fully washing with deionized water, drying to obtain the second carbon source), stirring at 350 ℃ for 2 hours (placing the second carbon source in the reaction kettle according to the mass ratio of 50:3), and heating at the rate of 3 ℃/min to obtain a product which is a mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) The mixed carbon source is sent to a heating furnace, then inactive gas argon is introduced to remove air in the heating furnace, the temperature of the heating furnace is controlled at 1500 ℃, carbonization is carried out for 4 hours, and hard carbon materials are obtained through crushing, demagnetizing and screening;
(4) Brominating a hard carbon material: adding a bromine mixture (containing 3.8wt% of sodium bromate in an ammonium phosphate aqueous solution with the mass of 0.7wt% into the hard carbon anode material) into the hard carbon anode material according to the mass ratio of 100:25, and carrying out hydrothermal bromination treatment for 1h at 80 ℃ in a reaction kettle, washing with water and drying to obtain a modified hard carbon material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 5 ℃/min, introducing carbon-containing gas acetylene, and depositing for 25min to obtain the modified hard carbon anode material with the surface carbon deposition layer.
Example 4:
1. preparation of modified hard carbon anode material:
(1) The preparation method comprises the steps of (1) placing a first carbon source (starch) and a second carbon source (graphite obtained by graphitizing needle coke, the length of the graphite is 3.2-46 mu m, the width of the graphite is 1.6-18 mu m, oxidizing 100g of graphite in 1L of solution containing 15.6wt% of oxidant (sodium persulfate), reacting in a reaction kettle at 60 ℃, stirring for 2 hours, finally fully washing with deionized water, drying to obtain the second carbon source), stirring at 320 ℃ for 10-5 hours (placing in the reaction kettle according to the mass ratio of 100:3), and heating at 5 ℃/min to obtain a mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) The mixed carbon source is sent to a heating furnace, then inactive gas argon is introduced to remove air in the heating furnace, the temperature of the heating furnace is controlled at 1300 ℃, carbonization is carried out for 4 hours, and hard carbon materials are obtained through crushing, demagnetizing and screening;
(4) Brominating a hard carbon material: adding a bromine mixture (containing 3.8wt% of sodium bromide in an ammonium phosphate aqueous solution with the mass of 0.2wt% into a hard carbon negative electrode material) into a reaction kettle according to the mass ratio of 100:25, carrying out hydrothermal bromination treatment for 1h at 80 ℃, washing with water, and drying to obtain a modified hard carbon material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 600 ℃ at a heating rate of 3 ℃/min, introducing carbon-containing gas methane, and depositing for 20min to obtain the modified hard carbon anode material of the surface carbon deposition layer.
2. Application:
(1) Primary mixing: placing the modified hard carbon anode material and the conductive material (90% of conductive carbon black and 10% of carbon nano tubes) in a stirring tank of a stirrer, and dry-mixing and stirring for 60min at a rotating speed of 1500r/min to obtain a mixture;
(2) Secondary mixing: adding bonding substance (33% sodium carboxymethylcellulose+33% sodium polyacrylate+33% styrene-butadiene rubber) and deionized water into container (95.0wt%, 2.0wt% and 3.0wt% of modified hard carbon anode material, conductive material and bonding substance) until the content of solid substance in stirring tank is 52%, regulating viscosity to 3Pa.s to obtain mixed hard carbon slurry, coating the mixed hard carbon slurry on carbon coated aluminum foil/aluminum foil of anode current collector, drying at 95deg.C, and compacting density of 0.94 g/cm after rolling 3 A hard carbon negative plate with the thickness of 125 mu m;
(3) And (3) manufacturing a battery: sequentially stacking and winding a positive plate (nickel iron sodium manganate with 97.8wt% of positive active substance), a polypropylene isolating film and a hard carbon negative plate to obtain a bare cell, ultrasonically welding a tab, putting the bare cell into a battery shell, drying at 180 ℃ to remove water, injecting electrolyte into the battery shell, and packaging to obtain the sodium ion secondary battery.
