CN116239116A - Method for preparing heteroatom doped porous carbon material with high specific surface area by ion activation method and application thereof - Google Patents
Method for preparing heteroatom doped porous carbon material with high specific surface area by ion activation method and application thereof Download PDFInfo
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- CN116239116A CN116239116A CN202111486386.8A CN202111486386A CN116239116A CN 116239116 A CN116239116 A CN 116239116A CN 202111486386 A CN202111486386 A CN 202111486386A CN 116239116 A CN116239116 A CN 116239116A
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- Prior art keywords
- acid
- carbon material
- porous carbon
- heteroatom
- doped porous
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 81
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000004913 activation Effects 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 150000007524 organic acids Chemical class 0.000 claims abstract description 29
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 25
- 239000011148 porous material Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 18
- 238000010000 carbonizing Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 21
- 150000002500 ions Chemical class 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 13
- 229910052783 alkali metal Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- 150000001340 alkali metals Chemical class 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- -1 3, 4-diaminophenylphosphoric acid Chemical compound 0.000 claims description 8
- ALYNCZNDIQEVRV-UHFFFAOYSA-N 4-aminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1 ALYNCZNDIQEVRV-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims description 6
- 239000011574 phosphorus Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 5
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- LDQMZKBIBRAZEA-UHFFFAOYSA-N 2,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C(N)=C1 LDQMZKBIBRAZEA-UHFFFAOYSA-N 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- JVMSQRAXNZPDHF-UHFFFAOYSA-N 2,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C(N)=C1 JVMSQRAXNZPDHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229950000244 sulfanilic acid Drugs 0.000 claims description 3
- VIIQCABVDRZIPC-UHFFFAOYSA-N (2,5-diaminophenyl) dihydrogen phosphate Chemical compound NC1=CC=C(N)C(OP(O)(O)=O)=C1 VIIQCABVDRZIPC-UHFFFAOYSA-N 0.000 claims description 2
- CZLJVZVIMFMGCH-UHFFFAOYSA-N (2-aminophenoxy)boronic acid Chemical compound NC1=CC=CC=C1OB(O)O CZLJVZVIMFMGCH-UHFFFAOYSA-N 0.000 claims description 2
- UTHULKKJYXJZLV-UHFFFAOYSA-N (3-aminophenoxy)boronic acid Chemical compound NC1=CC=CC(OB(O)O)=C1 UTHULKKJYXJZLV-UHFFFAOYSA-N 0.000 claims description 2
- ZPKSAIWDCQVXSQ-UHFFFAOYSA-N (4-aminophenoxy)boronic acid Chemical compound NC1=CC=C(OB(O)O)C=C1 ZPKSAIWDCQVXSQ-UHFFFAOYSA-N 0.000 claims description 2
- HEAHMJLHQCESBZ-UHFFFAOYSA-N 2,5-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(N)C(S(O)(=O)=O)=C1 HEAHMJLHQCESBZ-UHFFFAOYSA-N 0.000 claims description 2
- UONVFNLDGRWLKF-UHFFFAOYSA-N 2,5-diaminobenzoic acid Chemical compound NC1=CC=C(N)C(C(O)=O)=C1 UONVFNLDGRWLKF-UHFFFAOYSA-N 0.000 claims description 2
- FKSRSWQTEJTBMI-UHFFFAOYSA-N 3,4-diaminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1N FKSRSWQTEJTBMI-UHFFFAOYSA-N 0.000 claims description 2
- HEMGYNNCNNODNX-UHFFFAOYSA-N 3,4-diaminobenzoic acid Chemical compound NC1=CC=C(C(O)=O)C=C1N HEMGYNNCNNODNX-UHFFFAOYSA-N 0.000 claims description 2
- RSFDFESMVAIVKO-UHFFFAOYSA-N 3-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=CC(S)=C1 RSFDFESMVAIVKO-UHFFFAOYSA-N 0.000 claims description 2
- WUBBRNOQWQTFEX-UHFFFAOYSA-N 4-aminosalicylic acid Chemical compound NC1=CC=C(C(O)=O)C(O)=C1 WUBBRNOQWQTFEX-UHFFFAOYSA-N 0.000 claims description 2
- PQXPAFTXDVNANI-UHFFFAOYSA-N 4-azidobenzoic acid Chemical compound OC(=O)C1=CC=C(N=[N+]=[N-])C=C1 PQXPAFTXDVNANI-UHFFFAOYSA-N 0.000 claims description 2
- 239000005711 Benzoic acid Substances 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 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 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- 229960004909 aminosalicylic acid Drugs 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 claims description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 claims description 2
- 235000010233 benzoic acid Nutrition 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 230000003213 activating effect Effects 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 4
- 239000003513 alkali Substances 0.000 abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- 239000000243 solution Substances 0.000 description 30
