KR20210001662A - Metal organic framework, porous carbon structure comprising the same and method for preparing the same - Google Patents
Metal organic framework, porous carbon structure comprising the same and method for preparing the same Download PDFInfo
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- KR20210001662A KR20210001662A KR1020190078068A KR20190078068A KR20210001662A KR 20210001662 A KR20210001662 A KR 20210001662A KR 1020190078068 A KR1020190078068 A KR 1020190078068A KR 20190078068 A KR20190078068 A KR 20190078068A KR 20210001662 A KR20210001662 A KR 20210001662A
- Authority
- KR
- South Korea
- Prior art keywords
- metal organic
- porous carbon
- acid
- zinc
- producing
- Prior art date
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 75
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000011701 zinc Substances 0.000 claims abstract description 35
- 239000013110 organic ligand Substances 0.000 claims abstract description 28
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 25
- 229910052751 metal Inorganic materials 0.000 claims description 55
- 239000002184 metal Substances 0.000 claims description 55
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 45
- 239000002243 precursor Substances 0.000 claims description 37
- 238000004519 manufacturing process Methods 0.000 claims description 30
- -1 tetrachloroethylene, propylene Chemical group 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000003960 organic solvent Substances 0.000 claims description 19
- 239000003125 aqueous solvent Substances 0.000 claims description 15
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012046 mixed solvent Substances 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid Chemical compound OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 4
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical group COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 4
- 229940113088 dimethylacetamide Drugs 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- AJFDBNQQDYLMJN-UHFFFAOYSA-N n,n-diethylacetamide Chemical compound CCN(CC)C(C)=O AJFDBNQQDYLMJN-UHFFFAOYSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 4
- WFYASTPQDOUBSW-UHFFFAOYSA-N 1h-1,2,4-triazole Chemical compound C=1N=CNN=1.C1=NN=CN1 WFYASTPQDOUBSW-UHFFFAOYSA-N 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 3
- FZIPCQLKPTZZIM-UHFFFAOYSA-N 2-oxidanylpropane-1,2,3-tricarboxylic acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O.OC(=O)CC(O)(C(O)=O)CC(O)=O FZIPCQLKPTZZIM-UHFFFAOYSA-N 0.000 claims description 3
- ULMNNWOODRUGCA-UHFFFAOYSA-N 2H-triazole Chemical compound C=1C=NNN=1.C=1C=NNN=1 ULMNNWOODRUGCA-UHFFFAOYSA-N 0.000 claims description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- HCPOCMMGKBZWSJ-UHFFFAOYSA-N ethyl 3-hydrazinyl-3-oxopropanoate Chemical compound CCOC(=O)CC(=O)NN HCPOCMMGKBZWSJ-UHFFFAOYSA-N 0.000 claims description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 229960005137 succinic acid Drugs 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- RJLKIAGOYBARJG-UHFFFAOYSA-N 1,3-dimethylpiperidin-2-one Chemical compound CC1CCCN(C)C1=O RJLKIAGOYBARJG-UHFFFAOYSA-N 0.000 claims description 2
- AIDFJGKWTOULTC-UHFFFAOYSA-N 1-butylsulfonylbutane Chemical compound CCCCS(=O)(=O)CCCC AIDFJGKWTOULTC-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- CMJLMPKFQPJDKP-UHFFFAOYSA-N 3-methylthiolane 1,1-dioxide Chemical compound CC1CCS(=O)(=O)C1 CMJLMPKFQPJDKP-UHFFFAOYSA-N 0.000 claims description 2
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 2
- OHLUUHNLEMFGTQ-UHFFFAOYSA-N N-methylacetamide Chemical compound CNC(C)=O OHLUUHNLEMFGTQ-UHFFFAOYSA-N 0.000 claims description 2
- MZBKIGFCBRHMNR-UHFFFAOYSA-N OC=1C(C(C1O)=O)=O.OC=1C(C(C1O)=O)=O Chemical compound OC=1C(C(C1O)=O)=O.OC=1C(C(C1O)=O)=O MZBKIGFCBRHMNR-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical group C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims 1
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims 1
- QWCKCWSBAUZZLF-UHFFFAOYSA-L zinc sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O QWCKCWSBAUZZLF-UHFFFAOYSA-L 0.000 claims 1
- 230000009257 reactivity Effects 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 18
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004745 nonwoven fabric Substances 0.000 description 8
- 239000007774 positive electrode material Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical group [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- SGVYKUFIHHTIFL-UHFFFAOYSA-N 2-methylnonane Chemical compound CCCCCCCC(C)C SGVYKUFIHHTIFL-UHFFFAOYSA-N 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 239000004020 conductor Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229920000098 polyolefin Polymers 0.000 description 5
- 238000004626 scanning electron microscopy Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000758 substrate Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 4
- 150000005676 cyclic carbonates Chemical class 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 150000004820 halides Chemical class 0.000 description 4
- 229910003002 lithium salt Inorganic materials 0.000 description 4
- 159000000002 lithium salts Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- 239000011255 nonaqueous electrolyte Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 150000004687 hexahydrates Chemical class 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- CRZQGDNQQAALAY-UHFFFAOYSA-N Methyl benzeneacetate Chemical compound COC(=O)CC1=CC=CC=C1 CRZQGDNQQAALAY-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000002174 Styrene-butadiene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical class [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 2
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 2
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229940016681 dipropylacetamide Drugs 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- TVQGDYNRXLTQAP-UHFFFAOYSA-N ethyl heptanoate Chemical compound CCCCCCC(=O)OCC TVQGDYNRXLTQAP-UHFFFAOYSA-N 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- BYEVBITUADOIGY-UHFFFAOYSA-N ethyl nonanoate Chemical compound CCCCCCCCC(=O)OCC BYEVBITUADOIGY-UHFFFAOYSA-N 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- JBFHTYHTHYHCDJ-UHFFFAOYSA-N gamma-caprolactone Chemical compound CCC1CCC(=O)O1 JBFHTYHTHYHCDJ-UHFFFAOYSA-N 0.000 description 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 description 2
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- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
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Abstract
Description
본 발명은 새로운 형태의 금속 유기 골격체, 이를 포함하는 다공성 탄소 구조체 및 이들의 제조방법에 관한 것이다.The present invention relates to a new type of metal organic framework, a porous carbon structure including the same, and a method of manufacturing the same.
에너지 저장체인 리튬-황(Li-S) 이차전지는, 이론 에너지 밀도가 2600 Wh/kg 이고, 이론용량은 1672 mAh/g으로서 기존의 리튬 배터리의 3~5배에 높은 에너지 밀도를 나타내어 차세대 에너지 저장체로서 주목을 받고 있다. 하지만 상용화하여 사용하기에는 사이클 특성이 좋지 않아 다양한 방법을 사용하여 사이클 특성을 높이기 위한 연구가 진행 되어 왔다.The energy storage lithium-sulfur (Li-S) secondary battery has a theoretical energy density of 2600 Wh/kg and a theoretical capacity of 1672 mAh/g, which is 3 to 5 times higher than that of conventional lithium batteries. It is attracting attention as a storage body. However, since the cycle characteristics are not good for commercial use, research has been conducted to increase the cycle characteristics by using various methods.
특히, 탄소를 기반으로 한 물질인 그래핀 (Graphene)과 활성탄소 (Activated carbon)를 템플릿으로 이용하여 황의 부피팽창을 막음과 동시에 전도성을 높이는 방법이 주로 사용되었다. 하지만 이러한 방법들도 상용화를 실현하기 위해서는 부족한 점이 많이 있고 상용화를 위해 다른 방법이 제시되어야 하는 상황이다.In particular, a method of increasing conductivity while preventing volume expansion of sulfur by using carbon-based materials such as graphene and activated carbon as templates was mainly used. However, these methods are also lacking in order to realize commercialization, and other methods must be presented for commercialization.
금속 유기 골격체(Metal Organic Frameworks, MOF)는 금속 전구체 (Metal precursor)와 유기 리간드(Organic linker)를 특정 용매에 넣고 수열합성의 방법으로 합성하게 되면 제조되는 금속 블록과 유기 리간드가 반복된 배열을 가지는 3차원의 다공성 물질이다.Metal Organic Frameworks (MOF) are formed by adding a metal precursor and an organic linker to a specific solvent and synthesizing it by hydrothermal synthesis. Eggplant is a three-dimensional porous material.
MOF는 다양한 크기의 마이크로 포어(Micropore)와 메조 포어(Mesopore)를 가지고 있으며 비표면적이 매우 넓어서 기체 저장체로서 활용되어 왔다. 또한, MOF는 전도성이 떨어지는 문제점 때문에 전기화학적으로 이용되지는 못했지만 최근 나노 크기의 MOF를 합성하여 전기화학적 용도로 사용되어 금속 유기 골격체의 활용도가 높아지고 있다. MOF has micropores and mesopores of various sizes, and has a very large specific surface area, so it has been used as a gas storage. In addition, MOF has not been used electrochemically due to the problem of poor conductivity, but recently, nano-sized MOF is synthesized and used for electrochemical purposes, and the utilization of metal organic skeletons is increasing.
또한, MOF는 금속 전구체와 유기 리간드의 조합이 매우 다양하여 수천 가지의 결정구조로 구현될 수 있으며, 다양한 작용기 (Functional group)도 포함 될 수 있기 때문에 활용도 면에서 매우 유용하다.In addition, MOF can be implemented in thousands of crystal structures due to a very diverse combination of metal precursors and organic ligands, and it is very useful in terms of utilization because it can contain various functional groups.
이와 같은 MOF는 열처리에 의한 탄화 공정을 통하여 높은 비표면적과 큰 기공률을 가지는 다공성 탄소 구조체로 제조될 수 있다 (RSC Adv., Vol. 6, Issue. 97, pp. 94629-94635; 및 중국공개특허 제109267145호). Such MOF can be manufactured into a porous carbon structure having a high specific surface area and a large porosity through a carbonization process by heat treatment (RSC Adv., Vol. 6, Issue. 97, pp. 94629-94635; and Chinese Patent Publication No. 109267145).