Example 5:
the difference from example 4 is the preparation of a modified hard carbon anode material:
(1) The preparation method comprises the steps of (1) placing a first carbon source (starch) and a second carbon source (graphite obtained by graphitizing needle coke, the length of the graphite is 3.2-46 mu m, the width of the graphite is 1.6-18 mu m, oxidizing 150g of graphite in 1L of solution containing 15.6wt% of oxidant (sodium persulfate), reacting in a reaction kettle at 60 ℃, stirring for 2 hours, finally fully washing with deionized water, drying to obtain the second carbon source), stirring at 320 ℃ for 10-5 hours (placing in the reaction kettle according to the mass ratio of 100:6), and heating at 5 ℃/min to obtain a mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) The mixed carbon source is sent to a heating furnace, then inactive gas argon is introduced to remove air in the heating furnace, the temperature of the heating furnace is controlled at 1400 ℃, carbonization is carried out for 2 hours, and hard carbon materials are obtained through crushing, demagnetizing and screening;
(4) Brominating a hard carbon material: adding a bromine mixture (containing 3.8wt% of sodium bromide in an ammonium phosphate aqueous solution with the mass of 0.4wt% into a hard carbon negative electrode material) into a reaction kettle according to the mass ratio of 100:25, carrying out hydrothermal bromination treatment for 1h at 80 ℃, washing with water, and drying to obtain a modified hard carbon material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 600 ℃ at a heating rate of 3 ℃/min, introducing carbon-containing gas methane, and depositing for 20min to obtain the modified hard carbon anode material of the surface carbon deposition layer.
Example 6:
the difference from example 4 is the preparation of a modified hard carbon anode material:
(1) The preparation method comprises the steps of (1) placing a first carbon source (phenolic resin and starch with the mass ratio of 9.5:0.5) and a second carbon source (graphite obtained by graphitizing needle coke, wherein the length is 3.2-46 mu m, the width is 1.6-18 mu m, oxidizing treatment is carried out, 200g of graphite is placed in 1L of solution containing 15.6wt% of oxidant (sodium persulfate), reaction is carried out in a reaction kettle at 60 ℃ for 2 hours, finally, deionized water is used for fully washing and drying, the second carbon source is obtained), stirring is carried out for 10-5 hours at 320 ℃, the heating rate is 5 ℃/min, and the obtained product is a mixed carbon source;
(2) Pumping out gas generated in the reaction kettle, rapidly cooling the mixed carbon source to be less than 15 ℃ within 3 hours, and forming to obtain a blocky mixed carbon source;
(3) And (3) delivering the mixed carbon source to a heating furnace, introducing inactive gas argon to remove air in the heating furnace, controlling the temperature of the heating furnace at 1500 ℃, carbonizing for 4 hours, crushing, demagnetizing and screening to obtain the hard carbon material.
(4) Brominating a hard carbon material: adding a bromine mixture (containing 3.8wt% of sodium bromide in an ammonium phosphate aqueous solution with the mass of 0.6wt% into a hard carbon negative electrode material) into a reaction kettle according to the mass ratio of 100:25, carrying out hydrothermal bromination treatment for 1h at 80 ℃, washing with water, and drying to obtain a modified hard carbon material;
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the modified hard carbon material to a deposition furnace, controlling the temperature of the deposition furnace at 600 ℃ at a heating rate of 3 ℃/min, introducing carbon-containing gas methane, and depositing for 20min to obtain the modified hard carbon anode material of the surface carbon deposition layer.
Comparative example 1:
the difference from example 1 is that the step of "preparing a modified hard carbon anode material" in the step (2) is not included, the mixed carbon source is rapidly cooled to < 15 ℃ within 3h, and then formed, and a blocky mixed carbon source is obtained.
Comparative example 2:
the difference from example 1 is that the second carbon source is not added.
Comparative example 3:
the difference from example 1 is that the hard carbon material was not subjected to bromination treatment (step (4) in the preparation of the modified hard carbon anode material).
Comparative example 4:
the difference from comparative example 1 is that the second carbon source was not added and the hard carbon material was not subjected to bromination treatment.
