CN116613297A - Hard carbon negative electrode material, preparation method thereof, negative electrode plate and application thereof - Google Patents
Hard carbon negative electrode material, preparation method thereof, negative electrode plate and application thereof Download PDFInfo
- Publication number
- CN116613297A CN116613297A CN202310775855.0A CN202310775855A CN116613297A CN 116613297 A CN116613297 A CN 116613297A CN 202310775855 A CN202310775855 A CN 202310775855A CN 116613297 A CN116613297 A CN 116613297A
- Authority
- CN
- China
- Prior art keywords
- hard carbon
- organic polymer
- sodium
- layer
- negative electrode
- 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.)
- Pending
Links
- 229910021385 hard carbon Inorganic materials 0.000 title claims abstract description 171
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 147
- 229920000620 organic polymer Polymers 0.000 claims abstract description 76
- 239000002245 particle Substances 0.000 claims abstract description 76
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 70
- 230000008021 deposition Effects 0.000 claims abstract description 51
- 238000010438 heat treatment Methods 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 239000010405 anode material Substances 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 27
- 239000011734 sodium Substances 0.000 claims abstract description 27
- 238000003763 carbonization Methods 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 23
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 23
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 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 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 25
- 239000003795 chemical substances by application Substances 0.000 claims description 21
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000007800 oxidant agent Substances 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- -1 polyethylene Polymers 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 11
- 239000001099 ammonium carbonate Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 10
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 9
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 9
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- KDKYADYSIPSCCQ-UHFFFAOYSA-N but-1-yne Chemical compound CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 6
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims 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 claims description 5
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 claims description 4
- 239000003822 epoxy resin Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920000647 polyepoxide Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical compound CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 3
- 239000004254 Ammonium phosphate 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
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000005062 Polybutadiene Substances 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004280 Sodium formate Substances 0.000 claims description 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000001294 propane Substances 0.000 claims description 3
- 235000015424 sodium Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 3
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims description 3
- 235000019254 sodium formate Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 3
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 3
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 61
- 238000000151 deposition Methods 0.000 description 49
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 12
- 229910052786 argon Inorganic materials 0.000 description 11
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000007833 carbon precursor Substances 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005096 rolling process Methods 0.000 description 6
- 238000012216 screening Methods 0.000 description 6
- 239000004020 conductor Substances 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
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- 230000002441 reversible effect Effects 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000009830 intercalation Methods 0.000 description 4
- 230000002687 intercalation Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000005056 compaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 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 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000007580 dry-mixing Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
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- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 1
- 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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 229920002907 Guar gum Polymers 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
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 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
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- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000008859 change Effects 0.000 description 1
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- 235000010417 guar gum Nutrition 0.000 description 1
- 229960002154 guar gum Drugs 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- XSAOIFHNXYIRGG-UHFFFAOYSA-M lithium;prop-2-enoate Chemical compound [Li+].[O-]C(=O)C=C XSAOIFHNXYIRGG-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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- 239000000178 monomer Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 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 group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000002904 solvent Substances 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- 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
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- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a hard carbon negative electrode material, a preparation method thereof, a negative electrode plate and application thereof. The invention discloses a preparation method of a hard carbon anode material, which comprises the following steps: mixing oxidized graphene sheets with a dispersing agent solution to obtain a mixed dispersing liquid; adding a sodium source, hard carbon particles with oxidized surfaces and an organic polymer into the mixed dispersion liquid, and stirring and mixing to obtain a mixture of the hard carbon particles with the surfaces coated with the organic polymer; adding a pore former to the mixture, addingThermal stirring to form pores on the surface of the organic polymer in the mixture ， Cooling and solidifying; heating and carbonizing to obtain hard carbon particles coated by a porous organic polymer carbonized layer; and (3) introducing carbon-containing gas into the hard carbon particles coated by the porous organic polymer carbonization layer under the heating condition, and carrying out carbon deposition to obtain a carbon deposition layer coated on the surface of the porous organic polymer carbonization layer, thereby obtaining the hard carbon anode material. The hard carbon anode material has higher first coulombic efficiency and initial capacity.
Description
Technical Field
The invention relates to the technical field of secondary batteries, in particular to a hard carbon negative electrode material, a preparation method thereof, a negative electrode plate and application thereof.
Background
Electrochemical power storage devices play an important role in commercial electronics and electric automobiles. Among them, lithium Ion Batteries (LIBs) are the most popular devices. Nevertheless, LIBs are unable to achieve the ever-increasing electrochemical energy storage demands of the grid scale due to low abundance and maldistribution of lithium resources. Causing more research to turn to a richer, cheaper potential direction. Currently, most researchers consider Sodium Ion Batteries (SIBs) as a replacement for lithium ion batteries as a major direction of development for future power storage devices.
Among SIBs, carbonaceous materials are considered to be the most promising anode materials for commercial SIBs due to their variety of structure and sources, and wide availability and low cost. Commercial negative electrode materials in which graphite is LIBs, but is not suitable for SIBs because of Na + Cannot be intercalated into the graphite body and the Na-C binary compound formed is unstable.
In contrast, hard Carbon (HC) is a viable sodium ion intercalation negative electrode material. It has abundant microcrystalline structure and low embedded potential (about 0.1V), and is not only beneficial to absorbing more Na + And is favorable to Na + Is used for embedding and taking off. Porous structure design is generally considered as a reliable strategy for improving SIBs ion transport capacity and increasing the number of sodium storage active sites, but such strategy has a high probability of causing low first coulombic efficiency, limiting the practical application of hard carbon anode materials.