그러나, 높은 비표면적과 큰 기공률을 가지는 다공성 탄소 구조체도 에너지 소자에 적용시 에너지 효율 향상에 한계가 있으며, 이에 에너지 소자의 반응성을 개선시켜 에너지 효율을 향상시킬 수 있는 다공성 탄소 구조체의 개발이 필요하다.However, even a porous carbon structure having a high specific surface area and a large porosity has a limitation in improving energy efficiency when applied to an energy device. Accordingly, it is necessary to develop a porous carbon structure capable of improving energy efficiency by improving the reactivity of the energy device. .
본 발명자들은 상기 문제점을 해결하기 위해 다각적으로 연구를 수행한 결과, 금속 유기 골격체 제조시 원료 물질인 아연 전구체와 유기 리간드 전구체의 비율을 조절하고, 용매로서 사용되는 유기 용매와 수계 용매의 비율을 조절함으로써, 판상형 금속 유기 골격체와 이를 탄화시켜 판상형의 다공성 탄소 구조체를 제조할 수 있으며, 상기 판상형 다공성 탄소 구조체는 전기화학 반응의 반응성을 향상시킨다는 것을 확인하였다.As a result of conducting various studies to solve the above problems, the present inventors adjusted the ratio of the zinc precursor and the organic ligand precursor, which are raw materials, and the ratio of the organic solvent and the aqueous solvent used as a solvent when preparing a metal organic skeleton. By adjusting, it was confirmed that a plate-shaped metal organic framework and a plate-shaped porous carbon structure can be prepared by carbonizing the same, and the plate-shaped porous carbon structure improves the reactivity of the electrochemical reaction.
따라서, 본 발명의 목적은 판상형 금속 유기 골격체 및 이의 제조방법을 제공하는 것이다.Accordingly, an object of the present invention is to provide a plate-shaped metal organic skeleton and a method for manufacturing the same.
또한, 본 발명의 다른 목적은 전기화학 반응의 반응성을 향상시킬 수 있는 판상형 다공성 탄소 구조체 및 이의 제조방법을 제공하는 것이다.In addition, another object of the present invention is to provide a plate-shaped porous carbon structure capable of improving the reactivity of an electrochemical reaction and a method for manufacturing the same.
상기 목적을 달성하기 위해, 본 발명은, 판상형의 형태를 가지며, 아연; 및 유기 리간드;를 포함하는 금속 유기 골격체를 제공한다.In order to achieve the above object, the present invention has a plate-shaped form, zinc; And an organic ligand; it provides a metal organic skeleton comprising.
본 발명은 또한, (S1) 아연 전구체와 유기 리간드의 전구체를 유기 용매와 수계 용매의 혼합 용매에 용해시켜 혼합 용액을 제조하는 단계; (S2) 상기 혼합 용액을 가열하는 단계; 및 (S3) 상기 가열된 혼합 용액에서 상층액을 버린 후, 합성된 금속 유기 골격체를 세척하는 단계;를 포함하는, 금속 유기 골격체의 제조방법을 제공한다.The present invention also includes the steps of (S1) dissolving a precursor of a zinc precursor and an organic ligand in a mixed solvent of an organic solvent and an aqueous solvent to prepare a mixed solution; (S2) heating the mixed solution; And (S3) after discarding the supernatant from the heated mixed solution, washing the synthesized metal organic skeleton; containing, provides a method for producing a metal organic skeleton.
본 발명은 또한, 탄화된 상기 금속 유기 골격체를 포함하는 다공성 탄소 구조체를 제공한다.The present invention also provides a porous carbon structure comprising the carbonized metal organic skeleton.
본 발명은 또한, 상기 금속 유기 골격체를 탄화시키는 단계를 포함하는, 다공성 탄소의 제조방법을 제공한다.The present invention also provides a method for producing porous carbon, including the step of carbonizing the metal organic framework.
본 발명에 따르면, 금속 유기 골격체 제조시 사용되는 원료 물질인, 아연 전구체와 유기 리간드 전구체의 몰 비율(Molar ratio)을 조절하고, 용매로 사용되는 유기 용매와 수계 용매의 부피비를 조절함으로써, 판상형 금속 유기 골격체를 제조할 수 있다.According to the present invention, by adjusting the molar ratio of the zinc precursor and the organic ligand precursor, which is a raw material used in the manufacture of a metal organic skeleton, and by adjusting the volume ratio of the organic solvent and the aqueous solvent used as a solvent, plate-like Metal organic skeletons can be prepared.
또한, 상기 판상형 금속 유기 골격체를 탄화시킴으로써, 판상형 다공성 탄소 구조체를 제조할 수 있다. Further, by carbonizing the plate-shaped metal organic skeleton, a plate-shaped porous carbon structure can be manufactured.
또한, 상기 판상형 다공성 탄소 구조체는 반응 물질이 쉽게 이동 가능하므로, 리튬 이차전지의 전극 물질로 적용되어 반응성을 개선시킴으로서, 에너지 효율을 향상시킬 수 있다.In addition, since the plate-shaped porous carbon structure can easily move a reactive material, it is applied as an electrode material of a lithium secondary battery to improve reactivity, thereby improving energy efficiency.
도 1은 실시예에 따른 금속 유기 골격체 및 다공성 탄소 구조체의 제조 공정을 나타낸 모식도이다.
도 2는 실시예 1, 4, 6, 7 및 8에서 각각 제조된 금속 유기 골격체(에 대한 SEM(Scanning Electron Microscopy) 사진이다.
도 3a 및 3b 는 각각 실시예 5, 8 및 비교예 1에서 제조된 다공성 탄소 구조체에 대한 질소 흡탈착 등온선(nitrogen adsorption/desorption isotherms) 및 기공 크기분포를 나타낸 그래프이다.
도 4 는 실시예 3,4,5,6,7,8에서 제조된 금속 유기 골격체 및 다공성 탄소 구조체에 대한 XRD (X-Ray Diffraction) 그래프이다.
도 5는 실시예 5,8 및 비교예 1에서 각각 제조된 다공성 탄소 구조체를 양극에 적용한 리튬-황 이차전지의 초기 방전 실험 결과를 나타낸 그래프이다.
도 6a 및 6b는 실시예 8에서 제조된 다공성 탄소 구조체를 양극에 적용한 리튬-황 이차전지의 장기 방전 실험 결과를 나타낸 그래프이다.1 is a schematic diagram showing a manufacturing process of a metal organic skeleton and a porous carbon structure according to an embodiment.
FIG. 2 is a SEM (Scanning Electron Microscopy) photograph of a metal organic skeleton prepared in Examples 1, 4, 6, 7 and 8, respectively.
3A and 3B are graphs showing the nitrogen adsorption/desorption isotherms and pore size distribution for the porous carbon structures prepared in Examples 5 and 8 and Comparative Example 1, respectively.
4 is an XRD (X-Ray Diffraction) graph for a metal organic skeleton and a porous carbon structure prepared in Examples 3,4,5,6,7,8.
5 is a graph showing the results of an initial discharge experiment of a lithium-sulfur secondary battery in which the porous carbon structures each prepared in Examples 5 and 8 and Comparative Example 1 were applied to a positive electrode.
6A and 6B are graphs showing results of a long-term discharge experiment of a lithium-sulfur secondary battery in which the porous carbon structure prepared in Example 8 was applied to a positive electrode.
이하, 본 발명에 대한 이해를 돕기 위하여 본 발명을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail to aid understanding of the present invention.
본 명세서 및 청구범위에서 사용된 용어나 단어는 통상적이거나 사전적인 의미로 한정해서 해석되어서는 아니 되며, 발명자는 그 자신의 발명을 가장 최선의 방법으로 설명하기 위해 용어의 개념을 적절하게 정의할 수 있다는 원칙에 입각하여 본 발명의 기술적 사상에 부합하는 의미와 개념으로 해석되어야만 한다.The terms or words used in the specification and claims should not be construed as being limited to their usual or dictionary meanings, and the inventor may appropriately define the concept of terms in order to describe his own invention in the best way. It should be interpreted as a meaning and concept consistent with the technical idea of the present invention based on the principle that there is.
금속 유기 골격체Metal organic skeleton
본 발명은 판상형의 형태를 가지며, 아연; 및 유기 리간드;를 포함하는 금속 유기 골격체(Metal Organic Frameworks, MOF)에 관한 것이다.The present invention has a plate shape, zinc; And it relates to a metal organic framework (Metal Organic Frameworks, MOF) comprising an organic ligand.
상기 금속 유기 골격체는 판상형이라는 형태상의 특징으로 인하여, 종래 정육면체 형태의 금속 유기 골격체에 비하여 반응 물질이 잘 이동할 수 있어, 리튬 이차전지와 같은 전지의 전극 물질로 적용시 반응성을 개선하여 에너지 밀도를 향상시킬 수 있다.Due to the feature of the plate-like shape, the reactant material can move better than the conventional metal-organic skeleton in the form of a regular cube, so when applied as an electrode material of a battery such as a lithium secondary battery, the reactivity is improved and energy density Can improve.
본 발명에 있어서, 상기 아연과 유기 리간드의 몰 비율(Molar ratio)은 1:3 내지 1:6, 바람직하게는 1:4 내지 1:5일 수 있다. 상기 아연에 대한 유기 리간드의 몰 비율이 3 미만이면 금속 유기 골격체의 형상이 판상형으로 제조될 수 없거나, 낮은 수율을 가지거나, 원치 않는 부산물을 생성할 수 있고, 6 초과이면 역시 금속 유기 골격체의 형상이 판상형으로 제조될 수 없거나 낮은 결정성을 가질 수 있다. In the present invention, the molar ratio of the zinc and the organic ligand may be 1:3 to 1:6, preferably 1:4 to 1:5. If the molar ratio of the organic ligand to zinc is less than 3, the shape of the metal organic skeleton cannot be prepared in a plate shape, has a low yield, or may generate unwanted by-products. The shape of may not be manufactured in a plate shape or may have low crystallinity.