Analysis of results:
1. characterization of materials
As shown in fig. 1, the XRD patterns of the modified hard carbon anode materials obtained in example 4, comparative example 1 and example 1 from top to bottom show two broad diffraction peaks around 2θ=23° (002) crystal plane and 2θ=44° (100) crystal plane, which indicate that both diffraction peaks are disordered structures, and the diffraction peaks of the (002) (2θ=23°) crystal plane in example 4 and example 1 in the XRD patterns are slightly shifted to high angles, which indicates that the microcrystalline structures of the materials tend to be ordered (graphite-like crystals are induced by graphite).
As shown in fig. 2, the raman diagrams of comparative example 1, example 4 and example 1 are from top to bottom, and the relations SD/(sd+sg) of D-wave Duan Fengjiang SD and G-wave Duan Fengjiang SG of comparative example 1, example 4 and example 1 are 0.47, 0.49 and 0.52, respectively.
As shown in fig. 3, the modified hard carbon negative electrode material obtained in example 1 has an ordered graphite structure (left side) inside and is combined with amorphous carbon (right side), and a graphitized-like region is formed between the graphite structure and the amorphous carbon.
As shown in fig. 4, in the modified hard carbon negative electrode material obtained in example 1, the micro-pores in the partially modified hard carbon negative electrode material resulted from the addition of the second carbon source (oxidized graphene).
2. Performance testing
Cutting the negative electrode sheets prepared in examples 1-6 and comparative examples 1-4 into round pieces with the diameter of 12mm, then conveying the round pieces into a glove box to assemble 2032 type button cells, wherein the electrolyte is composed of a solvent EC&NaClO in DMC (volume ratio 1:1) 1M 4 . The polypropylene film is used as a separation film, and the metal sodium sheet is used as a counter electrode. The rechargeable battery was subjected to a 0-2.5 v discharge/charge test, the charge capacity of the rechargeable battery was the initial reversible capacity, and the initial coulomb efficiency (initial coulomb efficiency=initial charge/initial discharge) of the rechargeable battery was calculated, and the result is shown in table 1.
The sodium ion secondary batteries of examples 1 to 6 and comparative examples 1 to 4 were subjected to formation (0.02C to 3.7V at a high temperature of 45 ℃, then 0.5C to 4.0V, and 4.0V constant voltage to a current of 0.05C or less), and constant volume (1C to 2.0V at 25 ℃, then 0.1C to 2.0V). The sodium ion secondary batteries of examples 1 to 6 and comparative examples 1 to 3 were charged to 4.0V at 0.5C (constant current charge of 0.5C to 4.0V, constant voltage charge of 4.0V to current of 0.05C or less), then 0.5C was discharged to 2.0V, the discharge capacity was C1, full charge of 0.5C to 4.0V (constant current charge of 0.5C to 4.0V, constant voltage charge of 4.0V to current of 0.05C or less), discharge capacity was C2, full charge of 0.5C to 4.0V (constant current charge of 0.5C to 4.0V, constant voltage charge of 4.0V to current of 0.05C or less), discharge capacity was C1.5C to 2.0V, the discharge capacity was C3, the discharge ratio of 1.5 c=c2/c1×100%, and the results were shown in table 2.