Disclosure of Invention
In order to solve the technical problems, the invention provides a hard carbon negative electrode material, a preparation method thereof, a negative electrode plate and application thereof. For improving the electrochemical performance of the battery and improving the first coulombic efficiency.
The first object of the present invention is to provide a method for preparing a hard carbon anode material, comprising the steps of:
providing a surface oxidized hard carbon particulate;
mixing oxidized graphene sheets with a dispersing agent solution to obtain a mixed dispersing liquid;
adding a sodium source, the hard carbon particles with oxidized surfaces and an organic polymer into the mixed dispersion liquid, and stirring and mixing to obtain a mixture of the hard carbon particles with the surfaces coated with the organic polymer;
adding a pore opening agent into the mixture, heating and stirring the mixture, forming pores on the surface of an organic polymer in the mixture, cooling and solidifying the pores to obtain a porous mixture;
heating and carbonizing the porous mixture in inert atmosphere to obtain hard carbon particles coated with a porous organic polymer carbonized layer;
and (3) carrying out carbon deposition, namely introducing carbon-containing gas into the hard carbon particles wrapped with the porous organic polymer carbonization layer under the heating condition to obtain a carbon deposition layer wrapped on the surface of the porous organic polymer carbonization layer, and obtaining the hard carbon anode material.
In one embodiment of the invention, the surface oxidation method of hard carbon particles: heating and sintering the hard carbon particles in a mixed atmosphere of air and inactive gas to realize the surface oxidation of the hard carbon particles; the volume ratio of the air to the inactive gas is 1-5: 5 to 20.
In one embodiment of the present invention, the preparation method of the oxidized graphene sheet comprises: and mixing the graphene sheets with an oxidant solution, heating, stirring, reacting, and drying to obtain oxidized graphene sheets.
In one embodiment of the present invention, the oxidizing agent in the oxidizing agent solution is selected from one or more of nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate, and sodium persulfate.
In one embodiment of the invention, at least one of the following conditions is met:
the mass volume ratio of the oxidized graphene sheets to the dispersant solution is 1-5: 50-100 kg/L;
the concentration of the dispersant solution is 0.005-0.2 wt%.
The mass ratio of the hard carbon particles to the organic polymer to the pore-forming agent is 1-50: 5-200: 1 to 100.
In one embodiment of the invention, at least one of the following conditions is met:
the organic polymer is at least one selected from polyacrylonitrile, polybutadiene, polystyrene, polyethylene, polyethersulfone, polyetherimide, polyimide, phenolic resin and epoxy resin;
the sodium source is at least one of sodium oxalate, sodium hydroxide, sodium carbonate, sodium chloride, sodium formate, sodium bicarbonate and sodium citrate;
the dispersing agent in the dispersing agent solution is selected from one or more of dimethylformamide, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and sodium alkyl sulfonate;
the pore opening agent is one or more selected from ammonium bicarbonate, ammonium carbonate, ammonium hypophosphite, ammonium hydrogen phosphate, ammonium phosphate, methanol, ethanol, n-propanol, isopropanol, formic acid, acetic acid and styrene.
In one embodiment of the invention, at least one of the following conditions is met:
the heating temperature in the heating and stirring process is 60-200 ℃, and the stirring time is 10-60 minutes;
the temperature in the heating carbonization is controlled at 800-1600 ℃, and the heating carbonization time is 30 min-20 h;
the heating condition in the carbon deposition is 500-1000 ℃, and the carbon deposition time is 5-60 min;
the carbon-containing gas is selected from one or more of methane, ethane, propane, acetylene, propyne, butyne and ethylene.
In one embodiment of the invention, the mass ratio of the hard carbon particles, the organic polymer and the pore opening agent is 1-50: 5-200: 1 to 100.
The second object of the present invention is to provide a hard carbon anode material, wherein the hard carbon anode material has a core-shell structure, hard carbon particles are core, and a porous organic polymer carbonized layer is coated on the surface of the hard carbon particles; the surface of the porous organic polymer carbonization layer is coated with a carbon deposition layer;
the carbon layer of the porous organic polymer carbonization layer is embedded with nano graphene sheets;
the porous organic polymer carbonized layer is doped with sodium element.
In one embodiment of the invention, at least one of the following conditions is met:
the particle size of the hard carbon particles is 0.02-5 mu m; further, the hard carbon particles have a particle size of 0.3 to 5 μm;
the thickness of the porous organic polymer carbonized layer is 0.2-20 mu m;
the thickness of the carbon deposition layer is 0.002-0.6 mu m.
The third object of the invention is to provide a hard carbon negative electrode plate, which comprises the hard carbon negative electrode material.
The fourth object of the invention is to provide a sodium ion secondary battery comprising the hard carbon negative electrode sheet.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) The invention discovers the relation between the capacity of a slope area and the capacity of a platform area in the capacity of a battery, the surface defects of a hard carbon material and the internal closed pores, the capacity of the slope area is greatly influenced by the surface defects of the material, the capacity of the platform area is greatly influenced by the internal structure, and the capacity of the platform area occupies a larger proportion in the sodium storage capacity of the hard carbon, and the capacity of the platform area is improved by designing and optimizing the internal structure of the material so as to improve the capacity of the material, so that a pore-forming strategy for preparing a porous organic polymer carbonized layer on the surface of an organic polymer coating layer by using a pore-forming agent is utilized to form a proper internal porous structure, and the high-capacity hard carbon anode material is prepared.