상기 금속 유기 골격체에 포함된 유기 리간드는, 제조 과정에서 사용된 유기 리간드 전구체가 금속에 배위 혹은 공유 결합을 통해 연결되어 있는 것으로, 상기 유기 리간드 전구체는 벤젠-1,4-디카르복실산(benzene-1,4-dicarboxylic acid), 벤젠-1,3,5-트리카르복실산(benzene-1,3,5-tricarboxylic acid), 2-메틸이미다졸(2-methylimidazole), 에탄디오산(ethanedioic acid), 프로판디오산(propanedioic acid), 부탄디오산(butanedioic acid), 펜탄디오산(pentanedioic acid), o-프탈산(o-phthalic acid), m-프탈산(m-phthalic acid), p-프탈산(p-phthalic acid), 2-히드록시-1,2,3-프로판트리카르복실산(2-hydroxy-1,2,3-propanetricarboxylic acid), 1H-1,2,3-트리아졸(1H-1,2,3-triazole), 1H-1,2,4-트리아졸(1H-1,2,4-triazole) 및 3,4-디히드록시-3-사이클로부텐-1,2-디온(3,4-dihydroxy-3-cyclobutene-1,2-dione)로 이루어진 군에서 선택되는 1종 이상일 수 있다.The organic ligand included in the metal organic framework is that the organic ligand precursor used in the manufacturing process is connected to the metal through coordination or covalent bonds, and the organic ligand precursor is benzene-1,4-dicarboxylic acid ( benzene-1,4-dicarboxylic acid), benzene-1,3,5-tricarboxylic acid, 2-methylimidazole, ethanedioic acid (ethanedioic acid), propanedioic acid, butanedioic acid, pentanedioic acid, o-phthalic acid, m-phthalic acid, p -Phthalic acid (p-phthalic acid), 2-hydroxy-1,2,3-propanetricarboxylic acid (2-hydroxy-1,2,3-propanetricarboxylic acid), 1H-1,2,3-triazole (1H-1,2,3-triazole), 1H-1,2,4-triazole (1H-1,2,4-triazole) and 3,4-dihydroxy-3-cyclobutene-1,2 -It may be one or more selected from the group consisting of dione (3,4-dihydroxy-3-cyclobutene-1,2-dione).
금속 유기 골격체의 제조방법Method for producing metal organic skeleton
본 발명은 또한, 상술한 바와 같은 금속 유기 골격체의 제조방법에 관한 것으로, (S1) 아연 전구체와 유기 리간드의 전구체를 유기 용매와 수계 용매의 혼합 용매에 용해시켜 혼합 용액을 제조하는 단계; (S2) 상기 혼합 용액을 가열하는 단계; 및 (S3) 상기 가열된 혼합 용액에서 상층액을 버린 후, 합성된 금속 유기 골격체를 세척하는 단계;를 포함할 수 있다.The present invention also relates to a method for producing a metal organic skeleton as described above, comprising: (S1) dissolving a zinc precursor and a precursor of an organic ligand in a mixed solvent of an organic solvent and an aqueous solvent to prepare a mixed solution; (S2) heating the mixed solution; And (S3) after discarding the supernatant from the heated mixed solution, washing the synthesized metal organic skeleton; may include.
이하, 본 발명에 따른 금속 유기 골격체의 제조방법을 각 단계별로 보다 상세히 설명한다.Hereinafter, a method for producing a metal organic skeleton according to the present invention will be described in more detail for each step.
(S1)단계Step (S1)
(S1) 단계에서는, 아연 전구체와 유기 리간드의 전구체를 유기 용매와 수계 용매의 혼합 용매에 용해시켜 혼합 용액을 제조할 수 있다.In step (S1), a mixed solution may be prepared by dissolving a zinc precursor and a precursor of an organic ligand in a mixed solvent of an organic solvent and an aqueous solvent.
본 발명에 있어서, 상기 아연 전구체는 아연을 포함하는 질산염(nitrate), 암모늄염(ammonium salt), 황산염(sulfate), 할로젠화물(halide), 옥살레이트염(oxalate), 아세테이트염(acetate) 및 아세틸아세토네이트(acetylacetonate)로 이루어진 군에서 선택되는 1종 이상일 수 있다.In the present invention, the zinc precursor is nitrate, ammonium salt, sulfate, halide, oxalate, acetate, and acetyl containing zinc. It may be one or more selected from the group consisting of acetonate (acetylacetonate).
구체적으로, 상기 아연 전구체는 아연나이트레이트·6수화물 (Zn(NO3)2·6H2O), 아연아세테이트·2수화물 (Zn(CH3CO2)2·2H2O) 및 아연설페이트·6수화물(ZnSO4·6H2O)로 이루어진 군에서 선택되는 1종 이상일 수 있으며, 바람직하게는 아연나이트레이트·6수화물 (Zn(NO3)2·6H2O)일 수 있다.Specifically, the zinc precursor is zinc nitrate·hexahydrate (Zn(NO 3 ) 2 ·6H 2 O), zinc acetate·dihydrate (Zn(CH 3 CO 2 ) 2 ·2H 2 O) and zinc sulfate·6 It may be one or more selected from the group consisting of hydrates (ZnSO 4 ·6H 2 O), preferably zinc nitrate·hexahydrate (Zn(NO 3 ) 2 ·6H 2 O).
본 발명에 있어서, 상기 유기 리간드 전구체는 벤젠-1,4-디카르복실산(benzene-1,4-dicarboxylic acid), 벤젠-1,3,5-트리카르복실산(benzene-1,3,5-tricarboxylic acid), 2-메틸이미다졸(2-methylimidazole), 에탄디오산(ethanedioic acid), 프로판디오산(propanedioic acid), 부탄디오산(butanedioic acid), 펜탄디오산(pentanedioic acid), o-프탈산(o-phthalic acid), m-프탈산(m-phthalic acid), p-프탈산(p-phthalic acid), 2-히드록시-1,2,3-프로판트리카르복실산(2-hydroxy-1,2,3-propanetricarboxylic acid), 1H-1,2,3-트리아졸(1H-1,2,3-triazole), 1H-1,2,4-트리아졸(1H-1,2,4-triazole) 및 3,4-디히드록시-3-사이클로부텐-1,2-디온(3,4-dihydroxy-3-cyclobutene-1,2-dione)로 이루어진 군에서 선택되는 1종 이상일 수 있다. 바람직하게는, 상기 유기 리간드는 테레프탈산(benzene-1,4-dicarboxylic acid)일 수 있다.In the present invention, the organic ligand precursor is benzene-1,4-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid (benzene-1,3, 5-tricarboxylic acid), 2-methylimidazole, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, o-phthalic acid, m-phthalic acid, p-phthalic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid (2-hydroxy) -1,2,3-propanetricarboxylic acid), 1H-1,2,3-triazole (1H-1,2,3-triazole), 1H-1,2,4-triazole (1H-1,2, 4-triazole) and 3,4-dihydroxy-3-cyclobutene-1,2-dione (3,4-dihydroxy-3-cyclobutene-1,2-dione) can be at least one selected from the group consisting of have. Preferably, the organic ligand may be terephthalic acid (benzene-1,4-dicarboxylic acid).
본 발명에 있어서, 상기 아연 전구체와 유기 리간드 전구체의 몰 비율(Molar ratio)은 1:3 내지 1:6, 바람직하게는 1:4 내지 1:5일 수 있다. 상기 아연 전구체에 대한 유기 리간드 전구체의 몰 비율이 3 미만이면 금속 유기 골격체의 형상이 판상형으로 제조될 수 없거나, 낮은 수율을 가지거나, 원치 않는 부산물을 생성할 수 있고, 6 초과이면 역시 금속 유기 골격체의 형상이 판상형으로 제조될 수 없거나 낮은 결정성을 가질 수 있다. In the present invention, the molar ratio of the zinc precursor and the organic ligand precursor may be 1:3 to 1:6, preferably 1:4 to 1:5. If the molar ratio of the organic ligand precursor to the zinc precursor is less than 3, the shape of the metal organic skeleton cannot be prepared in a plate shape, has a low yield, or may generate unwanted by-products. The shape of the skeleton may not be manufactured in a plate shape or may have low crystallinity.
상기 아연 전구체; 및 상기 유기 리간드 전구체;를 상술한 바와 같은 몰 비율로 용매에 용해시켜 혼합 용액을 제조할 수 있다. The zinc precursor; And the organic ligand precursor; may be dissolved in a solvent in a molar ratio as described above to prepare a mixed solution.
상기 혼합 용액의 농도는 고형분 중량을 기준으로 1 내지 10%, 바람직하게는 2 내지 9%, 보다 바람직하게는 3 내지 8%일 수 있다. 상기 범위 미만이면 MOF가 형성될 수 없고, 상기 범위 초과이면 제조된 MOF의 비표면적과 기공율이 저하될 수 있다.The concentration of the mixed solution may be 1 to 10%, preferably 2 to 9%, and more preferably 3 to 8%, based on the weight of the solid content. If it is less than the above range, MOF cannot be formed, and if it exceeds the above range, the specific surface area and porosity of the prepared MOF may be lowered.
본 발명에 있어서, 상기 용매는 유기 용매와 수계 용매를 포함하는 혼합 용매일 수 있다.In the present invention, the solvent may be a mixed solvent including an organic solvent and an aqueous solvent.
상기 유기 용매와 수계 용매의 부피비는 4 내지 11 : 1, 바람직하게는 5 내지 10 : 1 일 수 있다. 상기 수계 용매에 대한 유기 용매에 대한 부피비가 4 미만이면 상기 금속 유기 골격체의 형상이 판상형으로 제조되지 않거나 수율이 매우 떨어지거나, 금속 유기 골격체가 제조되지 않을 수 있고, 11 초과이면 역시 금속 유기 골격체의 형상이 판상형으로 제조되지 않을 수 있다.The volume ratio of the organic solvent and the aqueous solvent may be 4 to 11: 1, preferably 5 to 10: 1. If the volume ratio of the organic solvent to the aqueous solvent is less than 4, the shape of the metal organic skeleton is not prepared in a plate shape or the yield is very low, or the metal organic skeleton may not be produced. The shape of the sieve may not be manufactured in a plate shape.