- 238000002360 preparation method Methods 0.000 description 17
- 238000001994 activation Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000002604 ultrasonography Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 3
- 238000004108 freeze drying Methods 0.000 description 3
- 238000001694 spray drying Methods 0.000 description 3
- FXZCCINCKDATPA-UHFFFAOYSA-N (4-aminophenyl) dihydrogen phosphate Chemical compound NC1=CC=C(OP(O)(O)=O)C=C1 FXZCCINCKDATPA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 2
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 2
- 229960004050 aminobenzoic acid Drugs 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- XKNKHVGWJDPIRJ-UHFFFAOYSA-N arsanilic acid Chemical compound NC1=CC=C([As](O)(O)=O)C=C1 XKNKHVGWJDPIRJ-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 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
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052754 neon Inorganic materials 0.000 description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- CPRMKOQKXYSDML-UHFFFAOYSA-M rubidium hydroxide Chemical compound [OH-].[Rb+] CPRMKOQKXYSDML-UHFFFAOYSA-M 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 1
- FRWYFWZENXDZMU-UHFFFAOYSA-N 2-iodoquinoline Chemical group C1=CC=CC2=NC(I)=CC=C21 FRWYFWZENXDZMU-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- TUBLEHGZOFOXGZ-UHFFFAOYSA-L [Fr+].[Fr+].[O-]C([O-])=O Chemical compound [Fr+].[Fr+].[O-]C([O-])=O TUBLEHGZOFOXGZ-UHFFFAOYSA-L 0.000 description 1
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 1
- CWQSNJSRIUPVNR-UHFFFAOYSA-M [OH-].[Fr+] Chemical compound [OH-].[Fr+] CWQSNJSRIUPVNR-UHFFFAOYSA-M 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- UCVMQZHZWWEPRC-UHFFFAOYSA-L barium(2+);hydrogen carbonate Chemical compound [Ba+2].OC([O-])=O.OC([O-])=O UCVMQZHZWWEPRC-UHFFFAOYSA-L 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000023 beryllium carbonate Inorganic materials 0.000 description 1
- ZBUQRSWEONVBES-UHFFFAOYSA-L beryllium carbonate Chemical compound [Be+2].[O-]C([O-])=O ZBUQRSWEONVBES-UHFFFAOYSA-L 0.000 description 1
- 229910001865 beryllium hydroxide Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- LTPBRCUWZOMYOC-UHFFFAOYSA-N beryllium oxide Inorganic materials O=[Be] LTPBRCUWZOMYOC-UHFFFAOYSA-N 0.000 description 1
- ZMCUDHNSHCRDBT-UHFFFAOYSA-M caesium bicarbonate Chemical compound [Cs+].OC([O-])=O ZMCUDHNSHCRDBT-UHFFFAOYSA-M 0.000 description 1
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- KEDRKJFXBSLXSI-UHFFFAOYSA-M hydron;rubidium(1+);carbonate Chemical compound [Rb+].OC([O-])=O KEDRKJFXBSLXSI-UHFFFAOYSA-M 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical group [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 description 1
- 229910000026 rubidium carbonate Inorganic materials 0.000 description 1
- 229910001952 rubidium oxide Inorganic materials 0.000 description 1
- CWBWCLMMHLCMAM-UHFFFAOYSA-M rubidium(1+);hydroxide Chemical compound [OH-].[Rb+].[Rb+] CWBWCLMMHLCMAM-UHFFFAOYSA-M 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- WJMMDJOFTZAHHS-UHFFFAOYSA-L strontium;carbonic acid;carbonate Chemical compound [Sr+2].OC([O-])=O.OC([O-])=O WJMMDJOFTZAHHS-UHFFFAOYSA-L 0.000 description 1
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/342—Preparation characterised by non-gaseous activating agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
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- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
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Abstract
The invention discloses a method for preparing a heteroatom doped porous carbon material with high specific surface area by an ion activation method and application thereof. The method comprises preparing precursor by utilizing the characteristic that organic acid containing benzene ring can react with alkali, carbonizing at high temperature in one step and activating with alkali ion to obtain the product with average pore diameter of 0.1-10 nm and specific surface area of 1000-4000m measured by nitrogen adsorption 2 And/g, the doping amount of the hetero atoms is between 0.5 and 20 weight percent. The porous carbon material has advantages in the aspect of super capacitorThe electrochemical stability window is 1.0V vs RHE when 6mol/LKOH is used as electrolyte, and the mass specific capacitance is as high as 350F/g when the scanning speed is 2 mV/s.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to a method for preparing a heteroatom doped porous carbon material with high specific surface area by an ion activation method and application thereof.
