WO2011117657A2 - Carbon materials comprising nano structures - Google Patents
Carbon materials comprising nano structures Download PDFInfo
- Publication number
- WO2011117657A2 WO2011117657A2 PCT/GB2011/050621 GB2011050621W WO2011117657A2 WO 2011117657 A2 WO2011117657 A2 WO 2011117657A2 GB 2011050621 W GB2011050621 W GB 2011050621W WO 2011117657 A2 WO2011117657 A2 WO 2011117657A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- carbon material
- nano
- carbon
- porosity
- porous carbon
- Prior art date
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- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 62
- 239000002086 nanomaterial Substances 0.000 title description 5
- 239000000463 material Substances 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002717 carbon nanostructure Substances 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000007769 metal material Substances 0.000 claims abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 100
- 229910052799 carbon Inorganic materials 0.000 claims description 54
- 239000002243 precursor Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 7
- 238000001994 activation Methods 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000012702 metal oxide precursor Substances 0.000 claims description 5
- 239000002028 Biomass Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910016287 MxOy Inorganic materials 0.000 claims description 3
- 239000005539 carbonized material Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- 230000004913 activation Effects 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 230000001419 dependent effect Effects 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000010348 incorporation Methods 0.000 claims 1
- 239000011369 resultant mixture Substances 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 claims 1
- 229910052720 vanadium Inorganic materials 0.000 claims 1
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 13
- 150000004706 metal oxides Chemical class 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 description 31
- 239000000203 mixture Substances 0.000 description 29
- 239000000243 solution Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- 238000011065 in-situ storage Methods 0.000 description 20
- 229910021392 nanocarbon Inorganic materials 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000002131 composite material Substances 0.000 description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 10
- 239000012299 nitrogen atmosphere Substances 0.000 description 10
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 9
- 239000003990 capacitor Substances 0.000 description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- -1 nanofibres Substances 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 229910001887 tin oxide Inorganic materials 0.000 description 7
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 5
- 230000021523 carboxylation Effects 0.000 description 5
- 238000006473 carboxylation reaction Methods 0.000 description 5
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910021653 sulphate ion Inorganic materials 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000010903 husk Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000001119 stannous chloride Substances 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 239000011592 zinc chloride Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- 244000060011 Cocos nucifera Species 0.000 description 2
- 235000013162 Cocos nucifera Nutrition 0.000 description 2
- 229920000742 Cotton Polymers 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000011343 solid material Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 240000003826 Eichhornia crassipes Species 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- 229910002674 PdO Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 244000085595 Zizania latifolia Species 0.000 description 1
- 235000004259 Zizania latifolia Nutrition 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 229960000359 chromic chloride Drugs 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- LJAOOBNHPFKCDR-UHFFFAOYSA-K chromium(3+) trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cr+3] LJAOOBNHPFKCDR-UHFFFAOYSA-K 0.000 description 1
- 239000011636 chromium(III) chloride Substances 0.000 description 1
- 235000007831 chromium(III) chloride Nutrition 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 239000011696 chromium(III) sulphate Substances 0.000 description 1
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940076286 cupric acetate Drugs 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- WCOATMADISNSBV-UHFFFAOYSA-K diacetyloxyalumanyl acetate Chemical compound [Al+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WCOATMADISNSBV-UHFFFAOYSA-K 0.000 description 1
- FYWVTSQYJIPZLW-UHFFFAOYSA-K diacetyloxygallanyl acetate Chemical compound [Ga+3].CC([O-])=O.CC([O-])=O.CC([O-])=O FYWVTSQYJIPZLW-UHFFFAOYSA-K 0.000 description 1
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229940044658 gallium nitrate Drugs 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 1
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 description 1
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 1
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 1
- 239000003077 lignite Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- NFSAPTWLWWYADB-UHFFFAOYSA-N n,n-dimethyl-1-phenylethane-1,2-diamine Chemical compound CN(C)C(CN)C1=CC=CC=C1 NFSAPTWLWWYADB-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- LSDSZZKMMNCFMR-UHFFFAOYSA-N nitric acid titanium Chemical compound [Ti].O[N+]([O-])=O LSDSZZKMMNCFMR-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000011146 organic particle Substances 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Inorganic materials [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 1
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical compound [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 239000011686 zinc sulphate Substances 0.000 description 1
- 235000009529 zinc sulphate Nutrition 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
Definitions
- This invention relates to carbon materials comprising nano-structures.
- Carbon comes in many forms, including as: amorphous materials; diamond or diamond-like materials; graphite and graphitic materials; as nano-structured materials such as graphene, nanofibres, nanotubes or fullerenes; and as combinations thereof.
- Activated carbon is one kind of carbon material used for many industrial and civil applications. Activated carbon is generally produced from carbonaceous source materials, for example nutshells, peat, wood, coir, lignite, coal and petroleum pitch. Activated carbon has a very strong adsorptive capacity for inorganic or organic matter because it has a well-developed hole structure and a high specific surface area. A typical specific surface area might be of the order of 500m 2 . g 1 to 1500 m 2 .g _1
- activated carbon is traditionally used in gas and water treatment.
- Activated carbon removes deleterious substances from gas or solution by absorbing them onto its interfaces and surfaces.
- the absorptive mechanism of activated carbon includes physical absorption and chemical absorption. Physical absorption is the primary mechanism for conventional activated carbon.
- porous carbon is also used in other industrial applications, such as catalyst support and energy storage, for their advantages of high porosity, good resistance to corrosion, electrochemical stability, high temperature resistance.
- technologies for loading functional organic or inorganic particles or membranes onto interfaces or surfaces of porous carbons have been explored to realize new applications of porous carbons.
- Electrochemical supercapacitors are a new type of energy storage device with capabilities between those of a normal capacitor and a secondary battery.
- Supercapacitors combine the features of high energy density, high power density, and long life. They have a wide range of working temperature, rapid charge and discharge, and long cycle life. Since no emissions are associated with the release of energy stored in a supercapacitor, supercapacitors have a wide range of potential applications in communication technology, information technology, home appliances, electric vehicles and aerospace.
- supercapacitors By their working principles, supercapacitors can be divided into two types:
- Electric double layer capacitors established on the basis of interface double electrical layers, and Faraday pseudo capacitor established by an oxidation and reduction process on two or three dimensional material surface. Carbon electrode materials with high specific surface area are typical electric double layer capacitors, but their specific capacitance is relatively lower
- Faraday pseudo capacitors are based on Faraday processes, and in particular on the electrochemical process of Faraday charge transfer. This not only happens in the surface of electrode, but also goes into the deep interior of the electrode, so it can achieve a capacitance and energy density higher than that of an electric double layer capacitor.
- Some metal oxides and hydrates are very good electrode materials for supercapacitor. Ruthenium (Ru) oxide and hydrate has a good performance as supercapacitor material, but Ru is a precious metal and expensive. There is therefore a need for other cheaper metal oxides in place of Ru.
- Ru Ruthenium
- manganese oxide, tin oxide, nickel oxide, cobalt oxide, vanadium pentoxide are some of the potential material for a supercapacitor.
- an oxide material can have a change in the valence state which may be accompanied by structural change: consequently the electrochemical performance can decay with use.
- carbon material with electrical double layer capacitor performance is very stable in its own. So, the hybrid supercapacitor, a composite of nano metal oxide and carbon composite material, combines the strength of both and makes a composite electrode material with better electrochemical performance.
- activated carbon materials can provide a suitable substrate for growth of nano-structured carbon within the porosity of the carbon and that the resultant materials are useful in a wide range of applications.
- the present invention provides a method of making a nano-structured carbon material by:-
- nano-structured carbon material a material in which a porous matrix carbon comprises carbon nano structures within the porosity of the material.
- Fig. 1 is a transmission electron microscope micrograph of a tin oxide/in-situ self growth nano carbon composite material
- Fig. 2 is an X-ray diffraction trace of a tin oxide/in-situ self growth nano carbon composite material.
- step 2) Impregnating the porous carbons made in step 2) with an element M precursor solution, and filtering and desiccating the mixture;
- M is one or two of Ti, Fe, Ni,Co, Zn, Cu, Mn, Zr, Cr, Al, Sn, Y, Ce, La, Pb, Pd, Ru, Sr, In, Ga, Bi or Si
- X is one of the 1 ,2 or 3
- Y is one of 1,2,3 or 4.
- the activation step 2) comprises either:
- Chinese patent application 201010204539.0 discloses carbon materials produced by a process comprising the steps of:- a) The preparation of in-situ self growth nano carbon matrix material; b) The surface treatment of the carbon matrix material;
- step (b) Placing the carbon material of step (b) into the precursor of step (c), and
- Step a) comprised:
- a porous carbon material having porosity e.g. activated carbon
- a metallic material capable of catalyzing carbon nano structure growth from the carbon of the carbon material is impregnated into the porosity of the porous carbon material [e.g. Fe(N03)3'9H 2 0];
- the impregnated porous carbon material is heated to a temperature sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano-structured carbon material.
- Step b) comprised treating the resultant material with concentrated nitric acid to oxidise the carbon surface
- Step c) comprised making a metal salt solution.
- Step d) comprised ultrasonically treating a suspension of the material of step b) in the solution of step c).
- steps 1) and 2) of Chinese patent application 201010133489.1 and steps a) and b) of Chinese patent application 201010204539.0 are capable of providing a nano-structured carbon material as the activator of Chinese patent application 201010133489.1 includes iron nitrate which is used to promote nanostructure growth in Chinese patent application 201010204539.0.
- nano-structured carbon material a material in which a porous matrix carbon comprises carbon nano structures within the porosity of the material.
- carbon nano structures is meant carbon structures different in form from the porous carbon matrix and having nanometric scale [e.g. less than ⁇ , or less than ⁇ , or even less than 0.1 ⁇ ] .
- Chinese patent application 201010133489.1 states that it uses biomass material as a source, including as examples agricultural wastes or aquatic plants such as straw, rice husk, coconut shell, husk shell, cotton fibre, fruit stone, wheat straw, corn cob, sawdust, bamboo or water bamboo, algae and water hyacinth.
- biomass material including as examples agricultural wastes or aquatic plants such as straw, rice husk, coconut shell, husk shell, cotton fibre, fruit stone, wheat straw, corn cob, sawdust, bamboo or water bamboo, algae and water hyacinth.
- biomass materials By using biomass materials as a precursor, it is disclosed as possible to provide both inexpensive starting materials, and materials whose morphology may be chosen to meet the demands of the application.
- the texture morphology and porous structure of the raw materials is to some extent inherited in the carbonized material. Since plant materials are abundant and vary in morphology, texture, and structure on a range of scales it is possible to select an appropriate biomass material whose morphology, texture and structure are likely to be beneficial, in carbonised form, to the intended application.
- Porous carbon may be obtained that not only has relatively large surface area, but also has a high proportion of mesopores [e.g. pore diameter 2-50nm] and macropores [pore diameter >50nm] through selecting the appropriate material and controlling the activation process.
- mesopores e.g. pore diameter 2-50nm
- macropores pore diameter >50nm
- 201010133489.1 may include, for example, one or more of the nitrate, chloride, sulphate, acetate or alkoxide of the element M, and may be, or include, ferric nitrate, cobaltous nitrate, nickel nitrate, zinc nitrate, cerium nitrate, cupric nitrate, aluminium nitrate, yttrium nitrate, manganous nitrate, zirconium nitrate, chromic nitrate, lanthanum nitrate, tin nitrate, lead nitrate, palladium nitrate, ruthenium nitrate, strontium nitrate, indium nitrate, gallium nitrate, bismuth nitrate, titanium trichloride, titanium tetrachloride, zinc chloride, cerium chloride, cupric chloride, aluminium chloride, tin tetrachloride, yttrium
- the above mentioned functional oxide MxOy may include, for example, one or more of Ti0 2 , Fe 3 0 4 , Fe 2 0 3 , FeO, NiO, Ni 2 0 3 , Co 3 0 4 , CoO, ZnO, CuO, MnO, Mn0 2 , Zr0 2 , Cr 2 0 3 , Cr0 2 , A1 2 0 3 , Sn0 2 , Y 2 0 3 , Ce0 2 , La 2 0 3 , PbO, Pb0 2 , PdO, Pd0 2 , Ru0 2 , Ru0 4 , SrO, Sr0 2 , ln 2 0 3 , Ga 2 0 3 , Bi 2 0 3 and Si0 2 .
- Rice husk is cleaned, dried and crushed to powder.
- the powder is then carbonized at 400°C for 6 hours at an increasing rate of l°C/min under a vacuum condition.
- the obtained powder is mixed with KOH by a weight ratio of 1 :0.1 , and the mixture is activated by increasing temperature to 1000°C for 1 hour at an increasing rate of 5°C/min under the protection of nitrogen atmosphere to produce porous carbon.
- Porous carbon is impregnated with a nitric acid titanium solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 1000 c for half an hour at an increasing rate of 20°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Ti0 2 .
- Wheat straw is cleaned, dried and crushed to powder.
- the powder is then carbonized at 1000°C for half an hour at an increasing rate of 10°C/min under a vacuum condition.
- the obtained powder is mixed with ZnCl 2 by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 650°C for 6 hours at an increasing rate of 10°C/min under the protection of nitrogen atmosphere to produce porous carbon.
- Porous carbon is impregnated with a tin nitrate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 400°C for 3 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Sn0 2 .
- coconut shell is cleaned, dried and crushed to powder.
- the powder is then carbonized at 1000 °C for 2 hours at an increasing rate of 20°C/min under a vacuum condition.
- the obtained powder is mixed with KOH by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 300°C for 12 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon.
- Porous carbon is impregnated with a nickel nitrate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 400°C for 6 hours at an increasing rate of 1°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded NiO.
- bamboo is cleaned, dried and crushed to powder.
- the powder is then carbonized at 650°C for 3.5 hours at an increasing rate of 5°C /min under a vacuum condition.
- the obtained powder is mixed with KOH by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 900 °C for 5 hours at an increasing rate of 5 °C /min under the protection of nitrogen atmosphere to produce porous carbon.
- Porous carbon is impregnated with a ferric acetate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 300 °C for 6 hours at an increasing rate of 1 °C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Fe 3 0 4 .
- Cotton fibre is cleaned and dried.
- the fibre is then carbonized at 650°C for 4 hours at an increasing rate of 15 c /min under a vacuum condition.
- the obtained sample is mixed with KOH by a weight rate of 1 :5, and the mixture is activated by increasing temperature to 900 °C for 3 hours at an increasing rate of 15 °C /min under the protection of nitrogen atmosphere to produce porous carbon.
- Porous carbon is impregnated with a copper acetate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 600°C for 1 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded CuO.
- Such metal loaded porous carbons may have use in the area of environmental protection, water treatment, photocatalyst support and energy storage
- Chinese patent application 201010204539.0 uses porous carbon materials such as activated carbon and, as discussed above, treats them to promote in-situ growth of carbon nano structure material from the carbon of the carbon material, the in-situ grown material having a graphite- like structure.
- Chinese patent application 201010204539.0 goes on to then generate and distribute nano metal oxide on the surface of carbon by ultrasonic reaction.
- this aspect of the invention permits the use of porous activated carbon as a matrix, with in-situ grown nano carbon with graphite-like layer structure in the porous carbon, the use of ultrasonic chemical reaction to create nano metal oxide on the surface of the base carbon.
- This process distributes the produced metal oxide uniformly on the surface of the matrix carbon material uniformly by preventing metal oxide agglomeration via the local high temperature and high pressure produced by ultrasonic reaction: this improves the specific capacitance.
- the nano carbon with graphite-like layer structure significantly improves the material conductivity.
- the porous carbon [such as activated carbon] provides channels for the flow of metal oxide and electrolytes.
- a higher specific surface area and conductivity also gives the produced material a higher energy density and power density, making it suitable material for a supercapacitor.
- the relatively low cost of activated carbon and in particular biologically produced porous carbons makes the invention still more useful.
- Disclosed examples include :- Example 6
- Step (3) Put the 0.2g carbon matrix material of Step (2) into the precursor of Step (3), ultrasonic 1-6 hours, rinse, rinse gently, dry, under nitrogen protection, sinter 5h at 450 °C. Nano metal oxide / in-situ self growth nano carbon composite material is made.
- the produced solid material is in-situ self growth nano carbon matrix material.
- nano Sn0 2 /in-situ self growth nano carbon composite material is made.
- the material made is measured by thermogravimetry to have tin oxide content 30%.
- the specific surface area is 190 m 2 /g.
- XRD shows Sn0 2
- transmission electron microscope analysis Fig. 1
- Electrochemical test shows 50mA/g initial discharge capacity to reach 760mAh/g, and maintain 335 niAh/g after 40 cycles.
- Example 8 Add 5g carbon material into 50 ml water and 5 g ⁇ ( ⁇ 03)3 ⁇ 9 ⁇ 2 0, mix uniformly, dry and reserve.
- the produced solid substance is in-situ self growth nano carbon matrix material.
- the produced solid substance is in-situ self growth nano carbon matrix material.
- stannous chloride alcohol-water solvent (10.000 g SnCl 2 , 10 ml alcohol, 20ml water) solution concentration is 1 M, agitation and reserve.
- the nano Sn0 2 /in-situ self growth nano carbon composite material is made.
- TG test shows the material produced has tin oxide content of 40%.
- Nitrogen adsorption test shows specific surface area 90 m 2 /g.
- Electrochemical test shows 50mA/g initial discharge capacity to reach 800mAh/g, and maintain 305 niAh/g after 40 cycles
- the produced solid substance is in-situ self growth nano carbon matrix material.
- nano structured carbon materials by virtue of their improved electrical conductivity over activated carbon will have a wide range of uses in electrical and electrochemical applications.
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- Crystallography & Structural Chemistry (AREA)
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Abstract
A method is disclosed of making a nano-structured carbon material by:- A)i)providing a porous carbon material having porosity; ii)impregnating a metallic material capable of catalyzing carbon nano structure growth within the porosity of the porous carbon material of step i) to provide an impregnated porous carbon material; or, B)providing an impregnated porous carbon material produced bysteps i) and ii); and, C)heating the impregnated porous carbon material to a temperature sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano-structured carbon material. The resulting material can be loaded with metal oxides.
Description
CARBON MATERIALS COMPRISING NANO STRUCTURES
This invention relates to carbon materials comprising nano-structures. Background
Carbon comes in many forms, including as: amorphous materials; diamond or diamond-like materials; graphite and graphitic materials; as nano-structured materials such as graphene, nanofibres, nanotubes or fullerenes; and as combinations thereof.
Activated carbon is one kind of carbon material used for many industrial and civil applications. Activated carbon is generally produced from carbonaceous source materials, for example nutshells, peat, wood, coir, lignite, coal and petroleum pitch. Activated carbon has a very strong adsorptive capacity for inorganic or organic matter because it has a well-developed hole structure and a high specific surface area. A typical specific surface area might be of the order of 500m2. g 1 to 1500 m2.g_1
[although the present invention is not limited to this range].
Therefore, activated carbon is traditionally used in gas and water treatment. Activated carbon removes deleterious substances from gas or solution by absorbing them onto its interfaces and surfaces. The absorptive mechanism of activated carbon includes physical absorption and chemical absorption. Physical absorption is the primary mechanism for conventional activated carbon. In recent years, there has been increasing interest in enhancing the chemical absorption of activated carbon by introducing functional groups onto the interfaces and surfaces of the activated carbon via a strong acid or alkali treatment method.
Besides environmental protection and water treatment, porous carbon is also used in other industrial applications, such as catalyst support and energy storage, for their advantages of high porosity, good resistance to corrosion, electrochemical stability, high temperature resistance. In recent years, technologies for loading functional organic or inorganic particles or membranes onto interfaces or surfaces of porous carbons have been explored to realize new applications of porous carbons.
Electrochemical supercapacitors are a new type of energy storage device with capabilities between those of a normal capacitor and a secondary battery.
Supercapacitors combine the features of high energy density, high power density, and long life. They have a wide range of working temperature, rapid charge and discharge, and long cycle life. Since no emissions are associated with the release of energy stored in a supercapacitor, supercapacitors have a wide range of potential applications in communication technology, information technology, home appliances, electric vehicles and aerospace.
By their working principles, supercapacitors can be divided into two types:
• Electric double layer capacitors established on the basis of interface double electrical layers, and Faraday pseudo capacitor established by an oxidation and reduction process on two or three dimensional material surface. Carbon electrode materials with high specific surface area are typical electric double layer capacitors, but their specific capacitance is relatively lower
(e.g. 50-100F g"1).
• Faraday pseudo capacitors are based on Faraday processes, and in particular on the electrochemical process of Faraday charge transfer. This not only happens in the surface of electrode, but also goes into the deep interior of the electrode, so it can achieve a capacitance and energy density higher than that of an electric double layer capacitor.
Some metal oxides and hydrates are very good electrode materials for supercapacitor. Ruthenium (Ru) oxide and hydrate has a good performance as supercapacitor material, but Ru is a precious metal and expensive. There is therefore a need for other cheaper metal oxides in place of Ru. For example, manganese oxide, tin oxide, nickel oxide, cobalt oxide, vanadium pentoxide are some of the potential material for a supercapacitor. However, in the oxidation and reduction process, an oxide material can have a change in the valence state which may be accompanied by structural change: consequently the electrochemical performance can decay with use. In contrast, carbon material with electrical double layer capacitor performance is very stable in its own. So, the hybrid supercapacitor, a composite of nano metal oxide and
carbon composite material, combines the strength of both and makes a composite electrode material with better electrochemical performance.
In the area of hybrid supercapacitor, Chinese Patent 200410013069.4 reported a preparation method to evenly coat nano metal oxide on the surface of carbon nanotubes. Carbon nanotubes have a graphite-like chemical bond, high crystallization, good conductivity, and a quasi one-dimensional electrical structure which allows them to carry high current, so they are regarded as suitable materials for
supercapacitor. However, carbon nanotubes have a high production cost.
The invention
The applicants have realised that activated carbon materials can provide a suitable substrate for growth of nano-structured carbon within the porosity of the carbon and that the resultant materials are useful in a wide range of applications.
Accordingly, in a first aspect, the present invention provides a method of making a nano-structured carbon material by:-
A) i) providing a porous carbon material having porosity; and
ii) impregnating a metallic material capable of catalyzing carbon nano structure growth within the porosity of the porous carbon material of step i) to provide an impregnated porous carbon material;
or,
B) providing an impregnated porous carbon material produced by steps i) and ii);
and,
C) heating the impregnated porous carbon material to a temperature
sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano-structured carbon material.
By nano-structured carbon material is meant a material in which a porous matrix carbon comprises carbon nano structures within the porosity of the material.
Further features and aspects of the invention are evident in the appended claims and in the light of the following illustrative but non- limitative description and the drawings in which :-
Fig. 1 is a transmission electron microscope micrograph of a tin oxide/in-situ self growth nano carbon composite material; and
Fig. 2 is an X-ray diffraction trace of a tin oxide/in-situ self growth nano carbon composite material.
Chinese patent application 201010133489.1, from which this application claims priority, discloses :-
1) Carbonising a biological precursor under vacuum or an inert atmosphere at temperatures between 400-1000°C.
2) Activating the carbonized material via an appropriate physical or chemical activation process to adjust its porous structure;
3) Impregnating the porous carbons made in step 2) with an element M precursor solution, and filtering and desiccating the mixture;
4) Calcining the resulting mixture between 300-1000°C under a vacuum or inert atmosphere to get porous carbons loaded with a functional oxide MxOy, where M is one or two of Ti, Fe, Ni,Co, Zn, Cu, Mn, Zr, Cr, Al, Sn, Y, Ce, La, Pb, Pd, Ru, Sr, In, Ga, Bi or Si, X is one of the 1 ,2 or 3, Y is one of 1,2,3 or 4.
The activation step 2) comprises either:
• heating samples at 300-1000°C for 1-12 h under a C02, steam or air
atmosphere;
or
• mixing an activator KOH, ZnCl2 or Fe(N03)2 with the carbonised material and heating the mixture 300-1000°C for 1-12 h under a vacuum or inert atmosphere.
Chinese patent application 201010204539.0 , from which this application claims priority, discloses carbon materials produced by a process comprising the steps of:- a) The preparation of in-situ self growth nano carbon matrix material;
b) The surface treatment of the carbon matrix material;
c) The preparation of metal oxide precursor;
d) Placing the carbon material of step (b) into the precursor of step (c), and
treating ultrasonically to make the material.
In detail:
Step a) comprised:
i) a porous carbon material having porosity [e.g. activated carbon] is provided; ii) a metallic material capable of catalyzing carbon nano structure growth from the carbon of the carbon material is impregnated into the porosity of the porous carbon material [e.g. Fe(N03)3'9H20];
iii) the impregnated porous carbon material is heated to a temperature sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano-structured carbon material.
Step b) comprised treating the resultant material with concentrated nitric acid to oxidise the carbon surface
Step c) comprised making a metal salt solution.
Step d) comprised ultrasonically treating a suspension of the material of step b) in the solution of step c).
It will be evident by comparison that steps 1) and 2) of Chinese patent application 201010133489.1 and steps a) and b) of Chinese patent application 201010204539.0 are capable of providing a nano-structured carbon material as the activator of Chinese patent application 201010133489.1 includes iron nitrate which is used to promote nanostructure growth in Chinese patent application 201010204539.0.
By nano-structured carbon material is meant a material in which a porous matrix carbon comprises carbon nano structures within the porosity of the material. By carbon nano structures is meant carbon structures different in form from the porous carbon matrix and having nanometric scale [e.g. less than ΙΟμιη, or less than Ιμιη, or even less than 0.1 μιη] .
The disclosure of Chinese patent application 201010133489.1
Chinese patent application 201010133489.1 states that it uses biomass material as a source, including as examples agricultural wastes or aquatic plants such as straw, rice husk, coconut shell, husk shell, cotton fibre, fruit stone, wheat straw, corn cob, sawdust, bamboo or water bamboo, algae and water hyacinth.
By using biomass materials as a precursor, it is disclosed as possible to provide both inexpensive starting materials, and materials whose morphology may be chosen to meet the demands of the application.
Traditional activated carbon normally has a large amount of micro-pores [pore diameter <2 nm] so it is difficult to introduce and load functional oxide materials into the holes.
By carbonizing biological materials, the texture morphology and porous structure of the raw materials is to some extent inherited in the carbonized material. Since plant materials are abundant and vary in morphology, texture, and structure on a range of scales it is possible to select an appropriate biomass material whose morphology, texture and structure are likely to be beneficial, in carbonised form, to the intended application.
Porous carbon may be obtained that not only has relatively large surface area, but also has a high proportion of mesopores [e.g. pore diameter 2-50nm] and macropores [pore diameter >50nm] through selecting the appropriate material and controlling the activation process.
The above mentioned M precursor of Chinese patent application
201010133489.1 may include, for example, one or more of the nitrate, chloride, sulphate, acetate or alkoxide of the element M, and may be, or include, ferric nitrate, cobaltous nitrate, nickel nitrate, zinc nitrate, cerium nitrate, cupric nitrate, aluminium nitrate, yttrium nitrate, manganous nitrate, zirconium nitrate, chromic nitrate, lanthanum nitrate, tin nitrate, lead nitrate, palladium nitrate, ruthenium nitrate, strontium nitrate, indium nitrate, gallium nitrate, bismuth nitrate, titanium trichloride, titanium tetrachloride, zinc chloride, cerium chloride, cupric chloride, aluminium
chloride, tin tetrachloride, yttrium chloride, manganese chloride, zirconium chloride, chromic chloride, ferric chloride, ferrous chloride, nickel chloride, cobaltous chloride, lanthanum chloride, lead chloride, palladium chloride, ruthenium chloride, strontium chloride, indium chloride, gallium chloride, bismuth chloride, titanium sulphate, aluminium sulphate, zinc sulphate, ferrous sulphate, chromic sulphate, nickel sulphate, cupric sulphate, palladous sulphate, cerous sulphate, indium sulphate, manganese sulphate, gallium sulphate, bismuth sulphate, zinc acetate, cerium acetate, cupric acetate, aluminium acetate, yttrium acetate, manganese acetate, zirconium acetate, ferrous acetate, ferric acetate, nickel acetate, cobalt acetate, lanthanum acetate, lead acetate, palladium acetate, ruthenium acetate, strontium acetate, indium acetate, gallium acetate, bismuth acetate, tetrabutyl titanate, tetrabutoxide, titanium tetraethoxide (TEOT), metatitanic acid, titanic acid, isopropyl titanate or tetraethyl orthosilicate (TEOS).
The above mentioned functional oxide MxOy may include, for example, one or more of Ti02, Fe304, Fe203, FeO, NiO, Ni203, Co304, CoO, ZnO, CuO, MnO, Mn02, Zr02, Cr203, Cr02, A1203, Sn02, Y203, Ce02, La203, PbO, Pb02, PdO, Pd02, Ru02, Ru04, SrO, Sr02, ln203, Ga203, Bi203 and Si02.
Example one
Rice husk is cleaned, dried and crushed to powder. The powder is then carbonized at 400°C for 6 hours at an increasing rate of l°C/min under a vacuum condition. The obtained powder is mixed with KOH by a weight ratio of 1 :0.1 , and the mixture is activated by increasing temperature to 1000°C for 1 hour at an increasing rate of 5°C/min under the protection of nitrogen atmosphere to produce porous carbon. Porous carbon is impregnated with a nitric acid titanium solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 1000 c for half an hour at an increasing rate of 20°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Ti02.
Example two
Wheat straw is cleaned, dried and crushed to powder. The powder is then carbonized at 1000°C for half an hour at an increasing rate of 10°C/min under a vacuum condition. The obtained powder is mixed with ZnCl2 by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 650°C for 6 hours at an
increasing rate of 10°C/min under the protection of nitrogen atmosphere to produce porous carbon. Porous carbon is impregnated with a tin nitrate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 400°C for 3 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Sn02.
Example three
Coconut shell is cleaned, dried and crushed to powder. The powder is then carbonized at 1000 °C for 2 hours at an increasing rate of 20°C/min under a vacuum condition. The obtained powder is mixed with KOH by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 300°C for 12 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon. Porous carbon is impregnated with a nickel nitrate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 400°C for 6 hours at an increasing rate of 1°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded NiO.
Example four
Bamboo is cleaned, dried and crushed to powder. The powder is then carbonized at 650°C for 3.5 hours at an increasing rate of 5°C /min under a vacuum condition. The obtained powder is mixed with KOH by a weight rate of 1 :3, and the mixture is activated by increasing temperature to 900 °C for 5 hours at an increasing rate of 5 °C /min under the protection of nitrogen atmosphere to produce porous carbon. Porous carbon is impregnated with a ferric acetate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 300 °C for 6 hours at an increasing rate of 1 °C /min under the protection of nitrogen atmosphere to produce porous carbon loaded Fe304.
Example five
Cotton fibre is cleaned and dried. The fibre is then carbonized at 650°C for 4 hours at an increasing rate of 15 c/min under a vacuum condition. The obtained sample is mixed with KOH by a weight rate of 1 :5, and the mixture is activated by increasing temperature to 900 °C for 3 hours at an increasing rate of 15 °C /min under the protection of nitrogen atmosphere to produce porous carbon. Porous carbon is
impregnated with a copper acetate solution for 12 hours, and is filtered and dried. Then, the mixture is heat-treated at 600°C for 1 hours at an increasing rate of 10°C /min under the protection of nitrogen atmosphere to produce porous carbon loaded CuO.
Such metal loaded porous carbons may have use in the area of environmental protection, water treatment, photocatalyst support and energy storage
The disclosure of Chinese patent application 201010204539.0
Chinese patent application 201010204539.0 uses porous carbon materials such as activated carbon and, as discussed above, treats them to promote in-situ growth of carbon nano structure material from the carbon of the carbon material, the in-situ grown material having a graphite- like structure.
Chinese patent application 201010204539.0 goes on to then generate and distribute nano metal oxide on the surface of carbon by ultrasonic reaction.
To solve the low specific capacitance of electric double layer capacitor and Faraday pseudo capacitor, and the low conductivity of electrode material, this aspect of the invention permits the use of porous activated carbon as a matrix, with in-situ grown nano carbon with graphite-like layer structure in the porous carbon, the use of ultrasonic chemical reaction to create nano metal oxide on the surface of the base carbon. This process distributes the produced metal oxide uniformly on the surface of the matrix carbon material uniformly by preventing metal oxide agglomeration via the local high temperature and high pressure produced by ultrasonic reaction: this improves the specific capacitance. The nano carbon with graphite-like layer structure significantly improves the material conductivity. The porous carbon [such as activated carbon] provides channels for the flow of metal oxide and electrolytes. A higher specific surface area and conductivity also gives the produced material a higher energy density and power density, making it suitable material for a supercapacitor. The relatively low cost of activated carbon and in particular biologically produced porous carbons makes the invention still more useful.
Disclosed examples include :- Example 6
(1) The preparation of in-situ self growth nano carbon matrix material
a. Add activated carbon of 1.0- 10 g into the aqueous solution of 2.2- 100 ml water and 0.55 -10 g Fe(N03)3'9H20, mix uniformly and dry.
b. To put above dried mixture into sinter furnace for heat treatment: raise temperature to 450 °C, preserve for half hour, then raise temperature to 700-1000 °C, preserve for one hour, and then cool to room temperature naturally.
c. Put above material into the 10-15 % hydrochloric acid solution, 50 °C mix 5h, then filter, 80 °C dry, then the solid material is in-situ self growth nano carbon matrix material.
(2) Carbon matrix material surface treatment
To evenly distribute the metal oxide on the surface of carbon material, before the preparation of composite material, treat the surface of carbon matrix material by concentrated nitric acid, 80 °C reflex 3 hours, and then 80 °C dry. The resulting carbon matrix material has an oxidised/carboxylated surface.
(3) Make the metal oxide precursor
Make metal salt into an aqueous solution or alcohol solution, solution concentration is 0.01- 1 M, reserve after agitation.
(4) Put the 0.2g carbon matrix material of Step (2) into the precursor of Step (3), ultrasonic 1-6 hours, rinse, rinse gently, dry, under nitrogen protection, sinter 5h at 450 °C. Nano metal oxide / in-situ self growth nano carbon composite material is made.
(5) Mix the nano metal oxide / in-situ self growth nano carbon composite material of Step (4) with adhesive uniformly and coat on electrode, then the polarizing electrode for supercapacitor is made.
Typical ultrasonic powers of 100-600 W, frequency of 20-60KHz, and duration of 1-6 hours are effective, but the invention in this aspect is not limited to these ranges.
Further specific examples include :-
Example 7
Add l .Og carbon into 2.2 ml water and 0.55 g Fe(N03)3'9H20, mix uniformly, dry and reserve.
Put above mixture into sintering furnace, in vacuum condition, raise temperature to 450 °C, preserve for half hour, raise temperature to 700 °C, preserve for one hour, and cool to room temperature naturally.
Put above material into 10-15% hydrochloric acid solution, at 50 °C, mix 5h, filter, dry at 80 °C, the produced solid material is in-situ self growth nano carbon matrix material.
Then, treat carbon matrix material surface by concentrated nitric acid, 80 °C reflux 3h, 80 °C dry, then carbon matrix material with carboxylation surface is made.
Prepare stannous chloride alcohol-water solvent (1.000 g SnCl2, 10 ml alcohol, 20ml water), solution concentration is 0.1 M, agitation and reserve.
Put the produced carbon material into the produced SnCl2 water solution, ultrasonic 6 hours, rinse gently, dry, under nitrogen protection, sinter at 450 °C 5 hours, nano Sn02/in-situ self growth nano carbon composite material is made.
The material made is measured by thermogravimetry to have tin oxide content 30%. By nitrogen adsorption test, the specific surface area is 190 m2/g. XRD shows Sn02, transmission electron microscope analysis (Fig. 1) shows nano tin oxide distributed evenly in carbon matrix, particle size is 3-5 nanometre. Electrochemical test shows 50mA/g initial discharge capacity to reach 760mAh/g, and maintain 335 niAh/g after 40 cycles.
Example 8
Add 5g carbon material into 50 ml water and 5 g Ρε(Ν03)3·9Η20, mix uniformly, dry and reserve.
Put above mixture into sintering furnace, in vacuum condition, raise temperature to 450 °C, preserve half hour, then raise temperature to 850 °C, preserve one hour, cool to room temperature naturally.
Put above material into 10-15% hydrochloric acid solution, at 50 °C, mix 5 hours, filter, 80 °C dry, the produced solid substance is in-situ self growth nano carbon matrix material.
Then, treat carbon matrix material surface by concentrated nitric acid, 80 °C reflux 3h, 80 °C dry, then carbon matrix material with carboxylation surface is made.
Prepare stannous chloride alcohol- water solvent (5.000 g SnCl2, 10 ml alcohol, 20ml water) solution concentration is 0.5 M, agitation and reserve. Add the produced carbon material into the produced SnCl2 water solution, ultrasonic 3 hours, rinse gently, dry, under nitrogen protection, sinter at 450 °C for 5 h. The nano Sn02/in-situ self growth nano carbon composite material is made. TG test shows the material produced has tin oxide content of 35%. Nitrogen adsorption test shows specific surface area 165 m2/g. Electrochemical test shows 50mA/g initial discharge capacity to reach 770mAh/g, and maintain 310 niAh/g after 40 cycles.
Example 9
Add lOg carbon material into 100 ml water and 10 g Fe(N03)3»9H20, mixing uniformly, dry and reserve.
Put above mixture into sintering furnace, in vacuum condition, raise temperature to 450 °C, preserve half hour, then raise temperature to 1000 °C, preserve one hour, cool to room temperature naturally.
Put above material into 10-15% hydrochloric acid solution, at 50 °C, mix 5 hours, filter, 80 °C dry, the produced solid substance is in-situ self growth nano carbon matrix material.
Treat the carbon matrix material surface with concentrated nitric acid, 80 °C reflux 3h, 80 °C dry, then carbon matrix material with carboxylation surface is made.
Prepare stannous chloride alcohol-water solvent (10.000 g SnCl2, 10 ml alcohol, 20ml water) solution concentration is 1 M, agitation and reserve. Add the produced carbon material into the produced SnCl2 water solution, ultrasonic 1 hours, rinse gently, dry, under nitrogen protection, sinter at 450 °C for 5 h. The nano Sn02/in-situ self growth
nano carbon composite material is made. TG test shows the material produced has tin oxide content of 40%. Nitrogen adsorption test shows specific surface area 90 m2/g. Electrochemical test shows 50mA/g initial discharge capacity to reach 800mAh/g, and maintain 305 niAh/g after 40 cycles
Example 10
Add l .Og carbon material into 50 ml water and 0.55 g Fe(N03)3»9H20, mixing uniformly, dry and reserve.
Put above mixture into sintering furnace, in vacuum condition, raise temperature to 450 °C, preserve half hour, then raise temperature to 700 °C, preserve one hour, cool to room temperature naturally.