TABLE 1 first circle coulombic efficiency, initial reversible capacity
| First circle coulombic efficiency | Initial reversible capacity (mAh/g) | |
| Example 1 | 92.1% | 342.6 |
| Example 2 | 91.4% | 339.5 |
| Example 3 | 91.3% | 340.2 |
| Example 4 | 90.4% | 339.0 |
| Example 5 | 90.3% | 337.4 |
| Example 6 | 89.7% | 336.6 |
| Comparative example 1 | 87.5% | 327.7 |
| Comparative example 2 | 83.1% | 313.2 |
| Comparative example 3 | 89.6% | 334.0 |
| Comparative example 4 | 82.6% | 308.6 |
TABLE 2 discharge ratio of 1.5C, 2.0C
| 1.5C discharge ratio | 2.0C discharge ratio | |
| Example 1 | 97.1% | 95.3% |
| Example 2 | 97.3% | 96.0% |
| Example 3 | 96.9% | 95.4% |
| Example 4 | 96.6% | 94.7% |
| Example 5 | 96.8% | 94.5% |
| Example 6 | 96.9% | 95.0% |
| Comparative example 1 | 96.6% | 94.1% |
| Comparative example 2 | 96.2% | 94.2% |
| Comparative example 3 | 95.6% | 93.8% |
| Comparative example 4 | 94.7% | 93.3% |
The results show that: in the examples, the enhanced hydrogen bonding interaction between the polymer intermediate and the graphite intermediate strengthens the tight anchoring of the polymer intermediate on the hydroxyl-rich surface layer of the graphite, and the addition of an oxidized secondary carbon source (graphite) favors graphitized carbon-like formation, thus contributing to the improved ICE and capacity of the modified hard carbon negative electrode material of the examples, while the ICE and capacity of comparative examples 1, 2 are lower; the discharge rates of 1.5C and 2.0C are improved to different degrees, and the discharge rates of 1.5C and 2.0C are reduced in comparative examples 3 and 4 relatively.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (9)
1. A preparation method of a modified hard carbon anode material is characterized by comprising the following steps of,
s1: performing heat treatment on the mixture of the first carbon source and the second carbon source to obtain a mixed carbon source;
the first carbon source is selected from one or more of starch, dextrin, sucrose, fructose, glucose, phenolic resin, epoxy resin, urea-formaldehyde resin, polyvinylpyrrolidone and polyamic acid; the second carbon source is graphitized carbon material subjected to oxidation treatment;
s2: performing rapid cooling treatment on the mixed carbon source obtained in the step S1 to obtain a formed mixed carbon source;
the rapid cooling treatment is to cool the temperature to below 15 ℃ within the cooling time of 2-4 hours;
s3: carbonizing the formed mixed carbon source obtained in the step S2 under the condition of an inactive atmosphere to obtain a hard carbon material;
s4: brominating the hard carbon material obtained in the step S3 to obtain a modified hard carbon material;
the specific operation of the bromination treatment is as follows: 4-1) dissolving a bromine compound in an ammonium salt solution to obtain a bromine mixture with the concentration of the bromine compound of 0.1-1wt%; 4-2) mixing the bromine mixture and the hard carbon material according to the mass ratio of 100:1-50, and reacting for 20 min-4 h at the temperature of 70-110 ℃; 4-3) washing the first product obtained in the step 4-2); 4-4) drying the second product obtained in the step 4-3) to obtain a modified hard carbon material;
s5: and (3) introducing carbon-containing gas into the modified hard carbon material under the heating condition, and carrying out carbon deposition to obtain the modified hard carbon negative electrode material.
2. The method of claim 1, wherein the mass ratio of the first carbon source to the second carbon source is 100:0.1 to 30.
3. The method of claim 1 or 2, wherein the graphitized carbon material is selected from one or more of graphite carbon microspheres, aphanitic graphite, crystalline graphite, bulk graphite, and graphene.
4. The preparation method according to claim 1, wherein in the step S1, the heat treatment is performed under stirring conditions, the stirring speed is 60 rpm to 480rpm, and the stirring time is 10min to 5h; the heat treatment temperature is 120-400 ℃, and the heating rate is 2-20 ℃/min.
5. The preparation method according to claim 1, wherein in the step S3, the carbonization treatment time is 30min to 8h; the carbonization treatment temperature is 1000-1800 ℃.
6. The method of claim 1, wherein the bromine compound is selected from the group consisting of sodium bromide, potassium bromide, lithium bromide, sodium bromate, potassium bromate, hypobromous acid, and ammonium bromide.
7. The preparation method according to claim 1, wherein in the step S5, the heating condition is 400 to 1000 ℃; the carbon-containing gas is selected from one or more of methane, ethane, propane, acetylene, propyne, butyne and ethylene; the carbon deposition time is 5 min-60 min.