(2) Oxidized graphene sheets are inserted into the carbon layer of the porous organic polymer carbonization layer, and the intercalation treatment of the graphene sheets can widen the interval between carbon layers, so that sodium insertion/extraction is easier, and sodium ion diffusion kinetics is improved.
(3) The carbon deposition layer is formed by depositing carbon-containing gas at 500-1000 ℃, and the surface of the carbon deposition layer is provided with an amorphous structure with less residual oxygen atoms and defects; the amorphous carbon layer can reduce Na + Diffusion resistance on the surface of the hard carbon anode material; the carbon deposition layer synthesizes super-micropores (about 0.5 nm) on the surface of the material and a hard carbon material rich in active sites for adsorbing sodium, wherein the super-micropores can prevent electrolyte from entering and sodium ions from excessively consuming on the surface, and can improve the first coulomb efficiency of the material.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic illustration of a hard carbon negative electrode material of the present invention;
FIG. 2 is a TEM image of a polymer carbonized layer of a hard carbon anode material in example 1 of the present invention;
FIG. 3 is XRD patterns of hard carbon negative electrode materials of example 1 and comparative example 1 of the present invention;
FIG. 4 is a graph showing the discharge/charge curves of 0 to 2.5V for button cells prepared from the hard carbon negative electrode sheets obtained in example 1 and comparative example 1 of the present invention;
description of the specification reference numerals: 1. a carbon deposition layer; 2. a porous organic polymer carbonized layer; 3. a nano graphene sheet; 4. hard carbon particles.
Detailed Description
The first object of the present invention is to provide a method for preparing a hard carbon anode material, comprising the steps of:
providing a surface oxidized hard carbon particulate;
mixing oxidized graphene sheets with a dispersing agent solution to obtain a mixed dispersing liquid;
adding a sodium source, the hard carbon particles with oxidized surfaces and an organic polymer into the mixed dispersion liquid, stirring and mixing to obtain a mixture of the hard carbon particles with the surfaces coated with the organic polymer (fully enabling the organic polymer to coat the hard carbon particles and the oxidized graphene sheets to form the nano graphene sheets of the interpolation layer), adding a pore opening agent into the mixture, stirring for 10-60 minutes at 60-200 ℃, forming pores on the surfaces of the organic polymer in the mixture, cooling to 0-40 ℃, stopping stirring, cooling and solidifying the pores (the organic polymer on the surfaces of the hard carbon particles overflows from gas openings at high temperature, solidifying the pores at low temperature) to obtain a porous mixture;
introducing inactive gas into the porous mixture to remove air in the porous mixture, heating and carbonizing for 30 min-20 h, crushing and screening to obtain hard carbon particles coated with a porous organic polymer carbonized layer;
and (3) introducing carbon-containing gas into the hard carbon particles coated with the porous organic polymer carbonized layer under the heating condition, and performing carbon deposition to obtain a carbon deposition layer coated on the porous organic polymer carbonized layer, thereby obtaining the hard carbon anode material.
In a specific embodiment, the surface oxidation method of the hard carbon particles comprises: and heating and sintering the hard carbon particles in a mixed atmosphere of air and inert gas to realize the surface oxidation of the hard carbon particles. The hard carbon particles subjected to surface oxidation treatment have improved compatibility with organic polymers and tighter bonding with oxygen-containing functional groups on the polymers.
Further, the volume ratio of air to inactive gas is 1-5: 5-20;
further, the inert gas is selected from one or more of nitrogen, helium and argon.
Further, the temperature of the heating sintering is 600-1500 ℃ and the sintering time is 1-5 h; the temperature rising rate is 2-20 ℃/min.
In a specific embodiment, the preparation method of the oxidized graphene sheet comprises the following steps: and mixing the graphene sheets with an oxidant solution, reacting in a reaction kettle at 40-90 ℃, and stirring for 30 min-8 h to obtain oxidized graphene sheets. The oxidation treatment of the graphene sheets can increase oxygen-containing functional groups on the surfaces of the graphene sheets, so that the graphene sheets are more active in performance, the compatibility with the organic polymer can be effectively improved, the graphene sheets are more tightly combined with the oxygen-containing functional groups on the organic polymer, and therefore the intercalation of the graphene sheets in the later stage is facilitated.
In a specific embodiment, the thickness of the graphene sheet is 2-500 nm, and the length is 10-5000 nm.
In a specific embodiment, the oxidant in the oxidant solution is selected from one or more of nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate and sodium persulfate.
In a specific embodiment, the concentration of the oxidizer solution is 0.2 to 38wt%.
In a specific embodiment, the dosage of the graphene sheets is 10-200 g/L.
In a specific embodiment, at least one of the following conditions is satisfied:
the mass volume ratio of the oxidized graphene sheets to the dispersant solution is 1-5: 50-100 kg/L;
the concentration of the dispersant solution is 0.005-0.2 wt%.
The sodium source is used in an amount of 0.1 to 10wt% of the mixed dispersion.
The mass ratio of the hard carbon particles to the organic polymer to the pore-forming agent is 1-50: 5-200: 1 to 100.
Further, in 1L of the mixed dispersion liquid, the mass volume ratio of the hard carbon particles to the organic polymer to the pore-forming agent is 10-500 g/L, 50-2000 g/L and 10-1000 g/L, namely, the hard carbon particles, the organic polymer, the pore-forming agent and the mixed dispersion liquid is respectively 10-500 g/L, 50-2000 g/L and 10-1000 g/L.
In a specific embodiment, at least one of the following conditions is satisfied:
the organic polymer is at least one selected from polyacrylonitrile, polybutadiene, polystyrene, polyethylene, polyethersulfone, polyetherimide, polyimide, phenolic resin and epoxy resin;
the sodium source is at least one of sodium oxalate, sodium hydroxide, sodium carbonate, sodium chloride, sodium formate, sodium bicarbonate and sodium citrate;
the dispersing agent in the dispersing agent solution is selected from one or more of dimethylformamide, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and sodium alkyl sulfonate;
the pore opening agent is one or more selected from ammonium bicarbonate, ammonium carbonate, ammonium hypophosphite, ammonium hydrogen phosphate, ammonium phosphate, methanol, ethanol, n-propanol, isopropanol, formic acid, acetic acid and styrene. The inner holes are formed by the pore opening agent, so that more nanopores are formed. The capacity of the platform area of the battery is more influenced by the internal structure, and more nano pores are formed in the battery, so that the capacity is improved.
In one embodiment of the invention, at least one of the following conditions is met:
the heating temperature in the heating and stirring process is 60-200 ℃, and the stirring time is 10-60 minutes;
the temperature of the reaction cavity in the heating carbonization is controlled at 800-1600 ℃, and the heating carbonization time is 30 min-20 h;
the heating condition in the carbon deposition is 500-1000 ℃, and the carbon deposition time is 5-60 min;
the carbon-containing gas is selected from one or more of methane, ethane, propane, acetylene, propyne, butyne and ethylene.
In a specific embodiment, the mass ratio of the hard carbon particles to the organic polymer to the pore-forming agent is 1-50: 5-200: 1 to 100.
The second object of the present invention is to provide a hard carbon anode material, wherein the hard carbon anode material has a core-shell structure, hard carbon particles are core, and a porous organic polymer carbonized layer is coated on the surface of the hard carbon particles; the porous organic polymer carbonization layer is coated with a carbon deposition layer;
the porous organic polymer carbonization layer is internally embedded with nano graphene sheets;
the porous organic polymer carbonized layer is doped with sodium element.
In a specific embodiment, at least one of the following conditions is satisfied:
the particle size of the hard carbon particles is 0.02-5 mu m; further, the hard carbon fine particles may have a particle size of 0.3 to 5. Mu.m, specifically, 0.3 to 0.5. Mu.m, 0.5 to 1. Mu.m, 1 to 2. Mu.m, 2 to 3. Mu.m, 3 to 4. Mu.m, 4 to 5. Mu.m, etc.
The thickness of the porous organic polymer carbonized layer is 0.2-20 mu m; further, the thickness may vary from 0.2 to 0.5. Mu.m, 0.5 to 1. Mu.m, 1 to 2. Mu.m, 2 to 3. Mu.m, 3 to 4. Mu.m, 4 to 5. Mu.m, 5 to 6. Mu.m, 6 to 7. Mu.m, 7 to 8. Mu.m, 8 to 10. Mu.m, 10 to 12. Mu.m, 12 to 15. Mu.m, 15 to 18. Mu.m, 18 to 20. Mu.m.
The thickness of the carbon deposition layer is 0.002-0.6 mu m. Further, the thickness may vary from 0.002 to 0.005 μm, 0.005 to 0.008 μm, 0.008 to 0.01 μm, 0.01 to 0.015 μm, 0.015 to 0.02 μm, 0.02 to 0.05 μm, 0.05 to 0.07 μm, 0.07 to 0.09 μm, 0.09 to 0.10 μm, 0.10 to 0.15 μm, 0.15 to 0.20 μm, 0.20 to 0.25 μm, 0.25 to 0.3 μm, 0.3 to 0.4 μm, 0.4 to 0.5 μm, 0.5 to 0.6 μm.
The third object of the invention is to provide a hard carbon negative electrode plate, which comprises the hard carbon negative electrode material.
The preparation method of the negative electrode plate comprises the following steps:
(1) Primary mixing: placing the 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;
(2) Secondary mixing: adding binding substances and deionized water into the mixture in a container until the content of solid substances in the stirring tank is 40-60% (preferably 45-55%), regulating 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 electrode current collector, drying at 80-105 ℃, rolling for one time, rolling for two times, and cutting to obtain the hard carbon negative electrode sheet.
In a specific embodiment, the mass percentage of the hard carbon anode material, the conductive material and the bonding substance added in the steps (1) and (2) is 85 to 99.6 weight percent, 0.2 to 7 weight percent and 0.2 to 8.0 weight percent.
In a specific embodiment, the conductive material in the steps (1) and (2) 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.
In specific embodiments, the binding substance in step (1) and (2) is different monomers, polymers, and copolymers of acrylonitrile, vinylidene fluoride, vinyl alcohol, carboxymethyl cellulose, lithium carboxymethyl cellulose, sodium carboxymethyl cellulose, methacryloyl, acrylic acid, lithium acrylate, acrylamide, amide, imide, acrylate, styrene butadiene rubber, sodium alginate, chitosan, ethylene glycol, and guar gum.
In a specific embodiment, the primary rolling and the secondary rolling in the step (2) are as follows: the first 10-80T pressure is pressed down to 40-80% of the required compaction density, and the second 10-80T pressure is pressed down to 80-110% of the required compaction density.
In a specific embodiment, the compacted density of the hard carbon negative plate cut in the step (2) is 0.80-1.80 g/cm 3 The thickness is 35-500 μm, preferably 0.90-1.1 g/cm 3 The thickness is 80-240 mu m;
in a specific embodiment, the negative electrode current collector or the positive electrode current collector in the step (2) 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 of the negative electrode current collector or the positive electrode current collector is 2-50 mu m.