Put above material into 10-15% hydrochloric acid solution, at 50 °C, agitation 5 hours, filter, 80 °C dry, the produced solid substance is in-situ self growth nano carbon matrix material.
Treat the carbon matrix material surface with concentrated nitric acid, 80 °C reflux 3h, 80 °C dry, then carbon matrix material with carboxylation surface is made.
Prepare potassium permanganate aqueous solution concentration is 0.01 M, mix and reserve.
Add the produced carbon matrix material into the produced precursor, ultrasonic 6 hours, rinse gently, dry, under nitrogen protection, sinter at 450 °C for 5 h. The nano manganese oxide/in-situ self growth nano carbon composite material is made. TG test shows the material produced has manganese oxide content of 45%. Nitrogen adsorption test shows specific surface area 226 m2/g.
Example 11
Add 5.0g carbon material into 100 ml water and 5 g Fe(N03)3»9H20, mix uniformly, dry and reserve.
Put above mixture into sintering furnace, in vacuum condition, raise temperature to 450 °C, preserve half hour, then raise temperature to 800 °C, preserve one hour, cool to room temperature naturally.
Put above material into 10-15% hydrochloric acid solution, at 50 °C, agitation 5 hours, filter, 80 °C dry, the produced solid substance is in-situ self growth nano carbon matrix material.
Treat the carbon matrix material surface with concentrated nitric acid, 80 °C reflux 3h, 80 °C dry, then carbon matrix material with carboxylation surface is made.
Prepare aqueous potassium permanganate solution, solution concentration is 0.5 M, mix and reserve.
Add 0.2g of the produced carbon matrix material into the produced precursor, ultrasonic 3 hours, rinse gently, dry, under nitrogen protection, sinter at 450 °C for 5 h. The nano manganese oxide/in-situ self growth nano carbon composite material is made. TG test shows the material produced has manganese oxide content of 38%. Nitrogen adsorption test shows specific surface area 291 m2/g.
General applicability of nano structured carbon
In addition to the uses disclosed in Chinese patent applications 201010133489.1 and 201010204539.0; nano structured carbon materials, by virtue of their improved electrical conductivity over activated carbon will have a wide range of uses in electrical and electrochemical applications.
The use of biological precursors to make the activated carbon enables a wide range of microstructures to be achieved which too will provide advantage in a wide range of uses in electrical and electrochemical applications.
Claims
1. A method of making a nano-structured carbon material by:-
A) i) providing a porous carbon material having porosity; ii) impregnating a metallic material capable of catalyzing carbon nano structure growth within the porosity of the porous carbon material of step i) to provide an impregnated porous carbon material;
or,
B) providing an impregnated porous carbon material produced by steps i) and ii);
and,
C) heating the impregnated porous carbon material to a
temperature sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano- structured carbon material.
2. A method as claimed in Claim 1 , in which the porous carbon material is
activated carbon.
3. A method as claimed in Claim 1, in which the porous carbon material is
produced by carbonising a biological precursor.
4. A method as claimed in any one of Claims 1 to 3, in which the heating step is to a temperature in the range between 300-1200°C, preferably 300-1000°C.
5. A method as claimed in any one of Claims 1 to 4, in which the carbon nano structures grown have a graphitic layer structure.
6. A method as claimed in any one of Claims 1 to 5, further comprising the step of treating the surface of the nano-structured carbon material.
7. A method as claimed in Claim 6, further comprising incorporating a metal oxide precursor into porosity of the nano-structured carbon material.
8. A method as claimed in Claim 7, in which the incorporation involves
ultrasonic agitation of the nano-structured carbon material in a solution of the metal oxide precursor.
9. A method as claimed in Claim 7 or Claim 8, in which the metal oxide
precursor comprises a precursor for one or more oxides of Ti, Zr, V, Sn, Cr, Co, Fe, Ni, Mn, or Ru.
10. A method as claimed in Claim 8 or Claim 9 as dependent on Claim 8, in which an ultrasonic power of 100-600 W, frequency of 20-60KHz, and duration of 1- 6 hours is used.
11. A nano structured carbon material comprising a porous carbon material having nano-structured carbon within the porosity and capable of being produced by the method of any preceding claim.
12. A method of making porous carbons comprising oxides within the porosity, the comprising the steps of:
• selecting a biomass material and carbonizing at a temperature of 400- 1000°C under vacuum or inert conditions
• activating the carbonized material via a appropriate physical or chemical activation process
• impregnating the resultant material with a precursor to one or more elements M and drying the resultant product
• calcining the resultant mixture under a vacuum or inert atmosphere to get porous carbon loaded with functional oxide MxOy, where M is one or more of Ti, Fe, Ni, Co, Zn, Cu, Mn, Zr, Cr,
Al, Sn, Y, Ce, La, Pb, Pd, Ru, Sr, In, Ga, Bi or Si, X is one of the 1,2 or 3, Y is one of 1,2,3 or 4.
13. A method as claimed in Claim 12 in which the activation step comprises
heating a porous carbon material impregnated with a metallic material to a temperature sufficient to promote carbon nano structure growth within the porosity of the carbon material to provide a nano-structured carbon material.
14. A method as claimed in any of Claims 1 to 10 or 12 to 13, in which the
metallic material comprises one or more salts of one or more transition metals.
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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CN201010133489.1 | 2010-03-26 | ||
CN201010133489A CN101780952A (en) | 2010-03-26 | 2010-03-26 | Method for preparing loading functional oxide porous carbon |
CN201010204539.0 | 2010-06-22 | ||
CN2010102045390A CN101872651B (en) | 2010-06-22 | 2010-06-22 | Method for preparing in-situ self-grown nano carbon composite material |
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WO2011117657A3 WO2011117657A3 (en) | 2012-01-12 |
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