Background
Among the supercapacitor materials currently in common use, porous carbon materials are considered as one of the most promising candidate materials in the potential electrodes of the next generation supercapacitors due to their unique characteristics such as high specific surface area, developed pores, excellent electrical conductivity and cycling stability. And the porous carbon material is easy to obtain, has lower cost and is an environment-friendly material. However, the types and the number of the functional groups on the surface of the pure porous carbon material are small, and the high specific surface area of the porous carbon material cannot be fully utilized. Because hetero atoms (nitrogen, phosphorus, sulfur, boron and the like) are very similar to carbon atoms in structure, the carbon atoms can be replaced by the hetero atoms by controlling the preparation process so as to introduce the hetero atoms into the porous carbon material, thereby being capable of adjusting the pore structure of the porous carbon material, changing the surface composition of the material, improving the hydrophilicity of the material and enhancing the conductivity of the material, and further greatly expanding the application range of the porous carbon material.
At present, a common method for preparing a porous carbon material is to chemically activate a carbon precursor by using an activating agent, and the process is to prepare the carbon material precursor by high-temperature carbonization, and then blend the carbon material precursor with the activating agent for high-temperature activation. The process is relatively complex, a two-step carbonization process is needed, in the process of mixing and activating the activated agent in the later stage, the activation process is insufficient due to the uneven mixing of the carbon and the activated agent, the pore-forming efficiency is low, and the specific surface area of the prepared porous carbon material is relatively low. And the hetero atoms in the raw materials are greatly consumed due to the addition of the activating agent, so that the doping content of the hetero atoms in the later period is low.
Disclosure of Invention
In order to solve the technical problems, the invention provides a method for preparing a heteroatom doped porous carbon material with high specific surface area by an ion activation method and application thereofThe method comprises introducing alkaline ion at the position of organic acid by utilizing the reaction characteristic of benzene ring-containing organic acid with alkaline substance and its derivative, carbonizing in one step and activating with alkaline ion to obtain the product with average pore diameter of 0.1-10 nm, and measuring specific surface area of 1000-4000m by nitrogen adsorption 2 g -1 The heteroatom doped porous carbon material with high specific surface area and heteroatom doping amount of 0.5-20wt%.
The invention aims at realizing the following technical scheme:
a method of preparing a heteroatom-doped porous carbon material, the method comprising the steps of: the heteroatom doped porous carbon material is prepared by reacting an organic acid containing a benzene ring with an alkaline substance and derivatives thereof, introducing alkaline ions at the position of the organic acid, and then performing one-step carbonization and alkaline ion activation reaction at high temperature.
According to the present invention, the benzene ring-containing organic acid is selected from one, two or more of benzoic acid, 3-mercaptobenzoic acid, 4-azidobenzoic acid, p-aminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 4-diaminobenzoic acid, 2, 4-diaminobenzoic acid, benzenesulfonic acid, p-aminobenzenesulfonic acid, 2, 5-diaminobenzenesulfonic acid, 3, 4-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid, p-aminophenylarsonic acid, p-aminosalicylic acid, 2-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylboric acid, p-aminophenylphosphoric acid, 2, 5-diaminophenylphosphoric acid, 3, 4-diaminophenylphosphoric acid, 2, 4-diaminophenylphosphoric acid.
According to the present invention, the alkaline substance and its derivative are one, two or more selected from the group consisting of an alkali metal oxide, hydroxide, alkali metal carbonate, alkali metal hydrogencarbonate, alkaline earth metal oxide, alkaline earth metal hydroxide, alkaline earth metal carbonate, alkaline earth metal hydrogencarbonate. Preferably selected from the hydroxides of alkali metals.
According to the present invention, the alkali metal is selected from at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); the alkaline earth metal is at least one selected from beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
Illustratively, the alkali metal oxide is selected from lithium oxide, sodium oxide, potassium oxide, rubidium oxide, cesium oxide; the hydroxide of the alkali metal is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide and francium hydroxide; the carbonate of alkali metal is selected from lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate, cesium carbonate and francium carbonate; the bicarbonate of the alkali metal is selected from lithium bicarbonate, sodium bicarbonate, potassium bicarbonate, rubidium bicarbonate and cesium bicarbonate; the alkaline earth metal oxide is selected from beryllium oxide, magnesium oxide, calcium oxide, strontium oxide and barium oxide; the hydroxide of alkaline earth metal is selected from beryllium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide and barium hydroxide; the carbonate of alkaline earth metal is selected from beryllium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate and barium carbonate; the bicarbonate of alkali metal is at least one selected from beryllium bicarbonate, magnesium bicarbonate, calcium bicarbonate, strontium bicarbonate and barium bicarbonate.
According to the invention, the reaction can be carried out in solvent or solvent-free systems.
Preferably, when the reaction is carried out in a solvent-free system, the benzene ring-containing organic acid is directly mixed with the basic substance and its derivatives by means of physical mixing. Preferably, the mixing means may be mixing means commonly used in the art. For example, an organic acid containing a benzene ring and an alkaline substance and its derivative are directly and uniformly mixed in a ball mill. Preferably, the molar ratio of the organic acid containing benzene ring to the alkaline substance and the derivative thereof is 3:1-1:3, and exemplary are 3:1, 2:1, 1:1, 1:2, and 1:3.
Preferably, when the reaction is carried out in the presence of a solvent system, the benzene ring-containing organic acid is mixed with the basic substance and its derivatives in the form of a solution. For example, an organic acid solution containing a benzene ring and an alkaline substance and its derivatives may be directly dissolved in a solvent to obtain a mixed solution; or dissolving one or two of organic acid and alkaline substance containing benzene ring and its derivatives in solvent, and mixing. Illustratively, an organic acid containing a benzene ring and an alkaline substance and a derivative thereof are dissolved in a solvent, respectively, to obtain an organic acid solution containing a benzene ring and an alkaline substance and a derivative thereof, respectively, and then the two solutions are mixed to obtain a mixed solution.
Preferably, the solvent used for preparing the benzene ring-containing organic acid solution is one or a mixture of any more of an organic solvent, water and the like. For example, the organic solvent may be at least one of ethanol, acetone, toluene, isopropyl alcohol, methanol, propanol, and the like.
Preferably, the benzene ring-containing organic acid is used in an amount ratio of 1g (0-100) mL, such as 1g:0mL (without solvent), 1g:5mL, 1g:10mL, 1g:15mL, 1g:20mL, 1g:25mL, 1g:30mL, 1g:35mL, 1g:40mL, 1g:45mL, 1g:50mL, 1g:55mL, 1g:60mL, 1g:65mL, 1g:70mL, 1g:75mL, 1g:80mL, 1g:85mL, 1g:90mL, 1g:95mL, 1g:100mL.
Preferably, the benzene ring-containing organic acid solution is stirred during preparation to completely dissolve the raw materials. The stirring mode and the stirring condition are not particularly limited in the invention, and materials can be mixed by adopting a magnetic stirring mode, for example. For another example, the stirring speed is 5-2000 RPM, and the stirring time is 0.1-24 hours.
Preferably, the preparation method further comprises drying the mixed material. Preferably, the drying mode may be at least one of spray drying, oven evaporation drying, rotary evaporation drying, freeze drying, and the like.
According to the invention, the molar concentration of the alkaline substance and its derivative solution is 0.1 to 6mol/L, such as 0.1mol/L, 0.4mol/L, 0.8mol/L, 1.2mol/L, 1.6mol/L, 2mol/L, 2.4mol/L, 2.8mol/L, 3.2mol/L, 3.6mol/L, 4.2mol/L, 4.6mol/L, 5mol/L, 5.4mol/L, 5.8mol/L, 6mol/L.
According to the invention, the alkaline substance and its derivative solution are added dropwise to an organic acid solution containing benzene rings.
According to the present invention, the alkaline substance and its derivative solution are preferably used in such an amount that the benzene ring-containing organic acid solution is titration neutral.
In the invention, the neutral titration means that the pH value of the solution is 7.0 by using conventional pH test paper, precision pH test paper, pH meter and the like.
According to the preparation method of the heteroatom doped porous carbon material, the reaction time for preparing the precursor by reacting the organic acid containing the benzene ring with the alkaline substance and the derivative thereof is 0.1-24 h, such as 0.1h, 0.5h, 1h, 2h, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h and 24h.
According to the invention, the preparation method of the heteroatom doped porous carbon material further comprises the step of drying the precursor. For example, the drying may be at least one of spray drying, oven evaporation drying, rotary evaporation drying, freeze drying, and the like.
According to the present invention, the carbonization-activation reaction is carried out at a temperature of 500 to 1200 ℃, such as 500 to 550 to 600 to 650, 700 to 750 to 800 to 850 to 900 to 950 to 1000 to 1050 to 1100 to 1150 to 1200 ℃.
According to the invention, the carbonization-activation reaction takes a period of 0.1 to 12 hours, such as 0.1 hours, 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 12 hours.
According to the invention, the carbonization activation reaction is carried out under an inert atmosphere and/or a reducing atmosphere.
For example, the inert atmosphere is one or a mixture of any of nitrogen, helium, neon, argon, and the like.
For example, the reducing atmosphere is pure hydrogen, or a gas in which hydrogen is mixed with one or more of nitrogen, helium, neon, argon, and the like.
According to the preparation method of the heteroatom-doped porous carbon material, the preparation method further comprises the step of acid washing of the dried product. Preferably, the acid washing is, for example, washing with 0.1mol/L to 6mol/L of an acid (one or a mixture of any of sulfuric acid, hydrochloric acid, nitric acid, oxalic acid, phosphoric acid, etc.).
According to the invention, the preparation method of the heteroatom-doped porous carbon material further comprises the step of drying the acid-washed product.
According to the invention, the preparation method of the heteroatom doped porous carbon material comprises the following steps:
(1) Mixing an organic acid containing a benzene ring with an alkaline substance and derivatives thereof;
(2) Drying the mixture prepared in the step (1) to obtain a solid;
(3) Carbonizing the product prepared in the step (2) under inert atmosphere or reducing atmosphere and performing alkaline ion activation reaction;
(4) And (3) carrying out acid washing and drying on the carbonized reaction product to obtain the heteroatom doped porous carbon material.
The invention also provides the heteroatom doped porous carbon material prepared by the method.
According to the present invention, in the heteroatom-doped porous carbon material, the heteroatom may be selected from at least one of nitrogen, sulfur, phosphorus, boron, and the like.
According to the invention, the nitrogen doping amount of the heteroatom-doped porous carbon material is 0.5-20 wt%, such as 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 15wt%, 18wt%, 20wt%.
According to the invention, the sulfur doping amount of the heteroatom-doped porous carbon material is 0.5-20 wt%, such as 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 15wt%, 18wt%, 20wt%.
According to the invention, the heteroatom doped porous carbon material has a phosphorus doping amount of 0.5 to 20wt%, such as 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 15wt%, 18wt%, 20wt%.
According to the invention, the boron doping amount of the heteroatom-doped porous carbon material is 0.5-20 wt%, such as 0.5wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 6wt%, 7wt%, 8wt%, 9wt%, 10wt%, 12wt%, 14wt%, 15wt%, 18wt%, 20wt%.
According to the invention, the average pore diameter of the heteroatom doped porous carbon material is 0.1-10 nm, such as 0.1nm, 0.5nm, 1nm, 2nm, 3nm, 4nm, 5nm, 6nm, 7nm, 8nm, 9nm and 10nm.
According to the invention, the specific surface area of the heteroatom doped porous carbon material is 1000-4000m 2 /g, e.g. 1000m 2 /g、1200m 2 /g、1400m 2 /g、1600m 2 /g、1800m 2 /g、2000m 2 /g、2200m 2 /g、2400m 2 /g、2600m 2 /g、2800m 2 /g、3000m 2 /g、3200m 2 /g、3400m 2 /g、3600m 2 /g、3800m 2 /g、4000m 2 /g。
The invention also provides application of the heteroatom doped porous carbon material in electrocatalytic aspect. For example, in the storage of super-capacitors.
The invention has the beneficial effects that:
the invention provides a heteroatom doped porous carbon material with high specific surface area prepared by an ion activation method and application thereof in the aspect of super capacitor energy storage. Compared with the existing preparation method of the heteroatom doped active carbon, the method of the invention utilizes the characteristic that the organic acid containing benzene ring can react with alkaline substances and derivatives thereof, introduces alkaline ions at the organic acid position, then carbonizes and activates the alkaline ions at high temperature in one step, and then sequentially soaks and washes by acid and water to obtain the active carbon with average pore diameter of 0.1-10 nm and specific surface area of 1000-4000m measured by nitrogen adsorption 2 Between/g of the heteroatom-doped porous carbon material. The porous carbon material has excellent performance in the aspect of super capacitor, the electrochemical stability window is 1.0V vs RHE when 6mol/L KOH is used as electrolyte, and the mass specific capacitance can be up to more than 350F/g when the scanning rate is 2 mV/s.
Drawings
FIG. 1 is an SEM topography of the heteroatom-doped porous carbon material prepared in example 1.
FIG. 2 is an isothermal desorption profile of the heteroatom-doped porous carbon material prepared in example 1.
FIG. 3 is a pore size distribution curve of the heteroatom-doped porous carbon material prepared in example 1.
FIG. 4 is a cyclic voltammogram of the heteroatom doped porous carbon material prepared in example 1 at various scan rates.
FIG. 5 is a graph showing the change in specific capacitance with scan rate of the heteroatom-doped porous carbon material prepared in example 1.
Detailed Description
The preparation method of the present invention will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; the reagents, materials, etc. used in the examples described below are commercially available unless otherwise specified.
Example 1
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: dissolving 1.0g of p-aminobenzoic acid in 50mL of pure water, fully stirring until no obvious solid matters exist, dropwise adding 3mol/L KOH solution into the solution until the solution is neutral, stirring at room temperature for reaction for 6h, and drying in a blast drying oven at 60 ℃ for 24h to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 2 hours at 800 ℃ under nitrogen atmosphere, 10mL of 1M HCl is used for soaking a sample, ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the obtained product is placed in a 60 ℃ blast drying box for drying for 24 hours, thus obtaining the porous carbon material with the nitrogen doping amount of 2wt% and the specific surface area of 2758.4m 2 And/g, the pore diameter of the carbon material model tested by the DFT model is 0.89nm, and the average pore diameter is 2.33nm.
When 6mol/L KOH is used as electrolyte and the electrochemical stability window is 1V vs RHE and the scanning speed is 2mV/s, the mass specific capacitance is measured to be 350F/g.
FIG. 1 is an SEM topography of the heteroatom-doped porous carbon material prepared in example 1. As can be seen from SEM images, the heteroatom doped porous carbon material prepared by the embodiment has a massive structure as a whole, and a plurality of macropores can be seen on the surface of the heteroatom doped porous carbon material, and a plurality of micropores are formed on the macropores. This shows that: the alkaline ions uniformly play an activating role on the surface of the carbon material.
FIG. 2 is an isothermal desorption profile of the heteroatom-doped porous carbon material prepared in example 1. The specific surface area of the material is 2758.4m according to the isothermal adsorption curve 2 /g。
FIG. 3 is a pore size distribution curve of the heteroatom-doped porous carbon material prepared in example 1. The pore size distribution curve of the material shows that the pore size of the material is mostly below 5nm, and the average pore size is 2.33nm.
Example 2
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: 1.0g of 2, 4-diaminobenzenesulfonic acid is dissolved in 30mL of ethanol, fully stirred until no obvious solid matters exist, then 5mol/L KOH solution is added dropwise into the solution until the solution is neutral, then the solution is stirred at room temperature for reaction for 4 hours, and then the reaction product is dried in a blast drying oven at 60 ℃ for 24 hours to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 3 hours at 800 ℃ under nitrogen atmosphere, 10mL of 1M HCl is used for soaking a sample, ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the mixture is dried for 24 hours in a blast drying box at 60 ℃ to obtain a nitrogen-sulfur co-doped porous carbon material with 5.6 weight percent of nitrogen doping amount and 6.4 percent of sulfur doping amount, and the specific surface area is 2780m 2 And/g, the model pore diameter is 0.95nm, and the average pore diameter is 1.8nm.
6mol/L KOH is used as electrolyte, the electrochemical stability window is 1V vs RHE, and the mass specific capacitance is 330F/g when the scanning rate is 2 mV/s.
Example 3
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: dissolving 1.0g of p-aminophenyl phosphoric acid in 60mL of methanol, fully stirring until no obvious solid matters exist, then dropwise adding 2mol/L KOH solution into the solution until the solution is neutral, stirring at room temperature for reaction for 3h, and then freeze-drying at-30 ℃ for 60h to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 2 hours under nitrogen atmosphere at 900 ℃, 10mL of 1M HCl is used for soaking a sample, ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the mixture is dried for 24 hours in a blast drying box at 60 ℃ to obtain a nitrogen-phosphorus co-doped porous carbon material with the nitrogen doping amount of 7.2 weight percent and the phosphorus doping amount of 3.4 percent, and the specific surface area of the nitrogen-phosphorus co-doped porous carbon material is 2890m 2 And/g, the model pore diameter is 1.15nm, and the average pore diameter is 2.45nm.
6mol/L KOH is used as electrolyte, the electrochemical stability window is 1V vs RHE, and the mass specific capacitance is 356F/g when the scanning rate is 2 mV/s.
Example 4
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: 1.0g of 2, 4-diaminobenzene phosphoric acid is dissolved in 100mL of propanol, fully stirred until no obvious solid matters exist, then 6mol/L KOH solution is added dropwise into the mixture until the solution is neutral, then stirred at room temperature for reaction for 12 hours, and then spray drying is carried out to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 2 hours at 500 ℃, 600 ℃, 700 ℃, 800 ℃ and 900 ℃ respectively under nitrogen atmosphere, 10mL of 1M HCl is used for soaking a sample, and ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the mixture is dried for 24 hours in a blast drying box at 60 ℃ to obtain nitrogen doped porous carbon materials with the nitrogen doping amounts of 14.2wt%, 12.3wt%, 10.5wt%, 8.4wt%, 6.3wt%, 9.4wt%, 8.1wt%, 6.8wt%, 5.6wt% and 4.2wt% respectively, and the specific surface areas of the nitrogen-phosphorus co-doped porous carbon materials are 880m respectively 2 /g、1485m 2 /g、1860m 2 /g、2400m 2 /g、3046m 2 And/g, the model pore diameter is in the range of 0.4-5 nm, and the average pore diameter is in the range of 1.2-2.5 nm.
6mol/L KOH is used as electrolyte, the electrochemical stability window is 1.0V vs RHE, and the mass specific capacitance is 210F/g, 256F/g, 287F/g, 320F/g and 358F/g when the scanning rate is 2 mV/s.
Example 5
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: dissolving 1.0g of p-aminophenylarsonic acid in 100mL of pure water, fully stirring until no obvious solid matters exist, then dropwise adding 1mol/L KOH solution into the solution until the solution is neutral, stirring at room temperature for reaction for 3 hours, and drying in a blast drying oven at 60 ℃ for 24 hours to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 2 hours at 800 ℃ under nitrogen atmosphere, 10mL of 1M HCl is used for soaking a sample, ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the mixture is dried for 24 hours in a blast drying box at 60 ℃ to obtain a nitrogen doped porous carbon material with the nitrogen doping amount of 8.6wt% and the specific surface area of 2660m 2 And/g, the model pore diameter is 1.3nm, and the average pore diameter is 1.89nm.
6mol/L KOH is used as electrolyte, the electrochemical stability window is 1V vs RHE, and the mass specific capacitance is 315F/g when the scanning rate is 2 mV/s.
Example 6
A preparation method of a heteroatom doped porous carbon material comprises the following steps:
the first step: adding 1.0g of para aminobenzoic acid and 3.0g of KOH into a ball mill for ball milling for 24 hours, and fully and uniformly mixing at the rotating speed of 250r/min to obtain a precursor;
and a second step of: 1.0g of the precursor is kept for 2 hours at 800 ℃ under nitrogen atmosphere, 10mL of 1M HCl is used for soaking a sample, ultrasound is carried out for 30 mm, then standing is carried out for 24 hours, suction filtration and full water washing are carried out, and the mixture is dried for 24 hours in a 60 ℃ blast drying box, thus obtaining the nitrogen doped porous carbon material with the nitrogen doping amount of 7.2wt% and the specific surface area of 2800m 2 The model pore diameter was 1.15nm and the average pore diameter was 1.73nm.
6mol/L KOH is used as electrolyte, the electrochemical stability window is 1V vs RHE, and the mass specific capacitance is 324F/g when the scanning speed is 2 mV/s.
Test example 1
40mg of the heteroatom-doped porous carbon material prepared in the above example 1 was taken, 9.5mL of an isopropanol solution (the volume ratio of isopropanol to water is 3:1) and 0.5mL of Nafion solution were dispersed by ultrasound. And (3) dripping the dispersed slurry on a glass carbon rod with the diameter of 5mm, drying the electrode, adopting a three-electrode system by using a Chenhua CHI760e electrochemical workstation, wherein a counter electrode is a platinum wire electrode, a reference electrode is a saturated Hg/HgO electrode, an electrolyte is 6mol/L KOH, and testing the specific capacitance of the electrolyte under the scanning rate of 2 mV/s-500 mV/s.
Fig. 4 and 5 are graphs showing cyclic voltammograms and specific capacitance changes with different scan rates for the heteroatom-doped porous carbon materials prepared in example 1, respectively. As can be seen from the figures: the specific capacitance was 350F/g at a scan rate of 2mV/s in a 6mol/L KOH solution, and was maintained at 264F/g when the scan rate was increased to 500 mV/s. This shows that: the heteroatom doped porous carbon material prepared by the invention has excellent specific capacitance and rate capability.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method of preparing a heteroatom-doped porous carbon material, the method comprising the steps of: the heteroatom doped porous carbon material is prepared by reacting an organic acid containing a benzene ring with an alkaline substance and derivatives thereof, introducing alkaline ions at the position of the organic acid, and then performing one-step carbonization and alkaline ion activation reaction at high temperature.
2. The method of claim 1, wherein the benzene ring-containing organic acid is selected from one, two or more of benzoic acid, 3-mercaptobenzoic acid, 4-azidobenzoic acid, para-aminobenzoic acid, 2, 5-diaminobenzoic acid, 3, 4-diaminobenzoic acid, 2, 4-diaminobenzoic acid, benzenesulfonic acid, sulfanilic acid, 2, 5-diaminobenzenesulfonic acid, 3, 4-diaminobenzenesulfonic acid, 2, 4-diaminobenzenesulfonic acid, sulfanilic acid, p-aminosalicylic acid, 2-aminophenylboric acid, 3-aminophenylboric acid, 4-aminophenylboric acid, para-aminophenylphosphoric acid, 2, 5-diaminophenylphosphoric acid, 3, 4-diaminophenylphosphoric acid, 2, 4-diaminophenylphosphoric acid.
3. The method according to claim 1 or 2, wherein the alkaline substance and its derivative are selected from one, two or more of an oxide, a hydroxide, a carbonate of an alkali metal, a bicarbonate of an alkali metal, an oxide, a hydroxide of an alkaline earth metal, a carbonate of an alkaline earth metal, a bicarbonate of an alkaline earth metal. Preferably selected from the hydroxides of alkali metals.
Preferably, the alkali metal is selected from at least one of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), and cesium (Cs); the alkaline earth metal is at least one selected from beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba).
4. A process according to any one of claims 1 to 3 wherein the molar ratio of benzene ring containing organic acid to basic material and derivatives thereof is from 3:1 to 1:3.
5. The method according to any one of claims 1 to 4, wherein the reaction time for preparing the precursor by reacting the organic acid containing benzene ring with the alkaline substance and the derivative thereof is 0.1 to 24 hours.
6. The method of any one of claims 1-4, wherein the carbonization-activation reaction is performed at a temperature of 500 ℃ to 1200 ℃; the carbonization and activation reaction time is 0.1-12h.
7. The method of any one of claims 1-6, wherein the method of preparing the heteroatom-doped porous carbon material comprises the steps of:
(1) Mixing an organic acid containing a benzene ring with an alkaline substance and derivatives thereof;
(2) Drying the mixture prepared in the step (1) to obtain a solid;
(3) Carbonizing the product prepared in the step (2) under inert atmosphere or reducing atmosphere and performing alkaline ion activation reaction;
(4) And (3) carrying out acid washing and drying on the carbonized reaction product to obtain the heteroatom doped porous carbon material.
8. A heteroatom-doped porous carbon material prepared by the method of any one of claims 1-7.
9. The heteroatom-doped porous carbon material of claim 8, wherein the heteroatom is at least one member selected from the group consisting of nitrogen, sulfur, phosphorus, boron, and the like.
Preferably, the nitrogen doping amount of the heteroatom doped porous carbon material is 0.5 to 20wt%.
Preferably, the sulfur doping amount of the heteroatom doped porous carbon material is 0.5 to 20wt%.
Preferably, the phosphorus doping amount of the heteroatom doped porous carbon material is 0.5 to 20wt%.
Preferably, the boron doping amount of the heteroatom doped porous carbon material is 0.5 to 20wt%.
Preferably, the average pore diameter of the heteroatom doped porous carbon material is 0.1-10 nm.
Preferably, the specific surface area of the heteroatom doped porous carbon material is 1000-4000m 2 /g。
10. The use of the heteroatom-doped porous carbon material prepared by the method of any one of claims 1-7 and/or the heteroatom-doped porous carbon material of claim 8 or 9 in electrocatalysis. For example, in the storage of super-capacitors.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182505A (en) * | 2002-12-02 | 2004-07-02 | Mitsubishi Gas Chem Co Inc | Porous carbon material for electric double layer capacitor, and production method therefor |
| CN104477877A (en) * | 2014-11-28 | 2015-04-01 | 江苏苏润高碳材股份有限公司 | Preparation method of supercapacitor porous carbon material by adopting polymer copolymerization and activation compounding method |
| US20180015440A1 (en) * | 2016-07-12 | 2018-01-18 | Farad Power, Inc., | Method of making hetero-atom doped activated carbon |
| CN109133030A (en) * | 2018-09-25 | 2019-01-04 | 桂林电子科技大学 | A kind of preparation method and applications of nitrogen-doped porous carbon material |
| CN109384223A (en) * | 2018-09-07 | 2019-02-26 | 北京理工大学 | A kind of preparation of the derivative porous carbon electrodes of inorganic salts |
| US20190119120A1 (en) * | 2016-05-03 | 2019-04-25 | Virginia Commonwealth University | Heteroatom-doped porous carbons for clean energy applications and methods for their synthesis |
| CN110371972A (en) * | 2019-08-06 | 2019-10-25 | 大连理工大学 | A kind of preparation and its application of the porous carbon materials of O-phthalic itrile group richness Heteroatom doping |
| CN112850685A (en) * | 2019-11-27 | 2021-05-28 | 厦门稀土材料研究所 | Two-dimensional carbon material and preparation method and application thereof |
-
2021
- 2021-12-07 CN CN202111486386.8A patent/CN116239116A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004182505A (en) * | 2002-12-02 | 2004-07-02 | Mitsubishi Gas Chem Co Inc | Porous carbon material for electric double layer capacitor, and production method therefor |
| CN104477877A (en) * | 2014-11-28 | 2015-04-01 | 江苏苏润高碳材股份有限公司 | Preparation method of supercapacitor porous carbon material by adopting polymer copolymerization and activation compounding method |
| US20190119120A1 (en) * | 2016-05-03 | 2019-04-25 | Virginia Commonwealth University | Heteroatom-doped porous carbons for clean energy applications and methods for their synthesis |
| US20180015440A1 (en) * | 2016-07-12 | 2018-01-18 | Farad Power, Inc., | Method of making hetero-atom doped activated carbon |
| CN109384223A (en) * | 2018-09-07 | 2019-02-26 | 北京理工大学 | A kind of preparation of the derivative porous carbon electrodes of inorganic salts |
| CN109133030A (en) * | 2018-09-25 | 2019-01-04 | 桂林电子科技大学 | A kind of preparation method and applications of nitrogen-doped porous carbon material |
| CN110371972A (en) * | 2019-08-06 | 2019-10-25 | 大连理工大学 | A kind of preparation and its application of the porous carbon materials of O-phthalic itrile group richness Heteroatom doping |
| CN112850685A (en) * | 2019-11-27 | 2021-05-28 | 厦门稀土材料研究所 | Two-dimensional carbon material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 李慧君等: "《化工商品600种》", 30 April 1989, 冶金工业出版社, pages: 956 * |
| 李松;郑青榕;冯玉龙;: "制备工艺对活性炭吸附船舶含油污水容量的影响", 船舶工程, no. 02, 15 February 2016 (2016-02-15) * |
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