A fourth object of the present invention is to provide a sodium ion secondary battery including the negative electrode tab. The preparation method of the sodium ion secondary battery comprises the following steps: and 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.
In a specific embodiment, the positive electrode active material in the positive electrode sheet 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.
In a specific embodiment, the separator is a polymer separator made of at least one of polyethylene, polypropylene, polysulfonyl, polyacrylonitrile, polyvinyl alcohol, polyarylethersulfone, polyvinylidene fluoride, and polymalonic acid.
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. Unless otherwise specified, all materials used are commercially available products.
Example 1:
the embodiment provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
1. preparation of hard carbon negative electrode material
(1) Surface oxidation of hard carbon particles: the volume ratio of the air to the argon of the hard carbon particles is 2: sintering for 2 hours at 1100 ℃ in 20 atmosphere, wherein the heating rate is 10 ℃/min, and obtaining the hard carbon particles with oxidized surfaces.
(2) Oxidized graphene sheets and a dispersing agent (sodium hexametaphosphate) solution with the mass concentration of 0.02 weight percent are mixed according to the mass volume ratio of 2:100kg/L of the mixture was placed in a reaction vessel to obtain a mixed dispersion.
(3) Adding sodium carbonate (the dosage of the sodium carbonate is 3wt% of the mass of the mixed dispersion liquid) into the mixed dispersion liquid, sequentially adding 100g of hard carbon particles and 800g of organic polymer (polystyrene) into the mixed dispersion liquid according to 1L, stirring and dispersing (fully enabling the organic polymer to wrap the hard carbon particles and oxidized graphene sheets to form nano graphene sheets of an interpolation layer), adding 20g of pore opening agent (ammonium carbonate), stirring at 90 ℃ for 30min, cooling to 25 ℃ and stopping stirring (the organic polymer on the surface of the hard carbon particles overflows from gas openings at high temperature and solidifying pores at low temperature).
(4) The temperature of the heating furnace is controlled at 1200 ℃, and then inactive gas argon is introduced to remove air in the heating furnace, and carbonization, crushing screening and the like are carried out for 8 hours, so as to obtain the porous hard carbon precursor.
(5) Carbon deposition (preparation of carbon deposition layer): and (3) delivering the hard carbon precursor to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 10 ℃/min, introducing carbon-containing gas acetylene/propyne, and depositing for 30min to obtain the sodium ion hard carbon anode material of the surface carbon deposition layer. A TEM image of the polymer carbonized layer of the obtained hard carbon anode material is shown in fig. 2. As can be seen from fig. 2, the lamellar structure of the nanographene sheets in the hard carbon negative electrode material is very evident. The XRD pattern of the obtained hard carbon negative electrode material is shown in FIG. 3.
Wherein, the preparation method of the oxidized graphene sheets in the step (2) comprises the following steps: 80g of graphene sheets are placed in 1L of solution containing 26wt% of oxidant (sulfuric acid), reacted in a reaction kettle at 60 ℃ and stirred for 1h, and finally, the graphene sheets are fully washed with deionized water and dried to obtain oxidized graphene sheets.
2. Porous hard carbon negative electrode plate:
(1) Primary mixing: placing the sodium ion hard carbon cathode material and the conductive material (90 wt% of conductive carbon black and 10wt% 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 binding substances (33 wt% of sodium carboxymethyl cellulose, 33wt% of lithium polyacrylate and 33wt% of styrene-butadiene rubber) and deionized water into a container (95.5 wt%, 1.5wt% and 3.0wt% of sodium ion hard carbon anode material, conductive material and binding substances) until the content of solid substances in a stirring tank is 52%, regulating viscosity to 3Pa.s to obtain mixed hard carbon slurry, coating the mixed hard carbon slurry on an anode current collector aluminum foil, drying at 95 ℃ and compacting density of 0.7g/cm after one-time rolling 3 The compaction density after secondary rolling is 0.95g/cm 3 A hard carbon negative plate with a thickness of 125 μm.
(3) And (3) manufacturing a battery: sequentially stacking and winding a positive plate (positive active material is sodium nickel iron manganate), 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 moisture, injecting electrolyte into the battery shell, and packaging to obtain the sodium ion secondary battery.
Example 2
The embodiment provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that:
1. preparation of hard carbon negative electrode material
(1) Oxidizing the surface of the hard carbon particles, wherein the volume ratio of the air to the argon of the hard carbon particles is 3: sintering for 2 hours at 1100 ℃ in 20 atmosphere, wherein the heating rate is 10 ℃/min, and obtaining the hard carbon particles with oxidized surfaces.
(2) Oxidized graphene sheets and a dispersing agent (sodium hexametaphosphate) solution with the mass concentration of 0.02 weight percent are mixed according to the mass volume ratio of 2:100kg/L of the mixture was placed in a reaction vessel to obtain a mixed dispersion.
(3) Adding sodium carbonate (the dosage of the sodium carbonate is 3wt% of the mass of the mixed dispersion liquid) into the mixed dispersion liquid, sequentially adding 100g of hard carbon particles and 1000g of organic polymer (epoxy resin) into the mixed dispersion liquid according to 1L, stirring and dispersing (fully enabling the organic polymer to wrap the hard carbon particles and oxidized graphene sheets to form nano graphene sheets of an interpolation layer), adding 20g of pore-forming agent (ammonium carbonate), stirring at 90 ℃ for 30min, and cooling to 25 ℃ to stop stirring.
(4) The temperature of the heating furnace is controlled at 1200 ℃, and then inactive gas argon is introduced to remove air in the heating furnace, and carbonization, crushing screening and the like are carried out for 10 hours, so as to obtain the porous hard carbon precursor.
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the hard carbon precursor to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 10 ℃/min, introducing carbon-containing gas acetylene, and depositing for 30min to obtain the sodium ion hard carbon anode material of the surface carbon deposition layer.
Wherein, the preparation method of the oxidized graphene sheets in the step (2) comprises the following steps: 80g of graphene sheets are placed in 1L of solution containing 26wt% of oxidant (sulfuric acid), reacted in a reaction kettle at 60 ℃ and stirred for 1h, and finally, the graphene sheets are fully washed with deionized water and dried to obtain oxidized graphene sheets.
2. Porous hard carbon negative electrode plate:
the preparation method is the same as in example 1.
Example 3
The embodiment provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that:
1. preparation of hard carbon negative electrode material
(1) Oxidizing the surface of the hard carbon particles, wherein the volume ratio of the hard carbon particles in air to argon is 3: sintering for 2 hours at 1100 ℃ in 20 atmosphere, wherein the heating rate is 10 ℃/min, and obtaining the hard carbon particles with oxidized surfaces.
(2) Oxidized graphene sheets and a dispersing agent (sodium hexametaphosphate) solution with the mass concentration of 0.05 weight percent are mixed according to the mass volume ratio of 2:100kg/L of the mixture was placed in a reaction vessel to obtain a mixed dispersion.
(3) Adding a sodium source (the dosage of the sodium source is 5wt% of the mass of the mixed dispersion liquid), sequentially adding 100g of hard carbon particles and 1500g of organic polymer (phenolic resin) into 1L of the mixed dispersion liquid, stirring and dispersing (fully enabling the organic polymer to wrap the hard carbon particles and oxidized graphene sheets to form nano graphene sheets of an interpolation layer), adding 20g of a pore opening agent (ammonium carbonate), stirring at 90 ℃ for 40min, and cooling to 25 ℃ to stop stirring.
(4) The temperature of the heating furnace is controlled at 1200 ℃, and then inactive gas argon is introduced to remove air in the heating furnace, and carbonization, crushing screening and the like are carried out for 8 hours, so that the hard carbon precursor is obtained.
(5) Carbon deposition (preparation of carbon deposition layer): and (3) conveying the hard carbon precursor to a deposition furnace, controlling the temperature of the deposition furnace at 700 ℃ at a heating rate of 10 ℃/min, introducing carbon-containing gas acetylene, and depositing for 30min to obtain the sodium ion hard carbon anode material of the surface carbon deposition layer.
Wherein, the preparation method of the oxidized graphene sheets in the step (2) comprises the following steps: 80g of graphene sheets are placed in 1L of solution containing 26wt% of oxidant (sulfuric acid), reacted in a reaction kettle at 60 ℃ and stirred for 1h, and finally, the graphene sheets are fully washed with deionized water and dried to obtain oxidized graphene sheets.
2. Porous hard carbon negative electrode plate:
the preparation method is the same as in example 1.
Example 4
The embodiment provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that:
1. preparation of hard carbon negative electrode material
(1) Surface oxidation of hard carbon particles: the volume ratio of the hard carbon particles to the inactive gas argon in the air is 5: sintering for 2 hours at 1100 ℃ in 20 atmosphere, wherein the heating rate is 10 ℃/min, and obtaining hard carbon particles with oxidized surfaces;
(2) Oxidized graphene sheets and a dispersing agent (dimethylformamide) solution with the mass concentration of 0.1 weight percent are prepared according to the mass volume ratio of 5:100kg/L is placed in a reaction kettle to obtain mixed dispersion liquid;
(3) Adding sodium carbonate (the dosage of the sodium carbonate is 5wt% of the mass of the mixed dispersion liquid) into the mixed dispersion liquid, sequentially adding 100g of hard carbon particles and 1000g of organic polymer (phenolic resin) into the mixed dispersion liquid according to 1L, stirring and dispersing (fully enabling the organic polymer to wrap the hard carbon particles and oxidized graphene sheets to form nano graphene sheets of an interpolation layer), adding 300g of pore-forming agent (methanol), stirring at 90 ℃ for 60min, and cooling to 25 ℃ to stop stirring.
(4) And (3) the mixture is sent to a heating furnace, the temperature is controlled at 1500 ℃, inactive gas argon is introduced to remove air in the heating furnace, carbonization, crushing screening and the like are carried out for 6 hours, and the porous hard carbon precursor is obtained.
(5) Carbon deposition (preparation of carbon deposition layer): and (3) delivering the porous hard carbon precursor to a deposition furnace, controlling the temperature of the deposition furnace at 750 ℃ at a heating rate of 10 ℃/min, introducing carbon-containing gas methane, and depositing for 20min to obtain the sodium ion hard carbon anode material of the surface carbon deposition layer.
Wherein, the preparation method of the oxidized graphene sheets in the step (2) comprises the following steps: 100g of graphene sheets are placed in 1L of solution containing 33wt% of oxidant (sodium persulfate), reacted in a reaction kettle at 50 ℃ and stirred for 1h, and finally, the graphene sheets are fully washed with deionized water and dried to obtain oxidized graphene sheets.
2. Porous hard carbon negative electrode plate:
the preparation method is the same as in example 1.
Example 5
The embodiment provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that:
1. preparation of hard carbon negative electrode material
(1) Surface oxidation of hard carbon particles: the volume ratio of the hard carbon particles to the inactive gas argon in the air is 5: sintering for 2 hours at 1100 ℃ in 20 atmosphere, and heating at a rate of 10 ℃/min to obtain the hard carbon particles with oxidized surfaces.
(2) Oxidized graphene sheets and a dispersing agent (dimethylformamide) solution with the mass concentration of 0.1wt% are mixed according to the mass volume ratio of 5:100kg/L of the mixture was placed in a reaction vessel to obtain a mixed dispersion.
(3) Adding a sodium source (the dosage of the sodium source is 5wt% of the mass of the mixed dispersion liquid) into the mixed dispersion liquid, sequentially adding 100g of hard carbon particles and 1000g of organic polymer (phenolic resin) into the mixed dispersion liquid according to 1L, stirring and dispersing (fully enabling the organic polymer to wrap the hard carbon particles and oxidized graphene sheets to form nano graphene sheets of an interpolation layer), adding 600g of pore-forming agent (methanol/ammonium hypophosphite), stirring at 90 ℃ for 60min, and cooling to 25 ℃ to stop stirring.
(4) The temperature of the heating furnace is controlled at 1500 ℃, then inactive gas argon is introduced to remove air in the heating furnace, carbonization, crushing screening and the like are carried out for 6 hours, and the porous hard carbon precursor is obtained.
(5) Carbon deposition (preparation of carbon deposition layer): and (3) delivering the porous hard carbon precursor to a deposition furnace, controlling the temperature of the deposition furnace at 750 ℃ at a heating rate of 10 ℃/min, introducing carbon-containing gas methane, and depositing for 20min to obtain the sodium ion hard carbon anode material of the surface carbon deposition layer.
The preparation method of the oxidized graphene sheets in the step (2) comprises the following steps: 100g of graphene sheets are placed in 1L of solution containing 33wt% of oxidant (sodium persulfate), reacted in a reaction kettle at 50 ℃ and stirred for 1h, and finally, the graphene sheets are fully washed with deionized water and dried to obtain oxidized graphene sheets.
2. Porous hard carbon negative electrode plate:
the preparation method is the same as in example 1.
Comparative example 1
The comparative example provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that the mixed dispersion in step (2) was not incorporated, and no intercalation was formed inside the oxidized graphene sheet in the organic polymer carbon layer. The structural characterization of the obtained hard carbon anode material is shown in fig. 3.
As can be seen from the characterization graph of fig. 3, two broad diffraction peaks appear around 2θ=23° ((002) crystal plane and 2θ=44° ((100) crystal plane), indicating that both diffraction peaks are disordered structures, and that the diffraction peak of the (002) (2θ=23°) crystal plane of example 1 in the XRD pattern is slightly shifted to a low angle, indicating that the microcrystalline structure of the material tends to be more disordered, according to Bragg equation 2dsin θ=nλ, where d is the corresponding crystal plane spacing, θ is the angle between the incident X-ray and the corresponding crystal plane, λ is the X-ray wavelength (θ refers to the Bragg angle of the peak, d refers to the distance between carbon layers, cukα radiation, λ= 0.15406 nm), the crystal plane spacing d= 0.3588nm, and the crystal plane spacing d= 0.3792nm, corresponding to example 1.
Comparative example 2
The comparative example provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is that the absence of the tapping agent ammonium carbonate results in a reduction of the internal nanopores of the organic polymer carbon layer.
Comparative example 3
The comparative example provides a hard carbon negative electrode material, a negative electrode piece and a sodium ion secondary battery, which are specifically as follows:
the difference from example 1 is the lack of a surface carbon deposit.
And (3) testing:
1. measurement of electric properties of Battery
(1) The sodium ion secondary batteries of examples 1 to 5 and comparative examples 1 to 3 were formed and fixed in volume at 25 ℃, and the first charge/discharge electric quantity of the battery during the formation and the fixed volume were recorded, and the first coulombic efficiency (first coulombic efficiency=first charge/first charge×100%) was calculated. The experimental results are shown in Table 1.
(2) Cutting the hard carbon negative plates of each example and comparative example into round pieces with the diameter of 12mm, and then conveying the round pieces into a glove box for assembly2032 type button cell is formed, the solvent of electrolyte is EC and DMC with volume ratio of 1:1, and sodium salt is NaClO with concentration of 1M 4 . The polypropylene film is used as a separation film, and the metal sodium sheet is used as a counter electrode. And carrying out 0-2.5V discharge/charge test on the button cell, wherein the charge capacity of the button cell is the initial reversible capacity. The experimental results are shown in Table 2.
(3) The discharge/charge curves of the button cells 0 to 2.5V prepared from the hard carbon negative electrode sheets obtained in example 1 and comparative example 1 are shown in FIG. 4.
The discharge plateau volume capacity of example 1 in fig. 4 is higher than the discharge plateau volume capacity of comparative example 1, so the plateau volume capacity can be increased by designing the pore-forming strategy in the organic polymer carbonized layer to create a suitable closed porous structure. (the end of the charge dotted line of example 1 coincides with the charge solid line of comparative example 1, and the resolution is not obvious).