또한, 상기 유기 용매는 디메틸 카보네이트, 디메틸 포름아미드, N-메틸 포름아미드, 술폴란(테트라히드로티오펜-1,1-디옥사이드), 3-메틸술폴란, N-부틸 술폰, 디메틸 설폭사이드, 피로리디논(HEP), 디메틸피페리돈(DMPD), N-메틸 피롤리디논(NMP), N-메틸 아세트아미드, 디메틸 아세트아미드(DMAc), 디메틸포름아미드(DMF), 디에틸아세트아마이드(DEAc) 디프로필아세트 아마이드(DPAc), 에탄올, 프로판올, 부탄올, 헥산올, 에틸렌글리콜, 테트라클로로에틸렌, 프로필렌글리콜, 톨루엔, 트르펜틴, 메틸 아세테이트, 에틸 아세테이트, 페트롤 에테르, 아세톤, 크레졸 및 글리세롤로 이루어진 군에서 선택된 1종 이상일 수 있고, 바람직하게는 디메틸포름아미드(DMF)일 수 있다.In addition, the organic solvent is dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl sulfone, dimethyl sulfoxide, pyro Lidinone (HEP), dimethylpiperidone (DMPD), N-methyl pyrrolidinone (NMP), N-methyl acetamide, dimethyl acetamide (DMAc), dimethylformamide (DMF), diethylacetamide (DEAc) In the group consisting of dipropylacetamide (DPAc), ethanol, propanol, butanol, hexanol, ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentine, methyl acetate, ethyl acetate, petroleum ether, acetone, cresol and glycerol It may be one or more selected, preferably dimethylformamide (DMF).
또한, 상기 수계 용매는 물일 수 있다.In addition, the aqueous solvent may be water.
(S2) 단계Step (S2)
(S2) 단계에서는, 상기 혼합 용액을 가열하여 반응시킬 수 있다. In step (S2), the mixed solution may be heated to react.
상기 가열 시간은 20 내지 40 시간, 바람직하게는 20 내지 35 시간, 보다 바람직하게는 20 내지 30 시간일 수 있다. 상기 범위 미만이면 상기 혼합 용액의 반응이 충분히 진행되지 않아 MOF가 형성될 수 없고, 상기 범위 초과이면 반응이 과도하게 진행되어 형성된 MOF 비표면적과 기공률이 저하될 수 있다.The heating time may be 20 to 40 hours, preferably 20 to 35 hours, more preferably 20 to 30 hours. If it is less than the above range, the reaction of the mixed solution does not sufficiently proceed to form MOF, and if it exceeds the above range, the reaction proceeds excessively and the formed MOF specific surface area and porosity may decrease.
상기 가열 온도는 80 내지 150℃, 바람직하게는 90 내지 140℃, 보다 바람직하게는 100 내지 130℃일 수 있다. 상기 범위 미만이면 상기 혼합 용액의 반응이 충분히 진행되지 않아 MOF가 형성될 수 없고, 상기 범위 초과이면 반응이 과도하게 진행되어 형성된 MOF 비표면적과 기공률이 저하될 수 있다. 상기 (S2) 단계에서, MOF가 합성될 수 있다.The heating temperature may be 80 to 150°C, preferably 90 to 140°C, and more preferably 100 to 130°C. If it is less than the above range, the reaction of the mixed solution does not sufficiently proceed to form MOF, and if it exceeds the above range, the reaction proceeds excessively and the formed MOF specific surface area and porosity may decrease. In the step (S2), MOF may be synthesized.
(S3) 단계Step (S3)
(S3) 단계에서는, 상기 가열된 혼합 용액에서 상층액을 버린 후, 합성된 금속 유기 골격체를 세척할 수 있다. In step (S3), after discarding the supernatant from the heated mixed solution, the synthesized metal-organic skeleton may be washed.
이때 사용하는 세척제는 휘발성 용제라면 특별히 제한되지 않으며, 상기 휘발성 용제로는 메탄올, 에탄올, 프로판올, 부탄올, 펜탄올, 헥산올, 벤젠, 톨루엔, 에틸벤젠, 클로로벤젠, o-자일렌, m-자일렌, p-자일렌, 스타이렌, 이소프로필벤젠, 노르말프로필벤젠, 클로로톨루엔, 부틸벤젠, 디클로로벤젠, 디이소프로필벤젠, 니트로톨루엔, 펜탄, 헥산, 옥탄, 노난, 데칸, 데칼린, 운데칸, 도데칸, 트리데칸, 테트라데칸, 이소노난, 이소데칸, 이소운데칸, 이소도데칸, 이소트리데칸, 이소테트라데칸, 사이클로노난, 사이클로데칸, 사이클로운데칸, 사이클로도데칸, 사이클로트리데칸, 사이클로테트라데칸, 클로로포름, 디클로로메탄, 벤질아세테이트, 알릴헥사노에이트, 부틸부티레이트, 에틸아세테이트, 에틸부티레이트, 에틸헥사노에이트, 에틸시나노에이트, 에틸헵타노에이트, 에틸노나노에이트, 에틸펜타노에이트, 이소부틸아세테이트,이소부틸포르메이트, 이소아밀아세테이트, 이소프로필아세테이트, 메틸페닐아세테이트, 아세톤, 메틸에틸케톤, 메틸이소부틸케톤, 디에틸에테르, 디메톡시에탄, 디메톡시메탄, 디옥산, 테트라하이드로퓨란, 안이솔, 크라운에테르, 모노- 및 폴리에틸렌글리콜로 이루어진 군에서 선택되는 1종 이상일 수 있다. 바람직하게는, 상기 휘발성 용제는 클로로포름일 수 있다.The detergent used at this time is not particularly limited as long as it is a volatile solvent, and the volatile solvents include methanol, ethanol, propanol, butanol, pentanol, hexanol, benzene, toluene, ethylbenzene, chlorobenzene, o-xylene, m-xyl Ene, p-xylene, styrene, isopropylbenzene, normalpropylbenzene, chlorotoluene, butylbenzene, dichlorobenzene, diisopropylbenzene, nitrotoluene, pentane, hexane, octane, nonane, decane, decalin, undecane, Dodecane, tridecane, tetradecane, isononane, isodecane, isodecane, isododecane, isotridecane, isotetradecane, cyclononane, cyclodecane, cyclodecane, cyclododecane, cyclotridecane, cyclo Tetradecane, chloroform, dichloromethane, benzyl acetate, allylhexanoate, butyl butyrate, ethyl acetate, ethyl butyrate, ethyl hexanoate, ethyl cinanoate, ethyl heptanoate, ethyl nonanoate, ethyl pentanoate, iso Butyl acetate, isobutyl formate, isoamyl acetate, isopropyl acetate, methylphenyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, diethyl ether, dimethoxyethane, dimethoxymethane, dioxane, tetrahydrofuran, ani It may be one or more selected from the group consisting of sol, crown ether, mono- and polyethylene glycol. Preferably, the volatile solvent may be chloroform.
다공성 탄소 구조체Porous carbon structure
본 발명은 또한, 상기 금속 유기 골격체를 포함하는 다공성 탄소 구조체에 관한 것으로, 상기 금속 유기 골격체는 탄화된 금속 유기 골격체를 가리키는 것이다.The present invention also relates to a porous carbon structure including the metal organic skeleton, wherein the metal organic skeleton refers to a carbonized metal organic skeleton.
또한, 상기 다공성 탄소 구조체는 판상형으로서, 리튬 이차전지와 같은 전지의 전극 물질로 적용시 반응 물질이 이동이 쉬워, 반응성이 개선되고, 이로 인하여 전지의 에너지 효율을 향상시킬 수 있다. In addition, the porous carbon structure has a plate shape, and when applied as an electrode material of a battery such as a lithium secondary battery, the reactive material is easily moved, thereby improving reactivity, thereby improving energy efficiency of the battery.
다공성 탄소 구조체의 제조방법Method of manufacturing porous carbon structure
본 발명은 또한, 다공성 탄소 구조체의 제조방법에 관한 것으로, 상기 판상형 금속 유기 골격체를 열처리하여 탄화시키는 단계를 포함할 수 있다.The present invention also relates to a method of manufacturing a porous carbon structure, and may include the step of heat-treating the plate-shaped metal organic framework to carbonize it.
상기 열처리는 불활성 분위기 하에서 실시하는 것일 수 있다.The heat treatment may be performed under an inert atmosphere.
상기 불활성 분위기는 질소 가스, 아르곤 가스, 헬륨 가스, 크립톤 가스 또는 크세논 가스에 의해 형성되는 것일 수 있으며, 바람직하게는 질소 가스에 의해 형성될 수 있다.The inert atmosphere may be formed by nitrogen gas, argon gas, helium gas, krypton gas or xenon gas, and preferably may be formed by nitrogen gas.
상기 열처리 온도는 500 내지 1500℃, 바람직하게는 600 내지 1400℃, 보다 바람직하게는 700 내지 1300℃일 수 있다. 상기 범위 미만이면 탄화가 충분히 되지 않아 다공성 탄소 구조체를 얻을 수 없고, 상기 범위 초과이면 제조되는 다공성 탄소 구조체의 물성이 저하될 수 있다.The heat treatment temperature may be 500 to 1500 °C, preferably 600 to 1400 °C, more preferably 700 to 1300 °C. If it is less than the above range, carbonization is not sufficiently performed to obtain a porous carbon structure, and if it exceeds the above range, physical properties of the produced porous carbon structure may be deteriorated.
상기 열처리 시간은 3 내지 10시간, 바람직하게는 4 내지 9시간, 보다 바람직하게는 5 내지 8 시간일 수 있다. 상기 범위 미만이면 탄화가 충분히 되지 않아 다공성 탄소 구조체를 얻을 수 없고, 상기 범위 초과이면 다공성 탄소 구조체의 물성이 저하될 수 있다.The heat treatment time may be 3 to 10 hours, preferably 4 to 9 hours, more preferably 5 to 8 hours. If it is less than the above range, carbonization is not sufficiently performed to obtain a porous carbon structure, and if it exceeds the above range, physical properties of the porous carbon structure may be deteriorated.
리튬 이차전지Lithium secondary battery
본 발명은 또한, 전술한 바와 같은 다공성 탄소 구조체를 포함하는 리튬 이차전지에 관한 것이다. 이때, 상기 다공성 탄소 구조체는 바람직하게는 양극 활물질로 포함될 수 있다. The present invention also relates to a lithium secondary battery comprising the porous carbon structure as described above. In this case, the porous carbon structure may preferably be included as a positive electrode active material.
본 발명에 따른 리튬 이차전지는 양극, 음극, 이들 사이에 개재된 분리막 및 전해질을 포함할 수 있다.The lithium secondary battery according to the present invention may include a positive electrode, a negative electrode, a separator and an electrolyte interposed therebetween.
본 발명에 있어서, 상기 리튬 이차전지의 양극은 양극 집전체 및 상기 양극 집전체 상에 형성된 양극 활물질을 갖는 양극 합제층을 포함할 수 있다. In the present invention, the positive electrode of the lithium secondary battery may include a positive electrode current collector and a positive electrode mixture layer having a positive electrode active material formed on the positive electrode current collector.
상기 양극 활물질로는 리튬함유 전이금속 산화물이 바람직하게 사용될 수 있으며, 예를 들면 LiCoO2, LiNiO2, LiMnO2, LiMn2O4, Li(NiaCobMnc)O2(0<a<1, 0<b<1, 0<c<1, a+b+c=1), LiNi1 - yCoyO2, LiCo1 - yMnyO2, LiNi1 - yMnyO2(O≤y<1), Li(NiaCobMnc)O4(0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn2 - zNizO4, LiMn2 - zCozO4(0<z<2), LiCoPO4 및 LiFePO4로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 혼합물을 사용할 수 있다. 또한, 이러한 산화물(oxide) 외에 황화물(sulfide), 셀렌화물(selenide) 및 할로겐화물(halide) 등도 사용될 수 있다.Lithium-containing transition metal oxide may be preferably used as the positive electrode active material, for example, LiCoO 2 , LiNiO 2 , LiMnO 2 , LiMn 2 O 4 , Li(Ni a Co b Mn c )O 2 (0<a< 1, 0<b<1, 0<c<1, a+b+c=1), LiNi 1 - y Co y O 2 , LiCo 1 - y Mn y O 2 , LiNi 1 - y Mn y O 2 ( O≤y<1), Li(Ni a Co b Mn c )O 4 (0<a<2, 0<b<2, 0<c<2, a+b+c=2), LiMn 2 - z Ni z O 4, LiMn 2 - z Co z O 4 (0 <z <2), LiCoPO may be used any one or a mixture of two or more of these four and is selected from the group consisting of LiFePO 4. In addition, in addition to these oxides, sulfide, selenide, and halide may be used.
또한, 상기 양극 집전체는 당해 전지에 화학적 변화를 유발하지 않으면서 높은 도전성을 가지는 것이라면 특별히 제한되지 않으며, 예를 들면 스테인리스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 또는 알루미늄이나 스테인리스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면 처리한 것 등이 사용될 수 있다. 이때, 상기 양극 집전체는 양극 활물질과의 접착력을 높일 수도 있도록, 표면에 미세한 요철이 형성된 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태를 사용할 수 있다.In addition, the positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes to the battery, for example, stainless steel, aluminum, nickel, titanium, calcined carbon, or on the surface of aluminum or stainless steel. Carbon, nickel, titanium, silver or the like surface-treated may be used. In this case, the positive electrode current collector may be in various forms such as a film, sheet, foil, net, porous material, foam, non-woven fabric having fine irregularities formed on the surface so as to increase adhesion to the positive electrode active material.
본 발명에 있어서, 상기 리튬 이차전지의 음극은 음극 집전체 및 상기 음극 집전체 상에 형성된 음극 활물질을 갖는 음극 합제층을 포함할 수 있다. In the present invention, the negative electrode of the lithium secondary battery may include a negative electrode current collector and a negative electrode mixture layer having a negative active material formed on the negative electrode current collector.
상기 음극 활물질로는 통상적으로 리튬이온이 흡장 및 방출될 수 있는 탄소재, 리튬금속, 규소 또는 주석 등을 사용할 수 있다. 바람직하게는 탄소재를 사용할 수 있는데, 탄소재로는 저결정 탄소 및 고결정성 탄소 등이 모두 사용될 수 있다. 저결정성 탄소로는 연화탄소(soft carbon) 및 경화탄소(hard carbon)가 대표적이며, 고결정성 탄소로는 천연 흑연, 키시흑연(Kish graphite), 열분해 탄소(pyrolytic carbon), 액정 피치계 탄소섬유(mesophase pitch based carbon fiber), 탄소 미소구체(meso-carbon microbeads), 액정피치(Mesophase pitches) 및 석유와 석탄계 코크스(petroleum or coal tar pitch derived cokes) 등의 고온 소성탄소가 대표적이다. 이때 음극은 결착제를 포함할 수 있으며, 결착제로는 비닐리덴플루오라이드-헥사플루오로프로필렌 코폴리머(PVDF-co-HFP), 폴리비닐리덴플루오라이드(polyvinylidenefluoride), 폴리아크릴로니트릴(polyacrylonitrile), 폴리메틸메타크릴레이트(polymethylmethacrylate) 등, 다양한 종류의 바인더 고분자가 사용될 수 있다.As the negative active material, a carbon material, lithium metal, silicon, tin, or the like, through which lithium ions can be inserted and released, may be used. Preferably, a carbon material may be used, and both low crystalline carbon and high crystalline carbon may be used as the carbon material. As low crystalline carbon, soft carbon and hard carbon are typical, and high crystalline carbon is natural graphite, kish graphite, pyrolytic carbon, liquid crystal pitch-based carbon fiber (mesophase pitch based carbon fiber), meso-carbon microbeads, mesophase pitches, and high-temperature calcined carbons such as petroleum or coal tar pitch derived cokes are typical. At this time, the negative electrode may include a binder, and as the binder, vinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidenefluoride, polyacrylonitrile, Various types of binder polymers, such as polymethylmethacrylate, may be used.
또한, 상기 음극 집전체는 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되지 않으며, 예를 들면 구리, 스테인리스 스틸, 알루미늄, 니켈, 티탄, 소성 탄소, 구리나 스테인리스 스틸의 표면에 카본, 니켈, 티탄, 은 등으로 표면 처리한 것, 알루미늄-카드뮴 합금 등이 사용될 수 있다. 또한, 상기 음극 집전체는 양극 집전체와 마찬가지로, 표면에 미세한 요철이 형성된 필름, 시트, 호일, 네트, 다공질체, 발포체, 부직포체 등 다양한 형태가 사용될 수 있다.In addition, the negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical changes to the battery, for example, copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel. Surface treatment with carbon, nickel, titanium, silver, or the like, aluminum-cadmium alloy, or the like may be used. In addition, the negative electrode current collector, like the positive electrode current collector, may be used in various forms such as a film, sheet, foil, net, porous body, foam, nonwoven fabric having fine irregularities on the surface thereof.
이때, 상기 양극 합제층 또는 음극 합제층은 바인더 수지, 도전재, 충진제 및 기타 첨가제 등을 추가로 포함할 수 있다.In this case, the positive electrode mixture layer or the negative electrode mixture layer may further include a binder resin, a conductive material, a filler, and other additives.
상기 바인더 수지는 전극 활물질과 도전재의 결합과 집전체에 대한 결합을 위해 사용한다. 이러한 바인더 수지의 예로는, 폴리비닐리덴플로라이드(PVDF), 폴리비닐알코올, 카르복시메틸셀룰로우즈(CMC), 전분, 하이드록시프로필셀룰로우즈, 재생 셀룰로우즈, 폴리비닐피롤리돈, 테트라플루오로에틸렌, 폴리에틸렌, 폴리프로필렌, 에틸렌-프로필렌-디엔 폴리머(EPDM), 술폰화-EPDM, 스티렌-부타디엔 고무, 불소 고무, 이들의 다양한 공중합체 등을 들 수 있다.The binder resin is used for bonding of an electrode active material and a conductive material and bonding to a current collector. Examples of such binder resins include polyvinylidene fluoride (PVDF), polyvinyl alcohol, carboxymethylcellulose (CMC), starch, hydroxypropylcellulose, regenerated cellulose, polyvinylpyrrolidone, tetra Fluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene polymer (EPDM), sulfonated-EPDM, styrene-butadiene rubber, fluorine rubber, and various copolymers thereof.
상기 도전재는 전극 활물질의 도전성을 더욱 향상시키기 위해 사용한다. 이러한 도전재는 당해 전지에 화학적 변화를 유발하지 않으면서 도전성을 가진 것이라면 특별히 제한되는 것은 아니며, 예를 들어, 천연 흑연이나 인조 흑연 등의 흑연; 카본블랙, 아세틸렌 블랙, 케첸 블랙, 채널 블랙, 퍼니스 블랙, 램프 블랙, 서머 블랙 등의 카본블랙; 탄소 섬유나 금속 섬유 등의 도전성 섬유; 불화 카본, 알루미늄, 니켈 분말 등의 금속 분말; 산화아연, 티탄산 칼륨 등의 도전성 휘스커; 산화티탄 등의 도전성 금속 산화물; 폴리페닐렌 유도체 등이 사용될 수 있다.The conductive material is used to further improve the conductivity of the electrode active material. Such a conductive material is not particularly limited as long as it has conductivity without causing a chemical change in the battery, and examples thereof include graphite such as natural graphite or artificial graphite; Carbon blacks such as carbon black, acetylene black, Ketjen black, channel black, furnace black, lamp black, and thermal black; Conductive fibers such as carbon fibers and metal fibers; Metal powders such as carbon fluoride, aluminum, and nickel powder; Conductive whiskers such as zinc oxide and potassium titanate; Conductive metal oxides such as titanium oxide; Polyphenylene derivatives and the like can be used.