8. A modified hard carbon negative electrode material produced by the production method of any one of claims 1 to 7.
9. A sodium ion secondary battery comprising a negative electrode tab comprising a negative electrode current collector and a negative electrode material layer, wherein the negative electrode material layer comprises the modified hard carbon negative electrode material of claim 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311314102.6A CN117049517B (en) | 2023-10-11 | 2023-10-11 | Modified hard carbon negative electrode material and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311314102.6A CN117049517B (en) | 2023-10-11 | 2023-10-11 | Modified hard carbon negative electrode material and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117049517A CN117049517A (en) | 2023-11-14 |
| CN117049517B true CN117049517B (en) | 2023-12-22 |
Family
ID=88664826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311314102.6A Active CN117049517B (en) | 2023-10-11 | 2023-10-11 | Modified hard carbon negative electrode material and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117049517B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244401A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Hard carbon coated graphite negative electrode material, lithium ion battery and preparation method and application thereof |
| WO2023174299A1 (en) * | 2022-03-14 | 2023-09-21 | 北京卫蓝新能源科技有限公司 | Negative electrode plate for lithium battery, and preparation method and application of negative electrode plate |
-
2023
- 2023-10-11 CN CN202311314102.6A patent/CN117049517B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111244401A (en) * | 2018-11-28 | 2020-06-05 | 上海杉杉科技有限公司 | Hard carbon coated graphite negative electrode material, lithium ion battery and preparation method and application thereof |
| WO2023174299A1 (en) * | 2022-03-14 | 2023-09-21 | 北京卫蓝新能源科技有限公司 | Negative electrode plate for lithium battery, and preparation method and application of negative electrode plate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117049517A (en) | 2023-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Sun et al. | Facile synthesis of high performance hard carbon anode materials for sodium ion batteries | |
| Dong et al. | Tailoring defects in hard carbon anode towards enhanced Na storage performance | |
| Ren et al. | Lath-shaped biomass derived hard carbon as anode materials with super rate capability for sodium-ion batteries | |
| KR20200039715A (en) | Carbon-based composite material, manufacturing method thereof, and lithium-ion battery including the same | |
| Feng et al. | A novel acetylene black/sulfur@ graphene composite cathode with unique three-dimensional sandwich structure for lithium-sulfur batteries | |
| Yuan et al. | Enhanced sodium storage performance in flexible free-standing multichannel carbon nanofibers with enlarged interlayer spacing | |
| Gaikwad et al. | Enhanced catalytic graphitization of resorcinol formaldehyde derived carbon xerogel to improve its anodic performance for lithium ion battery | |
| JP7253559B2 (en) | Method for preparing immobilized selenium | |
| CN110451475B (en) | Preparation method of asphalt-based carbon microspheres and application of asphalt-based carbon microspheres as sodium ion battery electrode material | |
| WO2023173772A1 (en) | Preparation method for and use of hard carbon negative electrode material | |
| Wu et al. | High-performance lithium-sulfur battery based on porous N-rich gC 3 N 4 nanotubes via a self-template method | |
| WO2024000815A1 (en) | Preparation method for and use of high-performance hard carbon material | |
| CN110395728B (en) | Preparation method of porous carbon sphere negative electrode material for lithium battery | |
| Jia et al. | In-situ formation of ultrafine ZnMn2O4-MnOOH composite nanoparticles embedded into porous carbon nanospheres for stable aqueous zinc-ion batteries | |
| Zhang et al. | Sulfur cathodes based on dual-functional GMs-MnOOH for high performance lithium sulfur batteries | |
| CN117049517B (en) | Modified hard carbon negative electrode material and preparation and application thereof | |
| CN111933908A (en) | Gamma irradiation regulated and controlled popcorn hard carbon/SnP3Method for preparing sodium ion battery cathode by composite material | |
| CN116613297A (en) | Hard carbon negative electrode material, preparation method thereof, negative electrode plate and application thereof | |
| Chen et al. | CoCl2 encapsulated in nitrogen-doped carbon hollow cubic nanobox enabling long-life and high-rate lithium storage | |
| CN114639809B (en) | Composite hard carbon negative electrode material, preparation method and application | |
| Liu et al. | Natural nori-based porous carbon composite for sustainable lithium-sulfur batteries | |
| CN113140705A (en) | Secondary battery cathode, preparation method thereof and secondary battery | |
| Zhang et al. | A high-rate and ultrastable anode for lithium ion capacitors produced by modifying hard carbon with both surface oxidation and intercalation | |
| CN114300663B (en) | Potassium ion secondary battery anode material and preparation method thereof, anode sheet and potassium ion secondary battery | |
| Ge et al. | Scale-Up Synthesis and Characterization of Epoxyphenolics Based Pyrolysis Carbons as Highly-Performed Anodes for Li-Ion Batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |