EP1789364A1 - Processes for producing monolithic porous carbon disks from aromatic organic precursors - Google Patents
Processes for producing monolithic porous carbon disks from aromatic organic precursorsInfo
- Publication number
- EP1789364A1 EP1789364A1 EP05808801A EP05808801A EP1789364A1 EP 1789364 A1 EP1789364 A1 EP 1789364A1 EP 05808801 A EP05808801 A EP 05808801A EP 05808801 A EP05808801 A EP 05808801A EP 1789364 A1 EP1789364 A1 EP 1789364A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon
- precursor
- polyimide
- aromatic
- porous carbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002243 precursor Substances 0.000 title claims abstract description 112
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 86
- 230000008569 process Effects 0.000 title claims abstract description 52
- 125000003118 aryl group Chemical group 0.000 title claims description 43
- 229920001721 polyimide Polymers 0.000 claims abstract description 96
- 239000004642 Polyimide Substances 0.000 claims abstract description 94
- 239000000843 powder Substances 0.000 claims abstract description 87
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 46
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 45
- 239000002131 composite material Substances 0.000 claims abstract description 18
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 239000000178 monomer Substances 0.000 claims description 47
- 239000002904 solvent Substances 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 239000000654 additive Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 23
- 239000002253 acid Substances 0.000 claims description 22
- -1 aromatic tetracarboxylic acids Chemical class 0.000 claims description 22
- 150000001875 compounds Chemical class 0.000 claims description 21
- 150000007513 acids Chemical class 0.000 claims description 20
- 150000002148 esters Chemical class 0.000 claims description 18
- 239000000835 fiber Substances 0.000 claims description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 238000000197 pyrolysis Methods 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 14
- 239000003990 capacitor Substances 0.000 claims description 13
- 150000000000 tetracarboxylic acids Chemical class 0.000 claims description 13
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000768 polyamine Polymers 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 150000004984 aromatic diamines Chemical class 0.000 claims description 10
- 238000007596 consolidation process Methods 0.000 claims description 10
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 claims description 9
- 229910000765 intermetallic Inorganic materials 0.000 claims description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical group 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 150000002739 metals Chemical class 0.000 claims description 6
- 229920003002 synthetic resin Polymers 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000000446 fuel Substances 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 239000000377 silicon dioxide Substances 0.000 claims description 5
- JTTIOYHBNXDJOD-UHFFFAOYSA-N 2,4,6-triaminopyrimidine Chemical compound NC1=CC(N)=NC(N)=N1 JTTIOYHBNXDJOD-UHFFFAOYSA-N 0.000 claims description 4
- ZNZYKNKBJPZETN-WELNAUFTSA-N Dialdehyde 11678 Chemical compound N1C2=CC=CC=C2C2=C1[C@H](C[C@H](/C(=C/O)C(=O)OC)[C@@H](C=C)C=O)NCC2 ZNZYKNKBJPZETN-WELNAUFTSA-N 0.000 claims description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 4
- ANUAIBBBDSEVKN-UHFFFAOYSA-N benzene-1,2,4,5-tetramine Chemical compound NC1=CC(N)=C(N)C=C1N ANUAIBBBDSEVKN-UHFFFAOYSA-N 0.000 claims description 4
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 claims description 4
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007772 electrode material Substances 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 4
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical class C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- VHNQIURBCCNWDN-UHFFFAOYSA-N pyridine-2,6-diamine Chemical compound NC1=CC=CC(N)=N1 VHNQIURBCCNWDN-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000002952 polymeric resin Substances 0.000 claims description 3
- IGUXFXNMXMXLCK-UHFFFAOYSA-N (3-aminophenyl)-(3,4-diaminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C(N)=CC=2)=C1 IGUXFXNMXMXLCK-UHFFFAOYSA-N 0.000 claims description 2
- YKAVPKYCQOKDAP-UHFFFAOYSA-N (3-aminophenyl)-(3,4-diaminophenyl)methanone;trihydrochloride Chemical compound Cl.Cl.Cl.NC1=CC=CC(C(=O)C=2C=C(N)C(N)=CC=2)=C1 YKAVPKYCQOKDAP-UHFFFAOYSA-N 0.000 claims description 2
- VGHSXKTVMPXHNG-UHFFFAOYSA-N 1,3-diisocyanatobenzene Chemical compound O=C=NC1=CC=CC(N=C=O)=C1 VGHSXKTVMPXHNG-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 2
- ILPWTQGYOZFLBN-UHFFFAOYSA-N 4-[(3,4-diaminophenyl)methyl]benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1CC1=CC=C(N)C(N)=C1 ILPWTQGYOZFLBN-UHFFFAOYSA-N 0.000 claims description 2
- GEYAGBVEAJGCFB-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)propan-2-yl]phthalic acid Chemical compound C=1C=C(C(O)=O)C(C(O)=O)=CC=1C(C)(C)C1=CC=C(C(O)=O)C(C(O)=O)=C1 GEYAGBVEAJGCFB-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- BZDGCIJWPWHAOF-UHFFFAOYSA-N benzene-1,2,4,5-tetramine;hydron;tetrachloride Chemical compound Cl.Cl.Cl.Cl.NC1=CC(N)=C(N)C=C1N BZDGCIJWPWHAOF-UHFFFAOYSA-N 0.000 claims description 2
- NOZDKQWTDYQXDO-UHFFFAOYSA-N benzene-1,2,4-triamine;trihydrochloride Chemical compound Cl.Cl.Cl.NC1=CC=C(N)C(N)=C1 NOZDKQWTDYQXDO-UHFFFAOYSA-N 0.000 claims description 2
- IZALUMVGBVKPJD-UHFFFAOYSA-N benzene-1,3-dicarbaldehyde Chemical compound O=CC1=CC=CC(C=O)=C1 IZALUMVGBVKPJD-UHFFFAOYSA-N 0.000 claims description 2
- 239000012965 benzophenone Substances 0.000 claims description 2
- NLNRQJQXCQVDQJ-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone Chemical compound C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 NLNRQJQXCQVDQJ-UHFFFAOYSA-N 0.000 claims description 2
- TUQQUUXMCKXGDI-UHFFFAOYSA-N bis(3-aminophenyl)methanone Chemical compound NC1=CC=CC(C(=O)C=2C=C(N)C=CC=2)=C1 TUQQUUXMCKXGDI-UHFFFAOYSA-N 0.000 claims description 2
- WKDNYTOXBCRNPV-UHFFFAOYSA-N bpda Chemical compound C1=C2C(=O)OC(=O)C2=CC(C=2C=C3C(=O)OC(C3=CC=2)=O)=C1 WKDNYTOXBCRNPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000004744 fabric Substances 0.000 claims description 2
- 150000002484 inorganic compounds Chemical class 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052745 lead Inorganic materials 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- UIMPSNPKHVULAQ-UHFFFAOYSA-N naphthalene-1,2,5,6-tetramine Chemical compound NC1=C(N)C=CC2=C(N)C(N)=CC=C21 UIMPSNPKHVULAQ-UHFFFAOYSA-N 0.000 claims description 2
- ABMFBCRYHDZLRD-UHFFFAOYSA-N naphthalene-1,4-dicarboxylic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1 ABMFBCRYHDZLRD-UHFFFAOYSA-N 0.000 claims description 2
- DKYADULMEONPQX-UHFFFAOYSA-N naphthalene-2,3,6,7-tetramine Chemical compound NC1=C(N)C=C2C=C(N)C(N)=CC2=C1 DKYADULMEONPQX-UHFFFAOYSA-N 0.000 claims description 2
- GOGZBMRXLADNEV-UHFFFAOYSA-N naphthalene-2,6-diamine Chemical compound C1=C(N)C=CC2=CC(N)=CC=C21 GOGZBMRXLADNEV-UHFFFAOYSA-N 0.000 claims description 2
- IQDQMRZGMILNMQ-UHFFFAOYSA-N naphthalene-2,6-dicarbaldehyde Chemical compound C1=C(C=O)C=CC2=CC(C=O)=CC=C21 IQDQMRZGMILNMQ-UHFFFAOYSA-N 0.000 claims description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- ZWLUXSQADUDCSB-UHFFFAOYSA-N phthalaldehyde Chemical compound O=CC1=CC=CC=C1C=O ZWLUXSQADUDCSB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 3
- 239000012779 reinforcing material Substances 0.000 claims 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims 1
- CKOFBUUFHALZGK-UHFFFAOYSA-N 3-[(3-aminophenyl)methyl]aniline Chemical compound NC1=CC=CC(CC=2C=C(N)C=CC=2)=C1 CKOFBUUFHALZGK-UHFFFAOYSA-N 0.000 claims 1
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims 1
- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 claims 1
- UYIWPVOKZZKUMC-UHFFFAOYSA-N 4-(3,4-diaminophenyl)benzene-1,2-diamine Chemical compound C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1.C1=C(N)C(N)=CC=C1C1=CC=C(N)C(N)=C1 UYIWPVOKZZKUMC-UHFFFAOYSA-N 0.000 claims 1
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 claims 1
- 229920000914 Metallic fiber Polymers 0.000 claims 1
- 239000011324 bead Substances 0.000 claims 1
- AZVOEEHCPIRDBR-UHFFFAOYSA-N bis(3,4-diaminophenyl)methanone;tetrahydrochloride Chemical compound Cl.Cl.Cl.Cl.C1=C(N)C(N)=CC=C1C(=O)C1=CC=C(N)C(N)=C1 AZVOEEHCPIRDBR-UHFFFAOYSA-N 0.000 claims 1
- ZLSMCQSGRWNEGX-UHFFFAOYSA-N bis(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=C(N)C=C1 ZLSMCQSGRWNEGX-UHFFFAOYSA-N 0.000 claims 1
- 239000002041 carbon nanotube Substances 0.000 claims 1
- 229910021393 carbon nanotube Inorganic materials 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- 239000011256 inorganic filler Substances 0.000 claims 1
- 229910003475 inorganic filler Inorganic materials 0.000 claims 1
- 229920000592 inorganic polymer Polymers 0.000 claims 1
- DOBFTMLCEYUAQC-UHFFFAOYSA-N naphthalene-2,3,6,7-tetracarboxylic acid Chemical class OC(=O)C1=C(C(O)=O)C=C2C=C(C(O)=O)C(C(=O)O)=CC2=C1 DOBFTMLCEYUAQC-UHFFFAOYSA-N 0.000 claims 1
- YTVNOVQHSGMMOV-UHFFFAOYSA-N naphthalenetetracarboxylic dianhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=C2C(=O)OC(=O)C1=C32 YTVNOVQHSGMMOV-UHFFFAOYSA-N 0.000 claims 1
- 150000002894 organic compounds Chemical class 0.000 claims 1
- 229920000620 organic polymer Polymers 0.000 claims 1
- 230000002787 reinforcement Effects 0.000 claims 1
- 125000003107 substituted aryl group Chemical group 0.000 claims 1
- 229910052721 tungsten Inorganic materials 0.000 claims 1
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- 238000003786 synthesis reaction Methods 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 17
- 239000000499 gel Substances 0.000 description 13
- 239000006229 carbon black Substances 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 239000000047 product Substances 0.000 description 11
- 238000013019 agitation Methods 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 238000002360 preparation method Methods 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000004821 distillation Methods 0.000 description 8
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- 239000011733 molybdenum Substances 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 5
- 239000006260 foam Substances 0.000 description 5
- 239000005011 phenolic resin Substances 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 239000004966 Carbon aerogel Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 150000008065 acid anhydrides Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 150000004982 aromatic amines Chemical class 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 238000000748 compression moulding Methods 0.000 description 3
- 238000006482 condensation reaction Methods 0.000 description 3
- 150000001991 dicarboxylic acids Chemical class 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
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Classifications
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- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
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- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to the preparation of precursors composed of either or both polyimide and polybenzimidazole as organic precursors for producing monolithic porous carbon with density less than or equal to 1.0 g/cc; and the processes for producing monolithic porous carbon from either or both polyimide and polybenzimidazole precursors in the powder form.
- the present invention further relates to the processes for producing monolithic porous carbon derived from either or both polyimide and polybenzimidazole precursors having one or more than one metals dispersed therein.
- the present invention even further relates to the processes for producing carbon-carbon composite prepared from precursors comprising either or both polyimide and polybenzimidazole and activated carbon in the form of powders and/or fibers.
- Monolithic porous carbon which possess interpenetrating pore structure, high density, high surface area, suitable pore size, and well defined pore size distribution, are highly desirable as electrode materials for lithium batteries, electrochemical capacitors, fuel cells, as well as other electrochemical devices.
- the following description will be directed to disk products although it will be understood that other such products can be made from the porous carbon.
- One approach to produce monolithic porous carbon disk is through sol-gel technologies.
- the sol-gel technology generally consists of preparation of gels from solution, drying the gel while minimizing the gel shrinkage. The pyrolysis of thin gel films yields porous monolithic carbon disks.
- RF carbon aerogel currently in the market as electrode material for supercapacitors is derived from resorcinol and formaldehyde organic precursors.
- RF carbon aerogel provide high surface area and narrow pore size distribution.
- the present invention provides processes for producing monolithic porous carbon, e.g., disks, from a group of aromatic organic precursors comprising either or both polyimide or polybenzimidazole.
- the processes include the steps of: (1) preparation of the organic precursors in the powder form; (2) consolidation of the powders into a monolith; (3) pyrolysis producing a monolithic porous carbon product such as a disk.
- the present invention further provides processes for producing monolithic porous carbon disks doped with transition metals from a group of aromatic organic precursors comprising either or both polyimide or polybenzimidazole and metallic compounds.
- the processes include the steps of: (1) preparation of the precursors in- situ doped with metallic compounds in the powder forms; (2) consolidation of the powders into a monolith; (3) pyrolysis producing monolithic porous carbon product such as a disk.
- the present invention even further provides processes for producing porous carbon-carbon composite from the precursors of this invention and carbon in the forms of powders, or fibers, or nanotubers, or bulky balls (C60, or C70, or others), or fullerenes, or a mixture thereof.
- the carbon that is used in the present processes is activated carbon powder and activated carbon fiber.
- the processes include the steps of: (1) preparation of the precursors either in the powder form or a viscous solution; (2) blending together the carbon and the precursor in which the case of the solvent is removed after mixing; (3) consolidation of the mixture into a monolith; (4) pyrolysis producing a porous carbon-carbon composite.
- the organic precursors of this invention have nitrogen-containing heterocyclic structures that connect monomer units into rod-like molecular chain structures with few flexible links or hinges.
- the chain architecture of the precursors consists of either linear chains, or a three-dimensional network, or hyberbranched chain structure.
- One group of the precursors comprises polyimide with imide group in the molecular structure.
- Another group of the precursors comprises polybenzimidazole with benzimidazole group in the molecular structure.
- another group of the precursors comprises both polyimide and polybenzimidazole with both imide and benzimidazole groups in the molecular structure.
- the monolithic porous carbon disks produced from this invention can be further reinforced by fibers or fiber pads or other additive by incorporating fibers, inorganic or organic particles, fiber pads, or other additives during the compression molding process.
- the precursor powders may be further assembled with other additives in addition to carbon before consolidation into a monolith.
- additives include transition metal oxide powders, organic particles, inorganic particles, graphite fibers or flakes, metal fibers, porous substrates including membranes, metallic meshes, carbon cloth, carbon felt, foams, and polymeric resins, such as phenolic resins and commercial polyimide resins.
- the precursors prepared from the aromatic organic monomers of this invention may comprise other components in the molecular chain structure, such as polybenzimidazole, polyamide, polyetherimide, siloxane, or silica, but have the polyimide and aromatic organic composition preferably greater than or equal to 50% by weight.
- the polyimide and polybenzimidazole may be represented by the formulas:
- Al and A4 represent difunctional phenyl, difunctional biphenyl, an optionally substituted difunctional aryl, optionally substituted difunctional alkylene, an optionally substituted difunctional heteroaryl, or a combination thereof; wherein A2 and A5 represents tetra functional phenyl, biphenyl, an optionally substituted tetra functional aryl group, or an optionally substituted heteroaryl group; wherein A3 represent multifunctional phenyl with functionality more than or equal to 2, multifunctional biphenyl with functionality more than or equal to 2, an optionally substituted multifunctional aryl with functionality more than or equal to 2, optionally substituted multifunctional alkylene with functionality more than or equal to 2, an optionally substituted multifunctional heteroaryl with functionality more than or equal to 2, or a combination thereof; n1 , n2 and n3 are greater or equal to 1 ; and (y+2) are more than or equal to 2.
- One application of this invention is to provide a novel carbon electrode for use in electrochemical capacitors, batteries, and fuel cells.
- Another application of this invention is to provide a novel composite of carbon and transition metal oxides, such as MnO2, as an electrode for use in lithium batteries or hybrid -battery/electrochemical capacitor systems.
- Another application of this invention is to provide a catalytic carbon support for use in fuel cells and electrochemical water purification systems.
- Fig. 1 is a cyclic voltammetry (CV) graph of Example 1 showing C (F/gram) versus voltage at a scan rate of 5 mV/sec.
- Fig. 2 is a cyclic voltammetry (CV) graph of Example 2 showing C (F/gram) versus Voltage at a scan rate of 5m V/sec.
- Fig. 3 is a cyclic voltammetry (CV) graph of Example 3 showing C (F/gram) versus Voltage at a scan rate of 5m V/sec.
- Fig. 4 is impedance data of Samples 9a and 9b at 0.75 V bias level with the sulfuric acid electrolyte. ( — black) from Sample 9a and ( — red) from the capacitor with Sample 9b. Mode(s) for Carryout Out the Invention
- the present invention provides processes for producing monolithic disks comprising either or both polyimide and polybenzimidazole as organic precursors for producing monolithic porous carbon which have surface area at or above 500 mVgram and sufficiently high mechanical strength.
- aromatic monomers for preparing polyimide precursors of this invention are preferably selected from one of the following groups: aromatic dianhydride, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or aromatic tetracarboxylic acids, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or ester(s) of aromatic tetracarboxylic acids, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or aromatic dianhydride, aromatic isocyanates including diisocyanate and polyisocyanate with functionality beyond 2.
- the aromatic monomers for preparing polybenzimidazole precursors are preferably selected from one of the following monomer groups: aromatic dialdehydes and aromatic tetraamines; or diesters of aromatic dicarboxylic acids and aromatic tetraamines; or aromatic dicarboxylic acids and aromatic tetraamines.
- the precursors comprising either or both polyimide and polybenzimidazole can preferably be synthesized from the monomers either in the presence of a solvent or in the melt state by the following procedures:
- the precipitate could be either a precipitated powder or a precipitated film onto another solid substrate.
- the solvent in the precursors is removed by distillation, assisted by vacuum if it is necessary.
- the precursors are further ground into fine powder or porous particles, filtered through a sieve if it is necessary.
- the polyimide precursors are preferably condensation products of aromatic diamines and aromatic tetracarboxylic dianhydride, or aromatic diamines and tetracarboxylic acids, or aromatic diamines and ester(s) of tetracarboxylic acids, or aromatic isocyanates and aromatic tetracarboxylic dianhydride.
- a small amount of polyamine compounds with amine functionality greater than two takes the place of some of the aromatic diamine to introduce chemical cross-links to the polyimide precursors. Therefore, polyimide precursors may possess linear molecular structure, or a hyper-branched molecular structure, or a three-dimensional network molecular structure.
- the synthesis of polyimide precursors generally proceeds in the synthesis of poly(amic acids) and then imidization to form polyimide.
- Procedure 1 the monomers and other additives are dissolved in a solvent to form a clear solution.
- the precursors in the form of fine powders are either a homogeneous mixture of monomers or a mixture of low molecular weight oligomers of polyimide and poly(amic acids).
- Procedure 2 the monomers and other additives are dissolved in an organic solvent. The reaction is carried out with a normal agitation at or above 100 0 C, preferably at or above 150 0 C 7 to produce polyimide precipitate.
- the polyimide precursors are in the form of either precipitated powder or gels.
- the solvent is removed from the product by distillation, assisted by vacuum if it is necessary.
- the esters of tetracarboxylic acids and aromatic amines are the monomers of choice.
- the condensation reaction at molten state of monomers releases phenol or an alcohol molecule in the gas phase to produce rigid polyimide foams.
- the product is further ground to produce polyimide powder.
- polyimide precursor is carried out according to Procedure 2 in two steps: synthesis of poly(amic acids) and imidization to form polyimide.
- the synthesis of poly(amic acids) is conducted by dissolving monomers and other additives in an organic solvent at ambient temperature with a normal agitation for a time period from several hours to overnight to yield product in the forms of either precipitated powder or viscous liquid solution or gels.
- the imidization of poly(amic acids) to form polyimide is carried out by either chemical imidization at ambient temperature or thermal imidization at elevated temperatures.
- the chemical imidization is conducted by addition of dehydrating agents to poly(amic acids).
- dehydrating agents are added before the reaction solvent is removed from the system.
- the addition of dehydrating agents to poly(amic acids) solution is carried out in such a way that the reaction at ambient temperature yields polyimide precipitate.
- the solvent is removed from the polyimide precipitate by distillation.
- the dehydrating agents consists of either an acid anhydride or a mixture of an acid anhydride and an organic base.
- Preferred acid anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride.
- Preferred organic bases include optionally substituted mono-, di-, tri alky I amines, and optionally substituted pyridines.
- the thermal imidization is conducted at elevated temperatures.
- the solvent is removed by distillation followed by a thermal imidization of poly(amic acids) powder at a temperature in the range of 5O 0 C to 500 0 C preferably in the range of 100 0 C to 400 0 C and preferably under protection of an inert gas, such as nitrogen or argon.
- an inert gas such as nitrogen or argon.
- the imidization is conducted at elevated temperatures in the range of 50 0 C to 400 0 C, preferably in the range of 100 0 C to 250 0 C to produce polyimide in the form of precipitated powder.
- the solvent is removed by distillation, assisted by vacuum if it is necessary.
- the synthesis of polyimide precursors is preferably carried out according to Procedure 1.
- the monomers and additives are admixed at ambient temperature in the presence of preferably a dipolar aprotic organic solvent. The solvent removal produces a homogeneous mixture in the powder form.
- polyimide precursors are prepared from aromatic monomers of tetracarboxylic dianhydride, aromatic diamine, and optionally, a polyamine compound according to Procedure 2 using thermal imidization method.
- the reaction of monomers and other additives are conducted in an organic solvent, such as di methyl acetamide (DMAc), at ambient temperature with agitation for a period of time.
- Temperature of the reaction system is then raised to the range of 13O 0 C to 200 0 C, preferably in the range of 150 0 C to 180 0 C to produce polyimide as precipitate.
- the solvent is distilled off to produce the dried polyimide precursor powder.
- the polybenzimidazole precursors are preferably condensation products of aromatic tetraamines and aromatic esters of dicarboxylic acids, or aromatic tetraamines and aromatic dialdehyde.
- the synthesis proceeds either in the molten state of monomers or in the presence of a solvent.
- aromatic tetraamine and aromatic dialdehyde as aromatic monomers the synthesis of polybenzimidazole is carried out according to Procedure 2 in two- stages: synthesis of poly(azomethines) as intermediate product in the presence of an organic solvent and synthesis of poly(benzimidazole).
- the reaction of the monomers in an organic solvent is carried out at temperatures in the range of -30 0 C and ambient temperature to produce poly(azomethines) in the forms of either precipitated powder or viscous liquid solution. Further reaction at an elevated temperature in the range of 5O 0 C to 35O 0 C, more preferably in the range of 100 0 C to 250 0 C, converts poly(azomethines) to polybenzimidazole.
- the solvent is removed from the system when the product precipitated from the solution either before or after second stage reaction at elevated temperatures.
- polybenzimidazole proceeds preferably according to Procedure 3 in the molten state of the monomers although not exclusive to the synthesis in the presence of a solvent.
- the reactions are conducted at or above melting temperatures of the monomers with strong agitation and in such conditions that side products of phenol, or water, or an alcohol in the gas phase are released from the system to produce the product in foams.
- the products are crushed and further ground to produce polybenzimidazole precursors in the form of porous powder.
- the precursors comprising both polyimide and polybenzimidazole segments in the molecular structure can be prepared preferably in the presence of an organic solvent.
- the synthesis can be conducted by either synthesizing one precursor of either polyimide or polybenzimidazole before adding the monomers for the other precursor to the reaction system. Or the reactions of polyimide and polybenzimidazole are carried out separately before combining two reactions into one reaction system. Or two sets of the monomers are mixed together simultaneously in the same reaction solution when the reaction conditions are compatible. Yet, such mixing would be generally prohibited if a relatively large amount of flexible amide links were introduced to the molecular chain structure so as to reduce the glass transition temperature of the material significantly.
- An alternative approach to prepare monolithic porous carbon disks from precursors comprising both polyimide and polybenzimidazole is mixing both powders of polyimide and polybenzimidazole precursors together during the process of consolidating the powders into a monolith disk.
- the precursor powders comprising either or both polyimide and polybenzimidazole are further broken down to smaller particle size by a shear stress and filtered through a sieve if it is necessary.
- the preferred particle size of precursors for the purpose of compression molding is in the range of 1//m to 300/zm, more preferably in the range of 5 ⁇ m to 75 ⁇ m, even more preferably in the range of 10 ⁇ m to 50 ⁇ m.
- the precursor powder comprising either or both polyimide and polybenzimidazole in the powder form is further thermally annealed at elevated temperatures before consolidating into a disk.
- the annealing is conducted in a temperature range of 5O 0 C to 600 0 C, more preferably in the range of 50 0 C to 500 0 C for a time period between 20 minutes to 2 hours under vacuum or under protection of argon or nitrogen atmosphere.
- the present invention provides processes for producing porous monolithic disks of transition metal doped precursors comprising either or both polyimide and polybenzimidazole as organic precursors for producing transition metal doped monolithic porous carbon disks which have surface area at or above 500 nrvVgram, sufficiently high mechanical strength, and macrocyclic pyridine structure wherein the transition metal atoms caged or complexed into to provide catalytic activities.
- a transition metallic compound in solution is added to the reaction system or to the dried precursor powder or to the dried disk precursor.
- the solvent used for dissolving the transition metallic compound is preferably the same solvent as the one for preparing the precursors.
- the transition metallic compounds are added during the early stages of the procedures. Even more preferably, the transmission metallic compounds are admixed with the organic precursors in the presence of an organic solvent before proceeding with the synthesis of the precursors.
- the solvent removal during the synthesis of the precursors comprising either or both of polyimide and polybenzimidazole are conducted by distillation, preferably assisted by vacuum.
- Metals suitable for use in the preparation of metal doped monolithic porous carbon of this invention are not limited and may include elemental metals, organometallic compounds, coordination inorganic compounds, metal salts or any combinations thereof.
- the preferred metals include Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P As, Li and combinations thereof.
- Exemplary transition metal compounds include cobalt chloride (CoCb), iron chloride (FeCb), nickel chloride (NiCb), molybdenum chloride (MoCIs), hydrogen hexachloroplatinate hydrate (H2PtCl6*xH2 ⁇ ), copper chloride (CuCb), tungsten chloride (WCI ⁇ ), zirconium chloride (ZrCU), cerium nitrate (Ce(NO3)3), ruthenium chloride (RuCb) and hafnium chloride (HfCU).
- CoCb cobalt chloride
- FeCb iron chloride
- NiCb nickel chloride
- MoCIs molybdenum chloride
- H2PtCl6*xH2 ⁇ hydrogen hexachloroplatinate hydrate
- CuCb copper chloride
- WCI ⁇ tungsten chloride
- ZrCU zirconium chloride
- Ce(NO3)3 cerium nitrate
- RuCb ruthenium
- the transition metallic compound is present in the precursor in an amount from 0.01 % to 20% by weight, or more.
- the present invention provides processes for producing monolithic porous carbon disks which has a rod density of less than or equal to 1.0 gram/cc comprising: producing the organic precursors in powders comprising either or both polyimide and polybenzimidazole; consolidation of the powder into a monolith under a pressure in the range of 3000 psi to 13000 psi; and pyrolysis under protection of an inert atmosphere.
- the present invention provides processes for producing monolithic porous carbon having one or more than one metals dispersed therein, which has a rod density of less than or equal to 1.0 gram/cc comprising: powders of transition metal doped precursors comprising either or both polyimide and polybenzimidazole; consolidation of the porous precursor powders into a monolith preferably at ambient temperature under a pressure in the range of 3000 psi to 13000 psi. and pyrolysis under protection of an inert atmosphere.
- the precursor powders are evenly placed in a mold or on a supporting substrate such as a fiber pad, before a sufficiently high compression pressure and a sufficient holding time are applied to produce a monolith disk with rod density in the range of 0.4g/c to 1.Og/c, preferably 0.6g/cc to 0.95g/cc.
- Pyrolysis of the compressed disks is carried out under protection of an inert gas atmosphere, such as argon, nitrogen or carbon dioxide, at a temperature in the range of 600 0 C to 3000 0 C, more preferably 750 0 C to 1500 0 C.
- an inert gas atmosphere such as argon, nitrogen or carbon dioxide
- the inert gas atmosphere may be changed to carbon dioxide during the pyrolysis, preferably in the later stage of the pyrolysis, to further activate the pore surface of the monolithic carbon disk.
- the heating rate shall be sufficiently slow as to optimize the properties of the monolithic carbon.
- the present invention provides processes for producing porous carbon-carbon composite with a rod density of less than or equal to 1.0 gram/cc from the precursors comprising either or both polyimide or polybenzimidazole and activated carbon in the forms of powder and fiber comprising: blending the precursor, carbon, and other additives thoroughly; removing the solvent in the mixture in cases that a solvent is involved in the mixture; consolidating the mixture into monolith under pressure conditions as to produce a homogeneous composition with desired rod density; and pyrolysis under an inert atmosphere for producing monolithic porous carbon.
- the present invention provides processes for producing porous carbon composites incorporating other additives in addition to the carbon comprising: blending the organic precursor of this invention, carbon, and other additives thoroughly; removing the solvent in the mixture in cases that a solvent is involved during the mixing; consolidating the mixture into monolith under pressure conditions as to produce a homogeneous composition with desired rod density; and pyrolysis under an inert atmosphere for producing monolithic porous carbon.
- additives include metallic compounds, silica, carbon in the forms of powders, fibers, nanotubes, and bulkyballs or fullerences, graphite, metal oxides and metal carbides, polymeric resins in either liquid or powder forms, such as commercial phenolic resins and commercial polyimide resins, and mixtures thereof.
- the additives can be in the forms of powders, fibers, flakes, liquids, or porous substrates composed of one or more than one kind of fibers, membranes, metallic meshes, and foams.
- polyimide precursors there are different ways to blend the polyimide precursor, carbon, and other ingredients together.
- one way of blending is to thoroughly mix polyimide powder with the carbon and other additives.
- Another way is to coat viscous solution of poly(amic acid) onto carbon and other additives before removing the solvent, then converting poly(amic acids) to polyimides.
- the present invention is directed in one aspect to simply mixing the polyimide precursor powder with the carbon and other additives, but is not intended to be limited to any particular way of blending the precursor with the carbon as well as other additives.
- the organic precursors comprising either or both polyimide and polybenzimidazole suitable for use in the method of making monolithic porous carbon disks of the present invention can incorporate other components during the synthesis, such as imidazopyrrolone, siloxane, silica, epoxy, bismaleimide, polyetherimide, but have the composition of polyimide and/or polybenzimidazole preferably greater than or equal to 70% by weight.
- Preferred aromatic tetracarboxylic dianhydride, or tetracarboxylic acids, or diester(s) of tetracarboxylic acids monomers suitable for use in the method of making polyimide precursors of the present invention include following dianhydride compounds and their derivatives of tetracarboxylic acids and dialkyl ester(s) of tetracarboxylic acids: pyromellitic dianhydride; pyromellitic tetracarboxylic acids, dialkyl ester(s) of pyromellitic tetracarboxylic acids and aromatic tetracarboxylic dianhydride or tetracarboxylic acids or esters of the tetracarboxylic acids including 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone dianhydride, 2,3,6,7-naphthylene tetracarbox
- ester(s) are alkyl esters
- the alkyl group preferably contains 1 to 5 carbon atoms and is more preferably methyl.
- Preferred aromatic diamine monomers suitable for use in the methods of making polyimide precursors of the present invention include 1 ,4-phenylene diamine, m-phenylene diamine, 4,4'diamino-biphenyl, 4,4' and 3,3'- diaminodiphenylmethanes, 4,4', and 3,3' -diaminobenzophenones, benzidine, 2,6 - diaminopyridine, 2,6-diaminonaphthalene, 1,4-diaminocyclohexane, 2,4 and 2,6 - diaminotoluene, and derivatives thereof (i.e.: substituted diamine having a substituent(s)).
- the above diamine monomers may be used alone or as a mixture of two or more of them.
- Preferred polyamine compounds with amine functionality greater than 2 suitable for use in the methods of making polyimide precursors of the present invention include 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5-benzenetetraamine, 3,3'4,4'-tetraaminodiphenyl ether, 3,3'4,4'-tetraaminodiphenylmethane, 3,3',4,4'- tetraaminobenzophenone, 3,3',4-triaminodiphenyl, 3,3',4-triaminodiphenylmethane, 3,3',4-triaminobenzophenone, 1 ,2,4-triaminobenzene, their mono-, di-, tri-, or tetra- acid salts., such as 3,3'4,4'-biphenyltetraamine tetrahydrochloride, 1,2,4,5- benzenetetraamine tetrahydrochloride,
- Preferred polyamine compounds with amine functionality greater than 2 suitable for use in the methods of making polyimide precursors composed of a three- dimensional molecular structure of the present invention also include a polyamine oligomer with the formula:
- Preferred aromatic isocyanate monomers suitable for use in the methods of making polyimide precursors of the present invention include 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 4 / 4'-diphenylmethane diisocyanate. Any of the above compounds may be used either alone or as a mixture of two or more of them.
- Preferred aromatic dialdehyde monomers suitable for use in the methods of making polybenzimidazole precursors of the present invention include isophthalaldehyde, terephthaldicarboxaldehyde, phthalic dicarboxaldehyde, and 2,6-naphthalenedicarboxaldehyde.
- Preferred monomers of aromatic acids and esters of dicarboxylic acids suitable for use in the methods of making polybenzimidazole precursors of the present invention include acids and esters of isophthalic acid, phthalic acid, terephthalic acid, 1 ,4-naphthalenedicarboxylic acid, and 2,6- naphthalenedicarboxylic acid.
- the ester(s) may be alkyl or phenyl esters. When ester(s) are alkyl esters the alkyl group preferably contains 1 to 5 carbon atoms and is more preferably methyl.
- Preferred monomers of aromatic tetraamines suitable for use in the methods of making polybenzimidazole precursors of the present invention include 3,3' ',4,4'- tetraaminobiphenyl (3,3'-dianninobenzidine); 1 ,2,4,5-tetraaminobenzene; 1, 2,5,6- tetraaminonaphthalene; 2,3,6,7-tetraaminonaphthalene; 3,3 ',4,4'- tetraaminodiphenyl methane; 3,3',4,4'-tetraaminodiphenyl ethane; 3,3',4,4'- tetraaminodiphenyl-2,2-propane; and combinations thereof.
- Preferred reaction solvents for the synthesis of the precursors comprising either or both polyimide and polybenzimidazole include N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), tyN-dimethyl formamide (DMF), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, methanol, toluene, chlorobenzene, ethanol, and mixtures thereof.
- NMP N-methyl-2-pyrrolidinone
- DMAc N,N-dimethylacetamide
- DMF tyN-dimethyl formamide
- THF tetrahydrofuran
- DMSO dimethyl sulfoxide
- acetone acetone
- methanol toluene
- chlorobenzene chlorobenzene
- ethanol dimethyl sulfoxide
- the monolithic carbon of this invention is suitable for use as an electrode material in electrochemical capacitors
- TAB 3,3'4,4'-biphenyltetraamine
- PMDA 1,2,4,5- benzenetetracarboxylic dianhydride
- PPD 1,4-phenylenediamine
- the powders were further broken down and filtered through a 50 micron-sized sieve.
- the polyimide powders were placed in a mold and compressed under pressure of 5000 psi at ambient temperature to produce a monolithic disk.
- the monolithic disk was pyrolyzed at 800 0 C for 3 hours under protection of nitrogen to produce a monolithic carbon disk.
- the cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 90 F/gram. See Figure 1.
- TAB 3,3'4,4'-biphenyltetraamine
- PMDA 1,4-phenylenediamine
- V molybdenum chloride
- the polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolithic disk.
- the monolithic disk was pyrolyzed at 800 0 C for 3 hours under protection of a nitrogen to produce a monolithic carbon disk.
- the cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 210 F/gram. See Figure 2.
- the polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolith. Pyrolysis of the monolith was carried out at 800 0 C for 2 hours under a nitrogen atmosphere and 1 hour under a carbon dioxide atmosphere. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s, shown in Figure 3, displayed the capacitance of the material at 200 F/gram.
- TAB 3,3'4,4'-biphenyltetraamine
- PMDA 1,2,4,5- benzenetetracarboxylic dianhydride
- PPD 1,4-phenylenediamine
- V molybdenum chloride
- the monolithic disk was pyrolyzed at 800 0 C for 3 hours under protection of nitrogen to produce a monolithic carbon disk.
- the cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 100 F/gram.
- Example 5 Synthesis of Polyimide Precursor with three-dimensional molecular structure doped with 1% Molybdenum by weight and Carbon Disk therefrom Starting monomers and additive: 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5- benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), diaminopyridine, and molybdenum chloride (V) (MoCl5).
- TAB 3,3'4,4'-biphenyltetraamine
- PMDA 1 ,2,4,5- benzenetetracarboxylic dianhydride
- PPD 1,4-phenylenediamine
- V molybdenum chloride
- the polyimide powder were compressed at 4000 psi pressure at ambient temperature to produce a monolithic disk.
- the monolithic disk was pyrolyzed at 800 0 C for 3 hours under protection of nitrogen to produce a monolithic carbon disk.
- the cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 100 F/gram.
- the polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolith. Pyrolysis of the monolith was carried out at 900 0 C for 3 hours under a nitrogen atmosphere. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 80 F/gram.
- a supercapacitor was constructed using the carbon prepared according to Example 3 as electrodes.
- the electrode dimension was 0.81 " in diameter and 0.012" in thickness.
- the prototype supercapacitor comprises a pair of carbon electrodes sandwiched between two current collector plates.
- a microporous separator was placed between two electrodes. 38% sulfuric acid electrolyte impregnates the electrodes and the separator before the current plates were sealed by a thermoplastic edge sealant. The result of characterization is shown in Table 1 ,
- Example 8 Synthesis of Polyimide Precursor doped with 0.5% Molybdenum and Porous Carbon therefrom Starting monomers and additive: 1 ,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1 ,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCI5).
- PMDA 1,2,4,5-benzenetetracarboxylic dianhydride
- PPD 1 ,4-phenylenediamine
- V molybdenum chloride
- the polyimide powders were compressed at 4500 psi pressure at ambient temperature to produce a monolith.
- the monolith was pyrolyzed at 900 0 C for 3 hours under protection of nitrogen to produce a monolithic carbon.
- the cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 150 F/gram.
- Polyimide precursor prepared in Example 6.
- Carbon Black Powder commercially available carbon black from a natural source
- Activated Carbon fiber phenolic resin based carbon fiber.
- Example 9b A Comparative Electrochemical Capacitor Cell Using Carbon Black Electrodes
- Example 10 Preparation of Carbon-Carbon Composite doped with 0.85% Molybdenum and An Electrochemical Capacitor Cell Therefrom Polyimide precursor: prepared in Example 1.
- Carbon Black Powder commercially available carbon black from a natural source
- Activated Carbon fiber phenolic resin based carbon fiber
- Molybdenum chloride (V) Molybdenum chloride (MoCl5).
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Abstract
Disclosed are processes for producing monolithic and metal doped monolithic porous carbon disks from prepolymer organic precursors in the powder form composed of either or both polyimide and polybenzimidazole. The powders are consolidated (compressed) into disks and then pyrolyzed to form the desired porous carbon disk. Porous carbon-carbon composite disks are also prepared by adding carbon to the prepolymer organic precursors.
Description
PROCESSES FOR PRODUCING MONOLITHIC POROUS CARBON DISKS FROM AROMATIC ORGANIC PRECURSORS
DESCRIPTION
This is a continuation-in-part of U.S. application serial no. 10/919,450, filed August 16, 2004.
Technical Field
The present invention relates to the preparation of precursors composed of either or both polyimide and polybenzimidazole as organic precursors for producing monolithic porous carbon with density less than or equal to 1.0 g/cc; and the processes for producing monolithic porous carbon from either or both polyimide and polybenzimidazole precursors in the powder form. The present invention further relates to the processes for producing monolithic porous carbon derived from either or both polyimide and polybenzimidazole precursors having one or more than one metals dispersed therein. The present invention even further relates to the processes for producing carbon-carbon composite prepared from precursors comprising either or both polyimide and polybenzimidazole and activated carbon in the form of powders and/or fibers.
Background Art
Monolithic porous carbon, which possess interpenetrating pore structure, high density, high surface area, suitable pore size, and well defined pore size distribution, are highly desirable as electrode materials for lithium batteries, electrochemical capacitors, fuel cells, as well as other electrochemical devices. The following description will be directed to disk products although it will be understood that other such products can be made from the porous carbon.
One approach to produce monolithic porous carbon disk is through sol-gel technologies. The sol-gel technology generally consists of preparation of gels from solution, drying the gel while minimizing the gel shrinkage. The pyrolysis of thin gel films yields porous monolithic carbon disks. RF carbon aerogel currently in the market as electrode material for supercapacitors is derived from resorcinol and formaldehyde organic precursors. RF carbon aerogel provide high surface area and narrow pore size distribution. Yet, the potential market of RF carbon aerogel as electrode and material for ultracapacitors and supercapacitors is severely limited by the low operating voltage of the capacitor (< =5V) and high manufacturing cost of monolithic RF carbon aerogel materials.
Another approach to produce monolithic porous carbon disks is from powders of porous polymeric precursors by compressing them into a monolith disk followed by pyrolysis. There are 2 obstacles in this approach. One is the compressibility of the polymer precursor and the other is the difficulty in retaining interpenetrating network of the pores during the compression process. U.S. Patent No. 6,544,648 discloses a process for making monolithic carbon disks by compressing carbon black powder with high surface area under vacuum at temperatures at or beyond 8000C and a pressure at or beyond 3000 psi. This approach produces carbon disks with more undesirable micro-pores with pore diameter less than 2 nm than the ones by the sol- gel approach. The compression of carbon powder under vacuum at 8000C displays severe technical challenges and high manufacturing costs.
Yet, another approach to produce monolithic porous carbon is from carbon black powder consolidated in a matrix of a carbonized synthetic resin. U.S. Patent Nos. 5,776,633; 5,172,307; and 5,973,912 described processes of producing such porous carbon-carbon composites. The synthetic resin is phenolic resin in the patents.
Although this approach has the merit of low cost by using inexpensive carbon black powder it has the difficulty in retaining open pores of synthetic resin, thus reducing the efficiency of pore surface area.
Bearing in mind the problems and deficiencies of prior art, it is therefore an object of the present invention to provide monolithic porous carbon disks with high
surface area, high pore volume, high surface activity, well defined pore structure and morphology, and good mechanical properties. It would also be desirable to provide a process for producing such monolithic porous carbon disks with significantly lower cost as compared to the ones currently in the market. Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification.
Disclosure of the Invention
The present invention provides processes for producing monolithic porous carbon, e.g., disks, from a group of aromatic organic precursors comprising either or both polyimide or polybenzimidazole. The processes include the steps of: (1) preparation of the organic precursors in the powder form; (2) consolidation of the powders into a monolith; (3) pyrolysis producing a monolithic porous carbon product such as a disk. The present invention further provides processes for producing monolithic porous carbon disks doped with transition metals from a group of aromatic organic precursors comprising either or both polyimide or polybenzimidazole and metallic compounds. The processes include the steps of: (1) preparation of the precursors in- situ doped with metallic compounds in the powder forms; (2) consolidation of the powders into a monolith; (3) pyrolysis producing monolithic porous carbon product such as a disk.
The present invention even further provides processes for producing porous carbon-carbon composite from the precursors of this invention and carbon in the forms of powders, or fibers, or nanotubers, or bulky balls (C60, or C70, or others), or fullerenes, or a mixture thereof. Preferably, the carbon that is used in the present processes is activated carbon powder and activated carbon fiber. The processes include the steps of: (1) preparation of the precursors either in the powder form or a viscous solution; (2) blending together the carbon and the precursor in which the case of the solvent is removed after mixing; (3) consolidation of the mixture into a monolith; (4) pyrolysis producing a porous carbon-carbon composite.
The organic precursors of this invention have nitrogen-containing heterocyclic structures that connect monomer units into rod-like molecular chain structures with few flexible links or hinges. The chain architecture of the precursors consists of either linear chains, or a three-dimensional network, or hyberbranched chain structure. One group of the precursors comprises polyimide with imide group in the molecular structure. Another group of the precursors comprises polybenzimidazole with benzimidazole group in the molecular structure. Yet, another group of the precursors comprises both polyimide and polybenzimidazole with both imide and benzimidazole groups in the molecular structure. The monolithic porous carbon disks produced from this invention can be further reinforced by fibers or fiber pads or other additive by incorporating fibers, inorganic or organic particles, fiber pads, or other additives during the compression molding process.
The precursor powders may be further assembled with other additives in addition to carbon before consolidation into a monolith. Such additives include transition metal oxide powders, organic particles, inorganic particles, graphite fibers or flakes, metal fibers, porous substrates including membranes, metallic meshes, carbon cloth, carbon felt, foams, and polymeric resins, such as phenolic resins and commercial polyimide resins. The precursors prepared from the aromatic organic monomers of this invention may comprise other components in the molecular chain structure, such as polybenzimidazole, polyamide, polyetherimide, siloxane, or silica, but have the polyimide and aromatic organic composition preferably greater than or equal to 50% by weight. The polyimide and polybenzimidazole may be represented by the formulas:
(2) Polybenzimidazole
wherein Al and A4 represent difunctional phenyl, difunctional biphenyl, an optionally substituted difunctional aryl, optionally substituted difunctional alkylene, an optionally substituted difunctional heteroaryl, or a combination thereof; wherein A2 and A5 represents tetra functional phenyl, biphenyl, an optionally substituted tetra functional aryl group, or an optionally substituted heteroaryl group; wherein A3 represent multifunctional phenyl with functionality more than or equal to 2, multifunctional biphenyl with functionality more than or equal to 2, an optionally substituted multifunctional aryl with functionality more than or equal to 2, optionally substituted multifunctional alkylene with functionality more than or equal to 2, an optionally substituted multifunctional heteroaryl with functionality more than or equal to 2, or a combination thereof; n1 , n2 and n3 are greater or equal to 1 ; and (y+2) are more than or equal to 2.
One application of this invention is to provide a novel carbon electrode for use in electrochemical capacitors, batteries, and fuel cells.
Another application of this invention is to provide a novel composite of carbon and transition metal oxides, such as MnO2, as an electrode for use in lithium batteries or hybrid -battery/electrochemical capacitor systems.
Another application of this invention is to provide a catalytic carbon support for use in fuel cells and electrochemical water purification systems.
While the present invention has been particularly described, in conjunction with a specific preferred embodiment, it is evident that many alternatives, modifications, and variations will be apparent to those skilled in the art of the foregoing description. It is therefore contemplated that the appended claims will embrace any such alternatives, modifications, and variations as falling within the true scope and spirit of the present invention.
Brief Description of the Drawings
The features of the invention believed to be novel and the elements characteristic of the invention are set forth with particularly in the appended claims. The figures are for illustration purposes only and are not drawn to scale.
The invention itself, however, both as to organization and method of operation, may best be understood by reference to the detailed description which follows taken in conjunction with the accompanying drawings in which:
Fig. 1 is a cyclic voltammetry (CV) graph of Example 1 showing C (F/gram) versus voltage at a scan rate of 5 mV/sec.
Fig. 2 is a cyclic voltammetry (CV) graph of Example 2 showing C (F/gram) versus Voltage at a scan rate of 5m V/sec. Fig. 3 is a cyclic voltammetry (CV) graph of Example 3 showing C (F/gram) versus Voltage at a scan rate of 5m V/sec.
Fig. 4 is impedance data of Samples 9a and 9b at 0.75 V bias level with the sulfuric acid electrolyte. ( — black) from Sample 9a and ( — red) from the capacitor with Sample 9b.
Mode(s) for Carryout Out the Invention
In describing the preferred embodiment of the present invention, reference will be made herein to Figs. 1-4 of the drawings in which like numerals refer to like features of the invention.
4. Detailed Description of the Invention
In a first aspect, the present invention provides processes for producing monolithic disks comprising either or both polyimide and polybenzimidazole as organic precursors for producing monolithic porous carbon which have surface area at or above 500 mVgram and sufficiently high mechanical strength.
The aromatic monomers for preparing polyimide precursors of this invention are preferably selected from one of the following groups: aromatic dianhydride, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or aromatic tetracarboxylic acids, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or ester(s) of aromatic tetracarboxylic acids, aromatic diamine, and as an option, an aromatic polyamine compounds with amine functionality beyond 2; or aromatic dianhydride, aromatic isocyanates including diisocyanate and polyisocyanate with functionality beyond 2.
The aromatic monomers for preparing polybenzimidazole precursors are preferably selected from one of the following monomer groups: aromatic dialdehydes and aromatic tetraamines; or diesters of aromatic dicarboxylic acids and aromatic tetraamines; or aromatic dicarboxylic acids and aromatic tetraamines. The precursors comprising either or both polyimide and polybenzimidazole can preferably be synthesized from the monomers either in the presence of a solvent or in the melt state by the following procedures:
• Procedure 1
Admixing all the ingredients in the presence of a solvent. The solvent is removed by distillation, assisted by vacuum if it is necessary to form a
homogeneous mixture in the powder form. Further chemical reactions to produce un-fusible and un-meltable high molecular weight polymeric materials proceed after solvent removal or even after consolidation compression molding of the powders into a monolith such as a disk.
• Procedure 2
Carrying out the condensation reaction of the aromatic monomers in the solution to produce precursors as a precipitate in the forms of either precipitate or gel. The precipitate could be either a precipitated powder or a precipitated film onto another solid substrate. The solvent in the precursors is removed by distillation, assisted by vacuum if it is necessary. The precursors are further ground into fine powder or porous particles, filtered through a sieve if it is necessary.
• Procedure 3
Heating the aromatic organic precursors into the melted state with stirring to form precursors in the solid form. Sometimes, evaporation of byproducts, such as a low molecular weight alcohol or water, produces foams instead of dense solid. The precursor is further ground into fine powder or porous particles, filtered through a sieve if it is necessary.
The polyimide precursors are preferably condensation products of aromatic diamines and aromatic tetracarboxylic dianhydride, or aromatic diamines and tetracarboxylic acids, or aromatic diamines and ester(s) of tetracarboxylic acids, or aromatic isocyanates and aromatic tetracarboxylic dianhydride. As an option, a small amount of polyamine compounds with amine functionality greater than two takes the place of some of the aromatic diamine to introduce chemical cross-links to the polyimide precursors. Therefore, polyimide precursors may possess linear molecular structure, or a hyper-branched molecular structure, or a three-dimensional network molecular structure. The synthesis of polyimide precursors generally
proceeds in the synthesis of poly(amic acids) and then imidization to form polyimide.
Using the monomers of aromatic amines including diamines and polyamine compounds and acids or ester(s) of tetracarboxylic acids the synthesis of polyimide precursors can be carried out according to any of Procedures 1 to 3. In Procedure 1, the monomers and other additives are dissolved in a solvent to form a clear solution. The precursors in the form of fine powders are either a homogeneous mixture of monomers or a mixture of low molecular weight oligomers of polyimide and poly(amic acids). In Procedure 2, the monomers and other additives are dissolved in an organic solvent. The reaction is carried out with a normal agitation at or above 1000C, preferably at or above 1500C7 to produce polyimide precipitate. The polyimide precursors are in the form of either precipitated powder or gels. The solvent is removed from the product by distillation, assisted by vacuum if it is necessary. In Procedure 3, preferably, the esters of tetracarboxylic acids and aromatic amines are the monomers of choice. The condensation reaction at molten state of monomers releases phenol or an alcohol molecule in the gas phase to produce rigid polyimide foams. The product is further ground to produce polyimide powder.
Using the monomers of aromatic dianhydride and aromatic amines including diamines and polyamines the synthesis of polyimide precursor is carried out according to Procedure 2 in two steps: synthesis of poly(amic acids) and imidization to form polyimide. The synthesis of poly(amic acids) is conducted by dissolving monomers and other additives in an organic solvent at ambient temperature with a normal agitation for a time period from several hours to overnight to yield product in the forms of either precipitated powder or viscous liquid solution or gels. The imidization of poly(amic acids) to form polyimide is carried out by either chemical imidization at ambient temperature or thermal imidization at elevated temperatures. The chemical imidization is conducted by addition of dehydrating agents to poly(amic acids). In the cases of poly(amic acids) in the form of precipitated powder, preferably, dehydrating agents are added before the reaction solvent is
removed from the system. In the cases of poly(amic acids) in the form of viscous solution, the addition of dehydrating agents to poly(amic acids) solution is carried out in such a way that the reaction at ambient temperature yields polyimide precipitate. The solvent is removed from the polyimide precipitate by distillation. The dehydrating agents consists of either an acid anhydride or a mixture of an acid anhydride and an organic base. Preferred acid anhydrides include acetic anhydride, propionic anhydride, n-butyric anhydride, benzoic anhydride, and trifluoroacetic anhydride. Preferred organic bases include optionally substituted mono-, di-, tri alky I amines, and optionally substituted pyridines. The thermal imidization is conducted at elevated temperatures.
In the cases of poly(amic acids) in the form of precipitated powder , the solvent is removed by distillation followed by a thermal imidization of poly(amic acids) powder at a temperature in the range of 5O0C to 5000C preferably in the range of 1000C to 4000C and preferably under protection of an inert gas, such as nitrogen or argon. In the cases of poly(amic acids) in the form of viscous liquid solution or gels the imidization is conducted at elevated temperatures in the range of 500C to 4000C, preferably in the range of 1000C to 2500C to produce polyimide in the form of precipitated powder. The solvent is removed by distillation, assisted by vacuum if it is necessary. Using aromatic dianhydride and aromatic isocyanate including diisocyanate and polyisocyanate as the organic precursor the synthesis of polyimide precursors is preferably carried out according to Procedure 1. In this procedure, the monomers and additives are admixed at ambient temperature in the presence of preferably a dipolar aprotic organic solvent. The solvent removal produces a homogeneous mixture in the powder form.
Although not exclusive to the other synthetic procedures, preferably, polyimide precursors are prepared from aromatic monomers of tetracarboxylic dianhydride, aromatic diamine, and optionally, a polyamine compound according to Procedure 2 using thermal imidization method. In this procedure, the reaction of monomers and other additives are conducted in an organic solvent, such as
di methyl acetamide (DMAc), at ambient temperature with agitation for a period of time. Temperature of the reaction system is then raised to the range of 13O0C to 2000C, preferably in the range of 1500C to 1800C to produce polyimide as precipitate. The solvent is distilled off to produce the dried polyimide precursor powder.
The polybenzimidazole precursors are preferably condensation products of aromatic tetraamines and aromatic esters of dicarboxylic acids, or aromatic tetraamines and aromatic dialdehyde. The synthesis proceeds either in the molten state of monomers or in the presence of a solvent. Using aromatic tetraamine and aromatic dialdehyde as aromatic monomers the synthesis of polybenzimidazole is carried out according to Procedure 2 in two- stages: synthesis of poly(azomethines) as intermediate product in the presence of an organic solvent and synthesis of poly(benzimidazole). In this procedure, the reaction of the monomers in an organic solvent is carried out at temperatures in the range of -300C and ambient temperature to produce poly(azomethines) in the forms of either precipitated powder or viscous liquid solution. Further reaction at an elevated temperature in the range of 5O0C to 35O0C, more preferably in the range of 1000C to 2500C, converts poly(azomethines) to polybenzimidazole. The solvent is removed from the system when the product precipitated from the solution either before or after second stage reaction at elevated temperatures.
Using the monomers of aromatic tetraamine and esters of dicarboxylic acids the synthesis of polybenzimidazole proceeds preferably according to Procedure 3 in the molten state of the monomers although not exclusive to the synthesis in the presence of a solvent. The reactions are conducted at or above melting temperatures of the monomers with strong agitation and in such conditions that side products of phenol, or water, or an alcohol in the gas phase are released from the system to produce the product in foams. The products are crushed and further ground to produce polybenzimidazole precursors in the form of porous powder.
The precursors comprising both polyimide and polybenzimidazole segments in the molecular structure can be prepared preferably in the presence of an organic
solvent. The synthesis can be conducted by either synthesizing one precursor of either polyimide or polybenzimidazole before adding the monomers for the other precursor to the reaction system. Or the reactions of polyimide and polybenzimidazole are carried out separately before combining two reactions into one reaction system. Or two sets of the monomers are mixed together simultaneously in the same reaction solution when the reaction conditions are compatible. Yet, such mixing would be generally prohibited if a relatively large amount of flexible amide links were introduced to the molecular chain structure so as to reduce the glass transition temperature of the material significantly. An alternative approach to prepare monolithic porous carbon disks from precursors comprising both polyimide and polybenzimidazole is mixing both powders of polyimide and polybenzimidazole precursors together during the process of consolidating the powders into a monolith disk.
As an option, the precursor powders comprising either or both polyimide and polybenzimidazole are further broken down to smaller particle size by a shear stress and filtered through a sieve if it is necessary. The preferred particle size of precursors for the purpose of compression molding is in the range of 1//m to 300/zm, more preferably in the range of 5μm to 75μm, even more preferably in the range of 10μm to 50μm. As another option, the precursor powder comprising either or both polyimide and polybenzimidazole in the powder form is further thermally annealed at elevated temperatures before consolidating into a disk. The annealing is conducted in a temperature range of 5O0C to 6000C, more preferably in the range of 500C to 5000C for a time period between 20 minutes to 2 hours under vacuum or under protection of argon or nitrogen atmosphere.
In a second aspect, the present invention provides processes for producing porous monolithic disks of transition metal doped precursors comprising either or both polyimide and polybenzimidazole as organic precursors for producing transition metal doped monolithic porous carbon disks which have surface area at or above 500 nrvVgram, sufficiently high mechanical strength, and macrocyclic pyridine
structure wherein the transition metal atoms caged or complexed into to provide catalytic activities.
In a general procedure, a transition metallic compound in solution is added to the reaction system or to the dried precursor powder or to the dried disk precursor. The solvent used for dissolving the transition metallic compound is preferably the same solvent as the one for preparing the precursors. Although not exclusive to the addition of the metallic compounds at any stage or any step during preparation of the monolith disk including each synthetic step of the condensation reaction and the consolidation process, preferably, the transition metallic compounds are added during the early stages of the procedures. Even more preferably, the transmission metallic compounds are admixed with the organic precursors in the presence of an organic solvent before proceeding with the synthesis of the precursors.
The solvent removal during the synthesis of the precursors comprising either or both of polyimide and polybenzimidazole are conducted by distillation, preferably assisted by vacuum.
Metals suitable for use in the preparation of metal doped monolithic porous carbon of this invention are not limited and may include elemental metals, organometallic compounds, coordination inorganic compounds, metal salts or any combinations thereof. The preferred metals include Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Rh, Ni, Pd, Pt, Cu, Ag, Zn, Si, Sn, Pb, Sb, Nb, Bi, Hf, Ba, Al, B, P As, Li and combinations thereof. Exemplary transition metal compounds include cobalt chloride (CoCb), iron chloride (FeCb), nickel chloride (NiCb), molybdenum chloride (MoCIs), hydrogen hexachloroplatinate hydrate (H2PtCl6*xH2θ), copper chloride (CuCb), tungsten chloride (WCIβ), zirconium chloride (ZrCU), cerium nitrate (Ce(NO3)3), ruthenium chloride (RuCb) and hafnium chloride (HfCU).
Typically, the transition metallic compound is present in the precursor in an amount from 0.01 % to 20% by weight, or more.
In a third aspect, the present invention provides processes for producing monolithic porous carbon disks which has a rod density of less than or equal to 1.0 gram/cc comprising: producing the organic precursors in powders comprising either
or both polyimide and polybenzimidazole; consolidation of the powder into a monolith under a pressure in the range of 3000 psi to 13000 psi; and pyrolysis under protection of an inert atmosphere.
In a fourth aspect, the present invention provides processes for producing monolithic porous carbon having one or more than one metals dispersed therein, which has a rod density of less than or equal to 1.0 gram/cc comprising: powders of transition metal doped precursors comprising either or both polyimide and polybenzimidazole; consolidation of the porous precursor powders into a monolith preferably at ambient temperature under a pressure in the range of 3000 psi to 13000 psi. and pyrolysis under protection of an inert atmosphere.
In a general consolidating procedure, the precursor powders are evenly placed in a mold or on a supporting substrate such as a fiber pad, before a sufficiently high compression pressure and a sufficient holding time are applied to produce a monolith disk with rod density in the range of 0.4g/c to 1.Og/c, preferably 0.6g/cc to 0.95g/cc.
Pyrolysis of the compressed disks is carried out under protection of an inert gas atmosphere, such as argon, nitrogen or carbon dioxide, at a temperature in the range of 6000C to 30000C, more preferably 7500C to 15000C. As an option, the inert gas atmosphere may be changed to carbon dioxide during the pyrolysis, preferably in the later stage of the pyrolysis, to further activate the pore surface of the monolithic carbon disk. The heating rate shall be sufficiently slow as to optimize the properties of the monolithic carbon.
In fifth aspect, the present invention provides processes for producing porous carbon-carbon composite with a rod density of less than or equal to 1.0 gram/cc from the precursors comprising either or both polyimide or polybenzimidazole and activated carbon in the forms of powder and fiber comprising: blending the precursor, carbon, and other additives thoroughly; removing the solvent in the mixture in cases that a solvent is involved in the mixture; consolidating the mixture into monolith under pressure conditions as to produce a homogeneous composition
with desired rod density; and pyrolysis under an inert atmosphere for producing monolithic porous carbon.
In a sixth aspect, the present invention provides processes for producing porous carbon composites incorporating other additives in addition to the carbon comprising: blending the organic precursor of this invention, carbon, and other additives thoroughly; removing the solvent in the mixture in cases that a solvent is involved during the mixing; consolidating the mixture into monolith under pressure conditions as to produce a homogeneous composition with desired rod density; and pyrolysis under an inert atmosphere for producing monolithic porous carbon. Other additives include metallic compounds, silica, carbon in the forms of powders, fibers, nanotubes, and bulkyballs or fullerences, graphite, metal oxides and metal carbides, polymeric resins in either liquid or powder forms, such as commercial phenolic resins and commercial polyimide resins, and mixtures thereof. The additives can be in the forms of powders, fibers, flakes, liquids, or porous substrates composed of one or more than one kind of fibers, membranes, metallic meshes, and foams.
There are different ways to blend the polyimide precursor, carbon, and other ingredients together. For example in the cases of polyimide precursors, one way of blending is to thoroughly mix polyimide powder with the carbon and other additives. Another way is to coat viscous solution of poly(amic acid) onto carbon and other additives before removing the solvent, then converting poly(amic acids) to polyimides. The present invention is directed in one aspect to simply mixing the polyimide precursor powder with the carbon and other additives, but is not intended to be limited to any particular way of blending the precursor with the carbon as well as other additives.
The organic precursors comprising either or both polyimide and polybenzimidazole suitable for use in the method of making monolithic porous carbon disks of the present invention can incorporate other components during the synthesis, such as imidazopyrrolone, siloxane, silica, epoxy, bismaleimide,
polyetherimide, but have the composition of polyimide and/or polybenzimidazole preferably greater than or equal to 70% by weight.
Preferred aromatic tetracarboxylic dianhydride, or tetracarboxylic acids, or diester(s) of tetracarboxylic acids monomers suitable for use in the method of making polyimide precursors of the present invention include following dianhydride compounds and their derivatives of tetracarboxylic acids and dialkyl ester(s) of tetracarboxylic acids: pyromellitic dianhydride; pyromellitic tetracarboxylic acids, dialkyl ester(s) of pyromellitic tetracarboxylic acids and aromatic tetracarboxylic dianhydride or tetracarboxylic acids or esters of the tetracarboxylic acids including 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone dianhydride, 2,3,6,7-naphthylene tetracarboxylic acid dianhydrides, 1 ,4,5,8- naphthalene tetracarboxylic acids, 2,2-bis (3,4-dicarboxy phenyl) propane acid dianhydride, and combinations thereof.
When ester(s) are alkyl esters the alkyl group preferably contains 1 to 5 carbon atoms and is more preferably methyl.
Preferred aromatic diamine monomers suitable for use in the methods of making polyimide precursors of the present invention include 1 ,4-phenylene diamine, m-phenylene diamine, 4,4'diamino-biphenyl, 4,4' and 3,3'- diaminodiphenylmethanes, 4,4', and 3,3' -diaminobenzophenones, benzidine, 2,6 - diaminopyridine, 2,6-diaminonaphthalene, 1,4-diaminocyclohexane, 2,4 and 2,6 - diaminotoluene, and derivatives thereof (i.e.: substituted diamine having a substituent(s)). The above diamine monomers may be used alone or as a mixture of two or more of them.
Preferred polyamine compounds with amine functionality greater than 2 suitable for use in the methods of making polyimide precursors of the present invention include 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5-benzenetetraamine, 3,3'4,4'-tetraaminodiphenyl ether, 3,3'4,4'-tetraaminodiphenylmethane, 3,3',4,4'- tetraaminobenzophenone, 3,3',4-triaminodiphenyl, 3,3',4-triaminodiphenylmethane, 3,3',4-triaminobenzophenone, 1 ,2,4-triaminobenzene, their mono-, di-, tri-, or tetra- acid salts., such as 3,3'4,4'-biphenyltetraamine tetrahydrochloride, 1,2,4,5-
benzenetetraamine tetrahydrochloride, 3,3'4,4'-tetraaminodiphenyl ether tetrahydrochloride, 3, 3'4,4^etraaminodiphenylmethane tetrahydrochloride, 3, 3 V4,4'-tetraaminobenzophenone tetrahydrochloride, 3,3',4-triaminodiphenyl trihydrochloride, 3,3/ /4-triaminodiphenylmethane tri hydrochloride, 3,3',4- triaminobenzophenone trihydrochloride, 1,2,4-triaminobenzene trihydrochloride, melamine, 2,4,6-triaminopyrimidine (TAP). The acid salts of above compounds usually exist in the form of hydrated compounds. Any of the above compounds may be used either alone or as a mixture of two or more of them.
Preferred polyamine compounds with amine functionality greater than 2 suitable for use in the methods of making polyimide precursors composed of a three- dimensional molecular structure of the present invention also include a polyamine oligomer with the formula:
Preferred aromatic isocyanate monomers suitable for use in the methods of making polyimide precursors of the present invention include 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate, 4/4'-diphenylmethane diisocyanate. Any of the above compounds may be used either alone or as a mixture of two or more of them. Preferred aromatic dialdehyde monomers suitable for use in the methods of making polybenzimidazole precursors of the present invention include isophthalaldehyde, terephthaldicarboxaldehyde, phthalic dicarboxaldehyde, and 2,6-naphthalenedicarboxaldehyde.