상기 충진제는 전극의 팽창을 억제하는 성분으로서 선택적으로 사용되며, 당해 전지에 화학적 변화를 유발하지 않으면서 섬유상 재료라면 특별히 제한되는 것은 아니며, 예를 들어, 폴리에틸렌, 폴리프로필렌 등의 올리핀계 중합체; 유리섬유, 탄소섬유 등의 섬유상 물질이 사용된다.The filler is selectively used as a component that suppresses the expansion of the electrode, and is not particularly limited as long as it is a fibrous material without causing chemical changes to the battery, and examples thereof include olefin-based polymers such as polyethylene and polypropylene; Fibrous materials such as glass fiber and carbon fiber are used.
본 발명에 있어서, 상기 분리막은 다공성 기재로 이루어질 수 있으며, 상기 다공성 기재는, 통상적으로 전기화학소자에 사용되는 다공성 기재라면 모두 사용이 가능하고, 예를 들면 폴리올레핀계 다공성 막(membrane) 또는 부직포를 사용할 수 있으나, 이에 특별히 한정되는 것은 아니다.In the present invention, the separator may be made of a porous substrate, and the porous substrate may be used as long as it is a porous substrate commonly used in an electrochemical device, for example, a polyolefin-based porous membrane or a nonwoven fabric. It can be used, but is not particularly limited thereto.
상기 폴리올레핀계 다공성 막의 예로는, 고밀도 폴리에틸렌, 선형 저밀도 폴리에틸렌, 저밀도 폴리에틸렌, 초고분자량 폴리에틸렌과 같은 폴리에틸렌, 폴리프로필렌, 폴리부틸렌, 폴리펜텐 등의 폴리올레핀계 고분자를 각각 단독으로 또는 이들을 혼합한 고분자로 형성한 막(membrane)을 들 수 있다.Examples of the polyolefin-based porous membrane include polyolefin-based polymers such as high-density polyethylene, linear low-density polyethylene, low-density polyethylene, and ultra-high molecular weight polyethylene, polyolefin-based polymers such as polypropylene, polybutylene, and polypentene, respectively, or a mixture of them. There is one membrane.
상기 부직포로는 폴리올레핀계 부직포 외에 예를 들어, 폴리에틸렌 테레프탈레이트 (polyethyleneterephthalate), 폴리부틸렌 테레프탈레이트 (polybutyleneterephthalate), 폴리에스테르 (polyester), 폴리아세탈 (polyacetal), 폴리아미드 (polyamide), 폴리카보네이트 (polycarbonate), 폴리이미드 (polyimide), 폴리에테르에테르케톤 (polyetheretherketone), 폴리에테르설폰 (polyethersulfone), 폴리페닐렌 옥사이드 (polyphenyleneoxide), 폴리페닐렌 설파이드 (polyphenylenesulfide) 및 폴리에틸렌 나프탈렌 (polyethylenenaphthalene) 등을 각각 단독으로 또는 이들을 혼합한 고분자로 형성한 부직포를 들 수 있다. 부직포의 구조는 장섬유로 구성된 스폰본드 부직포 또는 멜트 블로운 부직포일 수 있다.As the nonwoven fabric, in addition to the polyolefin nonwoven fabric, for example, polyethylene terephthalate, polybutyleneterephthalate, polyester, polyacetal, polyamide, polycarbonate ), polyimide, polyetheretherketone, polyethersulfone, polyphenyleneoxide, polyphenylenesulfide, and polyethylenenaphthalene, respectively, alone or Nonwoven fabrics formed of polymers obtained by mixing them are exemplified. The structure of the nonwoven fabric may be a spunbond nonwoven fabric composed of long fibers or a melt blown nonwoven fabric.
상기 다공성 기재의 두께는 특별히 제한되지 않으나, 1 ㎛ 내지 100 ㎛, 또는 5 ㎛ 내지 50 ㎛이다.The thickness of the porous substrate is not particularly limited, but is 1 µm to 100 µm, or 5 µm to 50 µm.
다공성 기재에 존재하는 기공의 크기 및 기공도 역시 특별히 제한되지 않으나 각각 0.001㎛ 내지 50㎛ 및 10% 내지 95%일 수 있다.The size and porosity of the pores present in the porous substrate are also not particularly limited, but may be 0.001 μm to 50 μm and 10% to 95%, respectively.
본 발명에 있어서, 상기 전해액은 비수 전해액일 수 있으며, 상기 비수 전해액에 포함되는 전해질 염은 리튬염이다. 상기 리튬염은 리튬 이차전지용 전해액에 통상적으로 사용되는 것들 것 제한 없이 사용될 수 있다. 예를 들어 상기 리튬염은 LiFSI, LiPF6, LiCl, LiBr, LiI, LiClO4, LiBF4, LiB10Cl10, LiPF6, LiCF3SO3, LiCF3CO2, LiAsF6, LiSbF6, LiPF6, LiAlCl4, CH3SO3Li, CF3SO3Li, (CF3SO2)2NLi, 클로로 보란 리튬 및 4-페닐 붕산 리튬으로 이루어진 군에서 선택되는 1종 이상일 수 있다.In the present invention, the electrolyte may be a nonaqueous electrolyte, and the electrolyte salt contained in the nonaqueous electrolyte is a lithium salt. The lithium salts may be used without limitation, those commonly used in an electrolyte solution for a lithium secondary battery. For example, the lithium salt is LiFSI, LiPF 6 , LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiSbF 6 , LiPF 6 , LiAlCl 4 , CH 3 SO 3 Li, CF 3 SO 3 Li, (CF 3 SO 2 ) 2 NLi, it may be one or more selected from the group consisting of lithium chloroborane and lithium 4-phenyl borate.
전술한 비수 전해액에 포함되는 유기용매로는 리튬 이차전지용 전해액에 통상적으로 사용되는 것들을 제한 없이 사용할 수 있으며, 예를 들면 에테르, 에스테르, 아미드, 선형 카보네이트, 환형 카보네이트 등을 각각 단독으로 또는 2종 이상 혼합하여 사용할 수 있다. 그 중에서 대표적으로는 환형 카보네이트, 선형 카보네이트, 또는 이들의 슬러리인 카보네이트 화합물을 포함할 수 있다.As organic solvents included in the above-described non-aqueous electrolyte, those commonly used in electrolytes for lithium secondary batteries can be used without limitation, and for example, ethers, esters, amides, linear carbonates, cyclic carbonates, etc. can be used alone or in two or more types. It can be mixed and used. Among them, representatively, a cyclic carbonate, a linear carbonate, or a carbonate compound that is a slurry thereof may be included.
상기 환형 카보네이트 화합물의 구체적인 예로는 에틸렌 카보네이트(ethylene carbonate, EC), 프로필렌 카보네이트(propylene carbonate, PC), 1,2-부틸렌 카보네이트, 2,3-부틸렌 카보네이트, 1,2-펜틸렌 카보네이트, 2,3-펜틸렌 카보네이트, 비닐렌 카보네이트, 비닐에틸렌 카보네이트 및 이들의 할로겐화물로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 슬러리가 있다. 이들의 할로겐화물로는 예를 들면, 플루오로에틸렌 카보네이트(fluoroethylene carbonate, FEC) 등이 있으며, 이에 한정되는 것은 아니다.Specific examples of the cyclic carbonate compound include ethylene carbonate (EC), propylene carbonate (PC), 1,2-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, Any one selected from the group consisting of 2,3-pentylene carbonate, vinylene carbonate, vinylethylene carbonate, and halides thereof, or two or more of these slurries. These halides include, for example, fluoroethylene carbonate (FEC), but are not limited thereto.
또한 상기 선형 카보네이트 화합물의 구체적인 예로는 디메틸 카보네이트(DMC), 디에틸 카보네이트(DEC), 디프로필 카보네이트, 에틸메틸 카보네이트(EMC), 메틸프로필 카보네이트 및 에틸프로필 카보네이트로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 슬러리 등이 대표적으로 사용될 수 있으나, 이에 한정되는 것은 아니다. 특히, 상기 카보네이트계 유기용매 중 환형 카보네이트인 에틸렌 카보네이트 및 프로필렌 카보네이트는 고점도의 유기용매로서 유전율이 높아 전해질 내의 리튬염을 보다 더 잘 해리시킬 수 있으며, 이러한 환형 카보네이트에 디메틸 카보네이트 및 디에틸 카보네이트와 같은 저점도, 저유전율 선형 카보네이트를 적당한 비율로 혼합하여 사용하면 보다 높은 전기 전도율을 갖는 전해액을 만들 수 있다.In addition, specific examples of the linear carbonate compound include any one selected from the group consisting of dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate, ethylmethyl carbonate (EMC), methylpropyl carbonate, and ethylpropyl carbonate, or these Two or more types of slurries may be representatively used, but are not limited thereto. Particularly, among the carbonate-based organic solvents, ethylene carbonate and propylene carbonate, which are cyclic carbonates, are organic solvents of high viscosity and have high dielectric constants, so that lithium salts in the electrolyte can be more easily dissociated.These cyclic carbonates include dimethyl carbonate and diethyl carbonate. If a low viscosity, low dielectric constant linear carbonate is mixed in an appropriate ratio and used, an electrolyte solution having a higher electrical conductivity can be prepared.
또한, 상기 유기 용매 중 에테르로는 디메틸 에테르, 디에틸 에테르, 디프로필 에테르, 메틸에틸 에테르, 메틸프로필 에테르 및 에틸프로필 에테르로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 슬러리를 사용할 수 있으나, 이에 한정되는 것은 아니다.In addition, as the ether of the organic solvent, any one selected from the group consisting of dimethyl ether, diethyl ether, dipropyl ether, methylethyl ether, methylpropyl ether, and ethylpropyl ether, or two or more types of slurry may be used. , But is not limited thereto.