Table 1 first-turn coulombic efficiency case of battery
| First circle coulombic efficiency | |
| Example 1 | 89.1％ |
| Example 2 | 88.4％ |
| Example 3 | 88.3％ |
| Example 4 | 88.4％ |
| Implementation of the embodimentsExample 5 | 89.3％ |
| Comparative example 1 | 85.7％ |
| Comparative example 2 | 87.5％ |
| Comparative example 3 | 86.1％ |
TABLE 2 initial reversible Capacity of hard carbon negative plates of examples and comparative examples
As can be seen from tables 1 and 2, in comparative example 1, compared with example 1, no oxidized graphene sheets were intercalated in the porous organic polymer carbon layer, and the initial coulomb efficiency of the corresponding battery was reduced, and the corresponding initial reversible capacity was also lower and the change was most obvious; comparative example 2, which lacks the pore former ammonium carbonate, resulted in a reduction of the internal nanopores of the organic polymer carbon layer and comparative example 3, which lacks the surface carbon deposition layer, also exhibited a decrease in first-turn coulombic efficiency and initial reversible capacity, compared to example 1, indicating that multiple treatments of forming oxidized graphene sheets in the organic polymer carbon layer, increasing the internal nanopores of the organic polymer carbon layer, and the amorphous structured carbon deposition layer, are beneficial to improving the first-turn coulombic efficiency and initial reversible capacity of the hard carbon material.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. 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 (10)
1. The preparation method of the hard carbon anode material is characterized by comprising the following steps of:
providing a surface oxidized hard carbon particulate;
mixing oxidized graphene sheets with a dispersing agent solution to obtain a mixed dispersing liquid;
adding a sodium source, the hard carbon particles with oxidized surfaces and an organic polymer into the mixed dispersion liquid, and stirring and mixing to obtain a mixture of the hard carbon particles with the surfaces coated with the organic polymer;
adding a pore opening agent into the mixture, heating and stirring the mixture, forming pores on the surface of an organic polymer in the mixture, cooling and solidifying the pores to obtain a porous mixture;
heating and carbonizing the porous mixture in inert atmosphere to obtain hard carbon particles coated with a porous organic polymer carbonized layer;
and (3) carrying out carbon deposition, namely introducing carbon-containing gas into the hard carbon particles wrapped with the porous organic polymer carbonization layer under the heating condition to obtain a carbon deposition layer wrapped on the surface of the porous organic polymer carbonization layer, and obtaining the hard carbon anode material.
2. The method of claim 1, wherein the surface oxidation of hard carbon particles is performed by: heating and sintering the hard carbon particles in a mixed atmosphere of air and inactive gas to realize surface oxidation of the hard carbon particles; the volume ratio of the air to the inactive gas is 1-5: 5 to 20.
3. The method of claim 1, wherein the oxidized graphene sheets are prepared by: mixing graphene sheets with an oxidant solution, heating, stirring, reacting, and drying to obtain oxidized graphene sheets; the oxidant in the oxidant solution is selected from one or more of nitric acid, sulfuric acid, ammonium persulfate, potassium persulfate and sodium persulfate.
4. The method of claim 1, wherein at least one of the following conditions is satisfied:
the mass volume ratio of the oxidized graphene sheets to the dispersant solution is 1-5: 50-100 kg/L;
the concentration of the dispersant solution is 0.005-0.2 wt%.
5. The method of claim 1, wherein at least one of the following conditions is satisfied:
the organic polymer is at least one selected from polyacrylonitrile, polybutadiene, polystyrene, polyethylene, polyethersulfone, polyetherimide, polyimide, phenolic resin and epoxy resin;
the sodium source is at least one of sodium oxalate, sodium hydroxide, sodium carbonate, sodium chloride, sodium formate, sodium bicarbonate and sodium citrate;
the dispersing agent in the dispersing agent solution is selected from one or more of dimethylformamide, sodium pyrophosphate, sodium tripolyphosphate, sodium hexametaphosphate and sodium alkyl sulfonate;
the pore opening agent is one or more selected from ammonium bicarbonate, ammonium carbonate, ammonium hypophosphite, ammonium hydrogen phosphate, ammonium phosphate, methanol, ethanol, n-propanol, isopropanol, formic acid, acetic acid and styrene;
the mass ratio of the hard carbon particles to the organic polymer to the pore-forming agent is 1-50: 5-200: 1 to 100.
6. The method of claim 1, wherein at least one of the following conditions is satisfied:
the heating temperature in the heating and stirring process is 60-200 ℃, and the stirring time is 10-60 minutes;
the temperature in the heating carbonization is controlled at 800-1600 ℃, and the heating carbonization time is 30 min-20 h;
the heating condition in the carbon deposition is 500-1000 ℃, and the carbon deposition time is 5-60 min;
the carbon-containing gas is selected from one or more of methane, ethane, propane, acetylene, propyne, butyne and ethylene.
7. The hard carbon anode material is characterized in that the hard carbon anode material is of a core-shell structure, hard carbon particles are of a core, and the surfaces of the hard carbon particles are coated with a porous organic polymer carbonization layer; the surface of the porous organic polymer carbonization layer is coated with a carbon deposition layer;
the carbon layer of the porous organic polymer carbonization layer is embedded with nano graphene sheets;
the porous organic polymer carbonized layer is doped with sodium element.
8. The hard carbon anode material according to claim 7, wherein at least one of the following conditions is satisfied:
the particle size of the hard carbon micro powder is 0.02-5 mu m;
the thickness of the porous organic polymer carbonized layer is 0.2-20 mu m;
the thickness of the carbon deposition layer is 0.002-0.6 mu m.
9. A hard carbon negative electrode sheet comprising the hard carbon negative electrode material as claimed in claim 7 or 8.
10. A sodium ion secondary battery comprising the hard carbon negative electrode sheet of claim 9.
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