Preferred monomers of aromatic acids and esters of dicarboxylic acids suitable for use in the methods of making polybenzimidazole precursors of the present invention include acids and esters of isophthalic acid, phthalic acid, terephthalic acid, 1 ,4-naphthalenedicarboxylic acid, and 2,6-
naphthalenedicarboxylic acid. The ester(s) may be alkyl or phenyl esters. When ester(s) are alkyl esters the alkyl group preferably contains 1 to 5 carbon atoms and is more preferably methyl.
Preferred monomers of aromatic tetraamines suitable for use in the methods of making polybenzimidazole precursors of the present invention include 3,3' ',4,4'- tetraaminobiphenyl (3,3'-dianninobenzidine); 1 ,2,4,5-tetraaminobenzene; 1, 2,5,6- tetraaminonaphthalene; 2,3,6,7-tetraaminonaphthalene; 3,3 ',4,4'- tetraaminodiphenyl methane; 3,3',4,4'-tetraaminodiphenyl ethane; 3,3',4,4'- tetraaminodiphenyl-2,2-propane; and combinations thereof. Preferred reaction solvents for the synthesis of the precursors comprising either or both polyimide and polybenzimidazole include N-methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), tyN-dimethyl formamide (DMF), tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), acetone, methanol, toluene, chlorobenzene, ethanol, and mixtures thereof. The monolithic carbon of this invention is suitable for use as an electrode material in electrochemical capacitors and related electrochemical devices. The porous monolithic carbon of the invention offer the advantage of a monolithic structure, high density, high surface area, and narrow pore size distribution.
Examples
Example 1. Synthesis of Polyimide Precursor with three-dimensional molecular structure and Carbon Disk therefrom.
Starting monomers: 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5- benzenetetracarboxylic dianhydride (PMDA), and 1 ,4-phenylenediamine (PPD).
Solvent: N,N-dimethylacetamide (DMAc).
1.30 gram (0.012 mole) PPD was dissolved in 40 ml DMAc in a flask. While stirring, 3.270 gram (0.015 mole) PMDA in the solid form was added to the reaction system. After PMDA was fully dissolved, 0.3215 gram (0.0015 mole) TAB was added to the reaction system. The reaction was carried out at ambient temperature with mechanical stirring until a very viscous solution, often gel lumps, were formed. The temperature of the reaction was gradually raised to 1500C with strong agitation to produce polyimide in precipitated powder form. The solvent was distilled off under vacuum at 500C. The powders were further broken down and filtered through a 50 micron-sized sieve. By using a hydraulic press, the polyimide powders were placed in a mold and compressed under pressure of 5000 psi at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed at 8000C for 3 hours under protection of nitrogen to produce a monolithic carbon disk. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 90 F/gram. See Figure 1.
Example 2. Synthesis of Polyimide Prepolymer with three-dimensional molecular structure doped with 1% Molybdenum by weight and Carbon Disk therefrom
Starting monomers and additive: 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5- benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCl5).
Solvent: N, N-di methyl acetamide (DMAc).
1.30 gram (0.012 mole) PPD and 0.135 gram MoCl5 were dissolved in 40 ml DMAc in a flask. While stirring, 3.270 gram (0.015 mole) PMDA in the solid form was added to the reaction system. After PMDA was fully dissolved, 0.3215 gram (0.0015 mole) TAB was added to the reaction system. The reaction was carried out at ambient temperature with mechanical stirring until a very viscous solution, often
gel lumps, were formed. The temperature of the reaction was gradually raised to 1500C with strong agitation to produce polyimide/MoCI5 in precipitated powder form. The solvent was distilled off under vacuum at 500C. The powders were further broken down and filtered through a 50 micron-sized sieve.
The polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed at 8000C for 3 hours under protection of a nitrogen to produce a monolithic carbon disk. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 210 F/gram. See Figure 2.
Example 3. Synthesis of Polyimide Prepolymer doped with 1% Molybdenum by weight and Carbon Disk therefrom
Starting monomers and additive: 1 ,2,4,5-benzenetetracarboxylic dianhydride
(PMDA), 1 ,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCl5).
Solvent: N/N-dimethylacetamide (DMAc).
1.622 gram (0.015 mole) PPD and 0.135 gram MoCl5 were dissolved in 40 ml DMAc in a flask. While stirring, 3.270 gram (0.015 mole) PMDA in the solid form was added to the reaction system. The reaction was carried out at ambient temperature with stirring until a very viscous solution was formed. The reaction temperature was raised to 15O0C with strong agitation to produce polyimide/MoCI5 precipitate in precipitated powder form. The solvent was distilled off under vacuum at 500C. The powders were further broken down and filtered through a 5-micron- sized sieve.
The polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolith. Pyrolysis of the monolith was carried out at 8000C for 2 hours under a nitrogen atmosphere and 1 hour under a carbon dioxide
atmosphere. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s, shown in Figure 3, displayed the capacitance of the material at 200 F/gram.
Example 4. Synthesis of Polyimide Precursor doped with 1% (by wt.) Molybdenum in Acetone and Carbon Disk therefrom
Starting monomers and additive: 3,3'4,4'-biphenyltetraamine (TAB), 1,2,4,5- benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCl5).
Solvent: acetone
3.270 gram (0.015 mole) PMDA was dissolved in 20 ml acetone. 1.30gram (0.012 mole) PPD, 0.3215 gram (0.0015mole) TAB, and 0.135 gram MoCl5 were dissolved in 20 ml acetone in a separate flask. The PMDA solution was gradually added to PPD/TAB/MoCIs solution to produce a white precipitate immediately. The solvent was distilled off and temperature of the product was raised to 150 0C to convert poly(amic acids) to polyimide in powder form. The powders are further broken down and filtered through a 50 micron-sized sieve. The polyimide powder was compressed at 4000psi pressure at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed at 800 0C for 3 hours under protection of nitrogen to produce a monolithic carbon disk. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 100 F/gram.
Example 5. Synthesis of Polyimide Precursor with three-dimensional molecular structure doped with 1% Molybdenum by weight and Carbon Disk therefrom
Starting monomers and additive: 3,3'4,4'-biphenyltetraamine (TAB), 1 ,2,4,5- benzenetetracarboxylic dianhydride (PMDA), 1,4-phenylenediamine (PPD), diaminopyridine, and molybdenum chloride (V) (MoCl5).
Solvent: N,N-dimethylacetamide (DMAc).
1.082 gram (0.01 mole) PPD, 0.218 gram diaminopyridine (0.002 mole) and 0.135 gram MoCl5 were dissolved in 40 ml DMAc in a flask. While stirring, 3.270 gram (0.015 mole) PMDA in the solid form was added to the reaction system. After PMDA was fully dissolved, 0.3215 gram (0.0015 mole) TAB was added to the reaction system. The reaction was carried out at ambient temperature with a normal agitation until a viscous solution was formed. The temperature of the reaction was raised to 1500C with strong agitation to produce polyimide/MoCl5 in precipitated powder form. The solvent was distilled off under vacuum at 500C. The powders were further broken down and filtered through a 50 micron-sized sieve.
The polyimide powder were compressed at 4000 psi pressure at ambient temperature to produce a monolithic disk. The monolithic disk was pyrolyzed at 800 0C for 3 hours under protection of nitrogen to produce a monolithic carbon disk. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 100 F/gram.
Example 6. Synthesis of Polyimide Prepolymer and Porous Carbon therefrom
Starting monomers: 1 ,2,4,5-benzenetetracarboxylic dianhydride (PMDA), and 1 ,4-phenylenediamine (PPD).
Solvent: N/N-dimethylacetamide (DMAc).
1.622 gram (0.015 mole) PPD was dissolved in 40 ml DMAc in a flask. While stirring, 3.270 gram (0.015 mole) PMDA in the solid form was added to the
reaction system. The reaction was carried out at ambient temperature with stirring until a very viscous solution was formed. The reaction temperature was raised to 15O0C with strong agitation to produce polyimide precipitate. The solvent was distilled off under vacuum at 500C. The powders were further annealed at 300 0C for 30 minutes.
The polyimide powders were consolidated at 4500 psi pressure at ambient temperature to produce a monolith. Pyrolysis of the monolith was carried out at 9000C for 3 hours under a nitrogen atmosphere. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 80 F/gram.
Example 7. Electrode for Supercapacitor
A supercapacitor was constructed using the carbon prepared according to Example 3 as electrodes. The electrode dimension was 0.81 " in diameter and 0.012" in thickness. The prototype supercapacitor comprises a pair of carbon electrodes sandwiched between two current collector plates. A microporous separator was placed between two electrodes. 38% sulfuric acid electrolyte impregnates the electrodes and the separator before the current plates were sealed by a thermoplastic edge sealant. The result of characterization is shown in Table 1 ,
Table 1
Example 8. Synthesis of Polyimide Precursor doped with 0.5% Molybdenum and Porous Carbon therefrom
Starting monomers and additive: 1 ,2,4,5-benzenetetracarboxylic dianhydride (PMDA), 1 ,4-phenylenediamine (PPD), and molybdenum chloride (V) (MoCI5).
Solvent: tetrahydrofuran (THF).
3.270 gram (0.015 mole) PMDA was dissolved in 20 ml THF. 1.62 gram (0.015 mole) PPD, and 0.065 gram MoCl5 were dissolved in 20 ml THF in a separate flask. The PMDA solution was gradually added to PPD/MoCl5 solution to produce a white precipitate immediately. The solvent was distilled off. The poly(amic acids) powder was converted to polyimide by thermally annealed at 3000C for 30 minutes.
The polyimide powders were compressed at 4500 psi pressure at ambient temperature to produce a monolith. The monolith was pyrolyzed at 900 0C for 3 hours under protection of nitrogen to produce a monolithic carbon. The cyclic voltammetry of the carbon disk at a scan rate of 5mV/s displayed the capacitance of the material at 150 F/gram.
Example 9a. Preparation of Carbon-Carbon Composite and An Electrochemical Capacitor Cell Therefrom
Polyimide precursor: prepared in Example 6.
Carbon Black Powder: commercially available carbon black from a natural source;
Activated Carbon fiber: phenolic resin based carbon fiber.
1.58 gram carbon black powder (66%), 0.68 gram polyimide powder (28%), and 0.14 gram carbon fiber (6%) were blended together by grinding and mixing 0.5
gram mixture was compressed at 6500 psi at ambient temperature to produce a monolithic disk about 1 mm thick and 2.5 cm in diameter. The disk was pyrolyzed at 800 0C for 3 hours under protection of nitrogen to produce a porous carbon- carbon composite disk.
Two carbon-carbon composite disks of 0.78 gram with diameter of 2.5 cm and thickness of 1.20 mm were used to assemble a symmetric single cell according to the procedure in Example 3. The result of characterization is listed in Table 2. A Z" vs. Z' plot of impedance data is displayed in Figure 4.
Example 9b. A Comparative Electrochemical Capacitor Cell Using Carbon Black Electrodes
Two carbon disks of 0.77 gram with diameter of 2.5 cm and thickness of 1.20 mm were prepared from same carbon black powder as used in Example 9a. The disks were used to assemble a symmetric single cell according to the procedure in Example 3. The result of characterization is listed in Table 2. A Z" vs. Z' plot of impedance data is displayed in Figure 4.
Table 2
Example 10. Preparation of Carbon-Carbon Composite doped with 0.85% Molybdenum and An Electrochemical Capacitor Cell Therefrom
Polyimide precursor: prepared in Example 1.