또한, 상기 유기 용매 중 에스테르로는 메틸 아세테이트, 에틸 아세테이트, 프로필 아세테이트, 메틸 프로피오네이트, 에틸 프로피오네이트, 프로필 프로피오네이트, γ-부티로락톤, γ-발레로락톤, γ-카프로락톤, σ-발레로락톤 및 ε-카프로락톤으로 이루어진 군에서 선택되는 어느 하나 또는 이들 중 2종 이상의 슬러리를 사용할 수 있으나, 이에 한정되는 것은 아니다.In addition, esters in the organic solvent include methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, γ-butyrolactone, γ-valerolactone, γ-caprolactone, Any one selected from the group consisting of σ-valerolactone and ε-caprolactone, or two or more types of slurry may be used, but is not limited thereto.
상기 비수 전해액의 주입은 최종 제품의 제조 공정 및 요구 물성에 따라, 전기화학소자의 제조 공정 중 적절한 단계에서 행해질 수 있다. 즉, 전기화학소자 조립 전 또는 전기화학소자 조립 최종 단계 등에서 적용될 수 있다.The injection of the non-aqueous electrolyte may be performed at an appropriate step in the manufacturing process of the electrochemical device, depending on the manufacturing process and required physical properties of the final product. That is, it can be applied before assembling the electrochemical device or at the final stage of assembling the electrochemical device.
본 발명에 따른 리튬 이차전지는, 일반적인 공정인 권취(winding) 이외에도 세퍼레이터와 전극의 적층(lamination, stack) 및 접음(folding) 공정이 가능하다.In the lithium secondary battery according to the present invention, in addition to winding, which is a general process, lamination, stacking, and folding of a separator and an electrode are possible.
그리고, 상기 전지케이스의 형상은 특별히 제한되지 않으며, 원통형, 적층형, 각형, 파우치(pouch)형 또는 코인(coin)형 등 다양한 형상으로 할 수 있다. 이들 전지의 구조와 제조 방법은 이 분야에 널리 알려져 있으므로 상세한 설명은 생략한다.Further, the shape of the battery case is not particularly limited, and may be in various shapes such as a cylindrical shape, a stacked type, a square shape, a pouch type, or a coin type. The structure and manufacturing method of these batteries are well known in this field, and thus detailed descriptions are omitted.
또한, 상기 리튬 이차전지는 사용하는 양극/음극 재질에 따라 리튬-황 이차전지, 리튬-공기 전지, 리튬-산화물 전지, 리튬 전고체 전지 등 다양한 전지로 분류가 가능하다.In addition, the lithium secondary battery can be classified into various batteries, such as lithium-sulfur secondary batteries, lithium-air batteries, lithium-oxide batteries, and lithium all-solid batteries, depending on the material of the positive electrode/cathode used.
본 발명은 또한, 상기 리튬 이차전지를 단위전지로 포함하는 전지모듈을 제공한다.The present invention also provides a battery module including the lithium secondary battery as a unit cell.
상기 전지모듈은 고온 안정성, 긴 사이클 특성 및 높은 용량 특성 등이 요구되는 중대형 디바이스의 전원으로 사용될 수 있다.The battery module can be used as a power source for medium and large-sized devices that require high temperature stability, long cycle characteristics, and high capacity characteristics.
상기 중대형 디바이스의 예로는 전지적 모터에 의해 동력을 받아 움직이는 파워 툴(power tool); 전기자동차(electric vehicle, EV), 하이브리드 전기자동차(hybrid electric vehicle, HEV), 플러그-인 하이브리드 전기자동차(plug-in hybrid electric vehicle, PHEV) 등을 포함하는 전기차; 전기 자전거(E-bike), 전기 스쿠터(E-scooter)를 포함하는 전기 이륜차; 전기 골프 카트(electric golf cart); 전력저장용 시스템 등을 들 수 있으나, 이에 한정되는 것은 아니다.Examples of the medium and large-sized devices include a power tool that is powered by an omniscient motor and moves; Electric vehicles including electric vehicles (EV), hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and the like; Electric two-wheeled vehicles including electric bicycles (E-bikes) and electric scooters (E-scooters); Electric golf cart; Power storage systems, etc., but are not limited thereto.
리튬-황 이차전지Lithium-sulfur secondary battery
본 발명은 따른 다공성 탄소 구조체는 리튬 이차전지 중에서도, 리튬-황 이차전지의 양극에 적용할 수 있다. 예컨대, 상기 다공성 탄소 구조체 내부에 양극 활물질이 담지되는 형태로 리튬-황 이차전지의 양극에 적용될 수 있다.The porous carbon structure according to the present invention can be applied to a positive electrode of a lithium-sulfur secondary battery, among lithium secondary batteries. For example, it may be applied to a positive electrode of a lithium-sulfur secondary battery in a form in which a positive electrode active material is supported inside the porous carbon structure.
이때, 상기 리튬-황 이차전지는 양극 활물질로서 황을 포함하는 전지일 수 있다. 구체적으로, 양극 활물질로서 황 원소(elemental sulfur, S8), 황 계열 화합물 또는 이들의 혼합물을 포함할 수 있다. 상기 황 계열 화합물은 구체적으로, Li2Sn(n≥1), 유기황 화합물 또는 탄소-황 폴리머((C2Sx)n: x=2.5 ~ 50, n≥2) 등일 수 있다. In this case, the lithium-sulfur secondary battery may be a battery containing sulfur as a positive electrode active material. Specifically, as the positive electrode active material, elemental sulfur (S8), a sulfur-based compound, or a mixture thereof may be included. Specifically, the sulfur-based compound may be Li 2 Sn (n≥1), an organosulfur compound or a carbon-sulfur polymer ((C 2 S x ) n : x=2.5 to 50, n≥2).
이들 황 물질의 경우, 단독으로는 전기 전도성이 없기 때문에 본 발명에 따른 다공성 탄소 구조체와 복합화하여 황-탄소 복합체의 형태로 리튬-황 이차전지의 양극에서 사용될 수 있다.Since these sulfur materials alone do not have electrical conductivity, they can be combined with the porous carbon structure according to the present invention and used in the positive electrode of a lithium-sulfur secondary battery in the form of a sulfur-carbon composite.
상기 다공성 탄소 구조체를 포함하는 황-탄소 복합체는 기공 내부까지 리튬 이온의 이동 경로를 확보함으로써 높은 이온 전도성을 나타낼 수 있고, 황 담지체의 역할을 하여 양극 활물질인 황과의 반응성을 높여 리튬-황 이차전지의 용량 및 수명 특성을 동시에 향상시킬 수 있다.The sulfur-carbon composite including the porous carbon structure can exhibit high ionic conductivity by securing a movement path of lithium ions to the inside of the pores, and acts as a sulfur carrier to increase reactivity with sulfur, which is a positive electrode active material. It is possible to improve the capacity and life characteristics of the secondary battery at the same time.
이하 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변경 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.Hereinafter, preferred embodiments are presented to aid the understanding of the present invention, but the following examples are only illustrative of the present invention, and it is obvious to those skilled in the art that various changes and modifications are possible within the scope and spirit of the present invention. It is natural that changes and modifications fall within the scope of the appended claims.
실시예 1 내지 12Examples 1 to 12
도 1은 실시예에 따른 금속 유기 골격체 및 다공성 탄소 구조체의 제조 공정을 나타낸 모식도이고, 표 1은 금속 유기 골격체 제조시 사용되는 아연 전구체와 유기 리간드 전구체의 몰 비율 및 혼합 용매에 포함된 유기 용매와 수계 용매의 부피비를 나타낸 것이다.1 is a schematic diagram showing a manufacturing process of a metal organic skeleton and a porous carbon structure according to an embodiment, and Table 1 is a molar ratio of a zinc precursor and an organic ligand precursor used in manufacturing a metal organic skeleton, and organic substances contained in a mixed solvent. It shows the volume ratio of the solvent and the aqueous solvent.
(Zn : Ligand)Molar ratio of zinc precursor and organic ligand precursor
(Zn: Ligand)
(DMF : water)Volume ratio of organic solvent and aqueous solvent contained in the mixed solvent
(DMF: water)
이하, 도 1을 참고하여, 상기 표 1에 기재된 바에 따라, 용매열합성법(solvothermal)에 의해 금속 유기 골격체 및 다공성 탄소 구조체를 제조하였다.Hereinafter, referring to FIG. 1, as described in Table 1, a metal organic skeleton and a porous carbon structure were prepared by a solvent thermal synthesis method (solvothermal).
(1)금속 유기 골격체 제조(1) Preparation of metal organic skeleton
아연 전구체 및 유기 리간드 전구체로서 각각 아연나이트레이트·6수화물 (Zn(NO3)2·6H2O) 및 벤젠-1,4-디카르복실산(benzene-1,4-dicarboxylic acid)을 사용하였다.Zinc nitrate·hexahydrate (Zn(NO 3 ) 2 ·6H 2 O) and benzene-1,4-dicarboxylic acid were used as a zinc precursor and an organic ligand precursor, respectively. .
혼합 용매는 유기 용매 및 수계 용매로서 각각 디메틸포름아미드(DMF)와 탈이온수(D.I. water)를 혼합하여 사용하였다.The mixed solvent was used by mixing dimethylformamide (DMF) and deionized water (D.I. water) as an organic solvent and an aqueous solvent, respectively.
상기 아연 전구체 및 유기 리간드 전구체를 상기 혼합 용매에 용해시켜 혼합 용액을 제조하였다.The zinc precursor and the organic ligand precursor were dissolved in the mixed solvent to prepare a mixed solution.
상기 혼합 용액을 오토클레이브(autoclave)에 넣고 120℃에서 24시간 동안 가열하여 반응시켜, 금속 유기 골격체를 합성하였다.The mixed solution was put in an autoclave and heated at 120° C. for 24 hours to react, thereby synthesizing a metal organic skeleton.
상기 금속 유기 골격체가 합성되어 포함된 혼합 용액에서 상층액을 버린 후, 상기 합성된 금속 유기 골격체를 DMF와 클로로포름을 사용해 세척하고, 진공상태에서 건조시켜, 금속 유기 골격체(MOF)를 제조하였다After discarding the supernatant from the mixed solution containing the synthesized metal organic skeleton, the synthesized metal organic skeleton was washed with DMF and chloroform, and dried in a vacuum to prepare a metal organic skeleton (MOF).