Carbon Black Powder: commercially available carbon black from a natural source;
Activated Carbon fiber: phenolic resin based carbon fiber;
Molybdenum chloride (V) (MoCl5).
0.06 gram molybdenum chloride was dissolved in 3.0 ml methanol. 2.6 gram carbon black powder was immersed in Mo/methanol solution with stirring for overnight before methanol was removed by distillation.
1.24 gram Mo doped carbon black powder (61 %), 0.665 gram polyimide powder (33%), and 0.12 gram activated carbon fiber (6%) were blended together by grinding and mixing. 0.5 gram mixture was compressed at 6500 psi at ambient temperature to produce a monolithic disk about 1 mm thick and 2.5 cm in diameter. The disk was pyrolyzed at 800 0C for 1.5 hours under protection of nitrogen and 1.5 hours under carbon dioxide to produce a porous carbon-carbon composite disk.
Two carbon-carbon composite disks with diameter of 2.5 cm and thickness of 1.20 mm were used to assemble a symmetric single cell according to the procedure in Example 3.
Thus, having described the invention, what is claimed is:
Claims
1. A process for producing monolithic porous carbon disks as electrode materials from precursors comprising either or both polyimide and polybenzimidazole in the powder form comprising the steps of: preparing a precursor powder comprising either or both polyimide and polybenzimidazole; consolidating the precursor powder into a monolith under pressure; and pyrolyzing the monolith in an inert atmosphere or carbon dioxide to form a monolithic porous carbon disk.
2. The process of claim 1 wherein a metallic compound is added to the precursor during any of the steps used to prepare the precursor powder or monolithic disks.
3. The process of claim 1 wherein the precursor is prepared as a powder precipitate in the presence of a solvent.
4. The process of claim 1 wherein the precursor powders for consolidation into a disk have the average particle size in the range of 1 μm to 200 μm.
5. The process of claim 1 wherein the precursor powder before consolidating into a disk is annealed at a temperature in the range of 150°C-500°C.
6. The process of claim 1 wherein the prepolymer powders are consolidated under a pressure in the range of 3000 psi to 13000 psi.
7. The process of claim 1 wherein the monolithic carbon disk has a density in the range of 0.4 gram/cc to 1.2 gram/cc, and a surface area at or above 300 mVgram.
8. The process of claim 2 wherein the metallic compound contains metals selected from the group consisting of Ti, Zr, V, Nb, Cr, Mo, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Zn, Pb, Hf, W, Ba, Al, Pt, Si, P, Rh, Sb, Sn, Bi, Li and combinations thereof.
9. The process of claim 2 wherein the addition of a metallic compound or metallic compounds to the prepolymer is conducted to form a true molecular solution of the metallic compound with the precursor reaction system.
10. The process of claim 2 wherein the addition of a metallic compound or compounds to the prepolymer is conducted by adding a metallic compound solution to the dried prepolymer in either the powder form or consolidated disk followed by removing the solvent from the prepolymer.
1 1. The process of claim 2 wherein weight percentage of the metal in the carbon is in the range of 0.01 % to 20%.
12. The process of claim 1 wherein an aromatic diamine monomer is used to form the polyimide segment of the precursor and is selected from 1 ,4- phenylenediamine; m-phenylenediamine, 4,4'diamino-biphenyl, 4,4'- diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 4,4'- diaminobenzophenone, 3,3'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, benzidine, 2,6-diaminonaphthalene, 2,6-diaminopyridine, and derivatives thereof or a combination thereof.
13. The process of claim 1 wherein an aromatic dianhydride monomer is used to form the polyimide segment of the precursor and is selected from pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'- benzophenone tetracarboxylic dianhydride, 2,3,6,7-naphthylene tetracarboxylic dianhydride 1 ,4,5,8-naphthalene tetracarboxylic dianhydride, 2,2-bis(3,4- dicarboxyphenyl) propane dianhydride and combinations thereof.
14. The process of claim 1 wherein a monomer of ester (s) and acids of aromatic tetracarboxylic acids used to form the polyimide segment of the precursor is selected from the group consisting of pyrometallitic tetracarboxylic acids, 3,3',4/4'- biphenyl tetracarboxylic acids, 3,3',4,4' benzophenone tetracarboxylic acids, 2,3,6,7 naphthalene tetracarboxylic acids, 1 ,4,5,8-naphthalene tetracarboxylic acids, and combinations thereof, including alkyl or phenyl esters, with the alkyl group containing 1-5 atoms.
15. The process of claim 1 wherein a polyamine compound with amine functionality greater than 2 is used to from the polyimide segment of the precursor and is selected from 3,3'4,4'-biphenyltetraamine (TAB), 1,2,4,5-benzenetetraamine, 3,3'4,4'-tetraaminodiphenyl ether, 3,3'4,4'-tetraaminodiphenylmethane, 3,3',4,4'- tetraaminobenzophenone, 3,3',4-triaminodipheny, I, 3,3',4- triaminodiphenylmethane, 3,3',4-triaminobenzophenone, 1 ,2,4-triaminobenzene, their mono-, di-, tri-, or tetra- acid salts, such as 3,3'4,4'-biphenyltetraamine tetrahydrochloride, 1 ,2,4,5-benzenetetraamine tetrahydrochloride, 3,3'4,4'- tetraaminodiphenyl ether tetrahydrochloride, 3,3'4,4'-tetraaminodiphenylmethane tetrahydrochloride, 3,3',4,4'-tetraaminobenzophenone tetrahydrochloride, 3,3',4- triaminodiphenyl tri hydrochloride, 3,3',4-triaminodiphenylmethane trihydrochloride, 3,3',4-triaminobenzophenone tri hydrochloride, 1 ,2,4- triaminobenzene trihydrochloride, melamine, 2,4,6-triaminopyrimidine (TAP), or a polyamine oligomer with the formula:
16. The process of claim 1 wherein an aromatic isocyanate monomer is used to form the polyimide segment of the precursor and is selected from 1 ,3-phenylene diisocyanate, 1 ,4-phenylene diisocyanate and 4,4'-diphenylmethane diisocyanate.
17. The process of claim 1 wherein a monomer of ester(s) or acids of aromatic dicarboxylic acids is used to form the polybenzimidazole segment of the precursor is selected from esters and acids of isophthalic acid, phthalic acid, terephthalic acid, 1 ,4 naphthalene dicarboxylic acid or 2,6-napthalene dicarboxylic acid.
18. The process of claim 1 wherein an aromatic dialdehyde monomer is used to from the polybenzimidazole segment of the precursor and is selected from isophthalaldehyde, terephthaldicarboxaldehyde, phthalic dicarboxaldehyde, and 2,6-naphthalenedicarboxaldehyde, and combinations thereof.
19. The process of claim 1 wherein an aromatic tetraamines monomer is used to form the polybenzimidazole segment of the precursor and is selected from 3,3',4,4'-tetraaminobiphenyl (3,3'-diaminobenzidine); 1,2,4,5-tetraaminobenzene; 1 ,2,5,6-tetraaminonaphthalene; 2,3,6,7-tetraaminonaphthalene; 3,3',4,4'- tetraami nodi phenyl methane; 3,3',4,4'-tetraaminodiphenyl ethane; 3,3',4,4'- tetraaminodiphenyl-2,2-propane; and combinations thereof.
20. The process of claim 3 wherein the organic solvent is selected from N- methyl-2-pyrrolidinone (NMP), N,N-dimethylacetamide (DMAc), N,N-dimethyl formamide (DMF), dioxane, dimethyl sulfoxide (DMSO), chlorobenzene, acetone, methanol, and tetrahydrofuran (THF), toluene, benzene, ethanol, 2-propanol, and mixtures thereof.
21. The process of claim 1 wherein said polyimide and polybenzimidazole have structures of the formulas:
(1) Polyimide
(2) Polybenzimidazole
wherein Al and A4 represent difunctional phenyl, difunctional biphenyl, an optionally substituted aryl, optionally substituted alkylene, an optionally substituted heteroaryl, or a combination thereof; wherein A2 and A5 represents tetrafunctional phenyl, biphenyl, an optionally substituted tetrafunctional aryl group, or an optionally substituted difunctional heteroaryl group; wherein A3 represent multifunctional phenyl with functionality more than or equal to 2, multifunctional biphenyl with functionality more than or equal to 2, an optionally substituted multifunctional aryl with functionality more than or equal to 2, optionally substituted multifunctional alkylene with functionality more than or equal to 2, an optionally substituted multifunctional heteroaryl with functionality more than or equal to 2, or a combination thereof; ni, n2 and n3 are greater or equal to 1; and (y+2) are more than or equal to 2.
22. The process of claim 1 in which the process further comprises incorporating reinforcing materials or other additives in solid form with the precursor powders during the consolidation process to produce the monolithic porous carbon disk composites therefrom.
23. The process of claim 22 wherein the reinforcing materials or other additives include reinforcement fiber pad in the form of either a non-woven or woven form composed of one or more than one kinds of an organic polymer fiber or inorganic polymer fiber or metal fibers, silica, carbon cloth, carbon paper, carbon nanotubes, metallic fibers or particles, polymeric micron beads, microcrystalline inorganic and organic compounds, silica powder, inorganic fillers, liquid polymer resins, or particles.
24. The process of claim 1 in which the process further comprises adding carbon to the precursor powders to form a monolithic porous carbon-carbon composite disk.
25. The process of claim 24 wherein the composition of the carbon-carbon composite before pyrolysis is in the range of 5 to 90%.
26. The process of claim 25 wherein the carbon is activated carbon powder and activated carbon fiber.
27. A monolithic porous carbon disk made by the method of claim 1.
28. A monolithic porous carbon-carbon composite made by the method of claim 24.
29. An electrochemical device comprising at least one cell, said cell comprising: two conductive electrodes; and a porous non-conductive separator disposed between the two electrodes, an electrolyte occupying pores of said electrodes and separator, wherein at least one of said electrodes comprises a monolithic porous carbon or a porous carbon composite according to claim 1.
30. The device of claim 29 wherein the cell includes capacitors, supercapacitors, electrochemical-electrolytic hybrid capacitors, hybrid battery/supercapacitor systems, lithium batteries, fuel cells, and other types of batteries.
31. An electrochemical device comprising at least one cell, said cell comprising: two conductive electrodes; and a porous non-conductive separator disposed between the two electrodes, an electrolyte occupying pores of said electrodes and separator, wherein at least one of said electrodes comprises a monolithic porous carbon or a porous carbon composite according to claim 24.
32. The device of claim 31 wherein the cell includes capacitors, supercapacitors, electrochemical-electrolytic hybrid capacitors, hybrid battery/supercapacitor systems, lithium batteries, fuel cells, and other types of batteries.
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Non-Patent Citations (3)
Title |
---|
BURGER A ET AL: "Polyimides as precursors for artificial carbon", CARBON, ELSEVIER, OXFORD, GB, vol. 13, no. 3, 1 June 1975 (1975-06-01), pages 149-157, XP024031117, ISSN: 0008-6223, DOI: DOI:10.1016/0008-6223(75)90225-0 [retrieved on 1975-06-01] * |
See also references of WO2006023419A1 * |
YUDIN V E ET AL: "Carbonization behaviour of some polyimide resins reinforced with carbon fibers", CARBON, ELSEVIER, OXFORD, GB, vol. 38, no. 1, 1 January 2000 (2000-01-01), pages 5-12, XP004243554, ISSN: 0008-6223, DOI: DOI:10.1016/S0008-6223(99)00073-1 * |
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