(2)다공성 탄소 구조체 제조(2) Porous carbon structure manufacturing
상기 (1)에서 제조된 금속 유기 골격체를, Ar 분위기 하에서, 1000℃ 온도 및 6시간 동안 탄화시켜, 다공성 탄소 구조체를 제조하였다. The organic metal skeleton prepared in (1) above was carbonized at a temperature of 1000° C. for 6 hours in an Ar atmosphere to prepare a porous carbon structure.
비교예 1Comparative Example 1
혼합 용매 대신 무수 디메틸포름아미드(anhydrous DMF, DMF:water = 100:0)를 사용한 것을 제외하고, 실시예 1과 동일한 방법으로 금속 유기 골격체 및 다공성 탄소 구조체를 제조하였다. A metal organic framework and a porous carbon structure were prepared in the same manner as in Example 1, except that anhydrous dimethylformamide (anhydrous DMF, DMF:water = 100:0) was used instead of the mixed solvent.
실험예 1: 금속 유기 골격체 및 다공성 탄소 구조체의 형태 확인Experimental Example 1: Confirmation of the shape of the metal organic skeleton and the porous carbon structure
(1-1)SEM 분석(1-1) SEM analysis
도 2는 실시예 1, 4, 6, 7 및 8에서 각각 제조된 금속 유기 골격체(에 대한 SEM(Scanning Electron Microscopy) 사진이다.FIG. 2 is a SEM (Scanning Electron Microscopy) photograph of a metal organic skeleton prepared in Examples 1, 4, 6, 7 and 8, respectively.
도 2를 참조하면, 실시예 1, 4, 6, 7 및 8에서 제조된 금속 유기 골격체는 판상형인 것을 알 수 있다.Referring to FIG. 2, it can be seen that the metal organic skeletons prepared in Examples 1, 4, 6, 7 and 8 have a plate shape.
(1-2)비표면적 및 기공 크기 분석(1-2) Specific surface area and pore size analysis
비표면적 및 기공 크기분포는 BET(Brunauer-Emmett-Teller; BET)법 및 BJH(Barrett-Joyner-Halenda) 분석법으로 측정하였다. 예를 들어, 기공분포 측정기(Porosimetry analyzer; Bell Japan Inc, Belsorp-II mini)를 사용하여 질소 가스 흡착 유통법에 의해 BET 6 점법으로 측정할 수 있다.The specific surface area and pore size distribution were measured by BET (Brunauer-Emmett-Teller; BET) method and BJH (Barrett-Joyner-Halenda) analysis method. For example, it can be measured by the BET 6-point method by the nitrogen gas adsorption flow method using a pore distribution analyzer (Porosimetry analyzer; Bell Japan Inc, Belsorp-II mini).
도 3a 및 3b는 각각 실시예 5, 8 및 비교예 1에서 제조된 다공성 탄소 구조체에 대한 질소 흡탈착 등온선(nitrogen adsorption/desorption isotherms) 및 기공 크기분포를 나타낸 그래프이다. 3A and 3B are graphs showing the nitrogen adsorption/desorption isotherms and pore size distribution for the porous carbon structures prepared in Examples 5 and 8 and Comparative Example 1, respectively.
또한, 하기 표 2는 실시예에서 제조된 다공성 탄소 구조체의 비표면적(BET surface area) 및 기공 부피(pore volume)를 나타낸 것이다.In addition, Table 2 below shows the specific surface area (BET surface area) and pore volume (pore volume) of the porous carbon structure prepared in Example.
(㎡/g)BET surface area
(㎡/g)
(cc/g)Pore volume
(cc/g)
도 3a, 3b 및 표 2를 참조하면, 실시예 5 및 8의 판상형 다공성 탄소 구조체는 비교예 1에 비해 비표면적은 증가하고 기공 부피는 감소하는 것을 알 수 있다.3A, 3B, and Table 2, it can be seen that the plate-shaped porous carbon structures of Examples 5 and 8 have an increased specific surface area and a decreased pore volume compared to Comparative Example 1.
(1-3) 금속 유기 골격체의 결정 구조(1-3) Crystal structure of metal organic skeleton
도 4는 실시예 3,4,5,6,7,8에서 제조된 금속 유기 골격체 및 다공성 탄소 구조체에 대한 XRD (X-Ray Diffraction) 그래프이다.4 is an XRD (X-Ray Diffraction) graph for the metal organic skeleton and the porous carbon structure prepared in Examples 3,4,5,6,7,8.
도 4를 참조하면, 실시예 3,4,5,6,7,8에서 제조된 금속 유기 골격체는 피크가 관측되며, 피크에 해당하는 각도를 통해 격자면 간격 등의 결정성을 알 수 있으며, 산화 아연(Zinc Oxide)의 피크는 관찰되지 않았다. Referring to FIG. 4, peaks are observed in the metal-organic skeletons prepared in Examples 3,4,5,6,7,8, and crystallinity such as lattice spacing can be known through an angle corresponding to the peak. , No peak of zinc oxide was observed.
또한, 상기 금속 유기 골격체를 탄화시켜 제조된 다공성 탄소 구조체는 피크가 관측되지 않으며 이에 따라 격자 구조가 아님을 알 수 있고, 역시 산화 아연의 피크는 관찰되지 않았으며, 탄소 그래프의 경향을 나타낸 것을 알 수 있다.In addition, it can be seen that the porous carbon structure produced by carbonizing the metal-organic skeleton does not have a peak and thus is not a lattice structure. Also, a peak of zinc oxide was not observed, indicating a tendency of a carbon graph. Able to know.
실험예 2: XPS (X-ray photoelectron spectroscopy) 분석Experimental Example 2: XPS (X-ray photoelectron spectroscopy) analysis
실시예에서 제조된 다공성 탄소 구조체에 대해서 XPS (X-ray photoelectron spectroscopy) 분석을 실시하여, 각각의 다공성 탄소 구조체에 포함된 원소를 분석하였으며, 그 결과를 하기 표 3에 기재하였다.XPS (X-ray photoelectron spectroscopy) analysis was performed on the porous carbon structures prepared in Examples, and elements included in each porous carbon structure were analyzed, and the results are shown in Table 3 below.
상기 표 3 참조하면, 실시예 4,5,8에서 Zn 원자가 검출되지 않아 가열시 금속 성분이 대부분 제거된 것을 알 수 있다. 실시예 3,7에서는 미량의 Zn이 검출되었으나, 이는 탄화 과정에서 완전히 제거되지 못하였거나, 반응의 부산물, 예를 들어, 산화아연 등이 미량 잔여한 것일 수 있다.Referring to Table 3, it can be seen that in Examples 4, 5, and 8, since Zn atoms were not detected, most of the metal components were removed during heating. In Examples 3 and 7, a trace amount of Zn was detected, but this may not be completely removed during the carbonization process, or a trace amount of a by-product of the reaction, for example, zinc oxide, etc. may remain.
실험예Experimental example 3: 다공성 탄소 구조체에 의한 리튬-황 이차전지의 성능 개선 효과 분석 3: Analysis of the performance improvement effect of lithium-sulfur secondary battery by porous carbon structure
실시예 5,8 및 비교예 1에서 각각 제조된 다공성 탄소 구조체를 양극에 적용한 리튬-황 이차전지의 성능에 대한 실험을 실시하였다.Experiments were conducted on the performance of lithium-sulfur secondary batteries in which the porous carbon structures prepared in Examples 5 and 8 and Comparative Example 1 were applied to a positive electrode, respectively.
실험 조건으로서, 리튬 금속 음극, 황 로딩량이 60 중량%인 양극, 이들 사이에 개재된 폴리우레탄 분리막을 포함하는 전지에 전해액을 주입하여, 리튬-황 이차전지를 조립하였다. 이때, 양극에는 상기 실시예 5,8에서 각각 제조된 다공성 탄소 구조체, 도전재인 케첸 블랙 및 바인더(SBR/CMC)를 80:10:10의 중량비로 혼합한 혼합물이 포함되도록 하였고, 상기 전해액은 3wt% LiNO3, 1M LiTFSi 및 용매(DOL:DME=1:1(v/v))를 포함하는 것이다 (SBR: Styrene Butadiene Rubber, CMC: Carboxylmethyl Cellulose, DOL: Dioxolane, DME: Dimethoxyethane). As an experimental condition, an electrolyte was injected into a battery including a lithium metal negative electrode, a positive electrode having a sulfur loading of 60% by weight, and a polyurethane separator interposed therebetween to assemble a lithium-sulfur secondary battery. At this time, the cathode was made to contain a mixture of the porous carbon structure prepared in Examples 5 and 8, a conductive material, Ketjen Black, and a binder (SBR/CMC) in a weight ratio of 80:10:10, and the electrolyte solution was 3wt. % LiNO 3 , 1M LiTFSi and a solvent (DOL:DME=1:1(v/v)) (SBR: Styrene Butadiene Rubber, CMC: Carboxylmethyl Cellulose, DOL: Dioxolane, DME: Dimethoxyethane).
도 5는 실시예 5,8 및 비교예 1에서 각각 제조된 다공성 탄소 구조체를 양극에 적용한 리튬-황 이차전지의 초기 방전 실험 결과를 나타낸 그래프이다.5 is a graph showing the results of an initial discharge experiment of a lithium-sulfur secondary battery in which the porous carbon structures each prepared in Examples 5 and 8 and Comparative Example 1 were applied to a positive electrode.
도 5를 참조하면, 실시예 8에서 제조된 다공성 탄소 구조체를 양극에 적용할 경우, 리튬-황 이차전지의 성능이 상대적으로 개선되는 것을 알 수 있다.Referring to FIG. 5, when the porous carbon structure prepared in Example 8 is applied to a positive electrode, it can be seen that the performance of a lithium-sulfur secondary battery is relatively improved.
도 6a 및 6b는 각각 실시예 8에서 제조된 다공성 탄소 구조체를 양극에 적용한 리튬-황 이차전지의 장기 방전 실험 결과를 나타낸 그래프로서, 그 성능이 우수한 것을 알 수 있다.6A and 6B are graphs showing long-term discharge test results of a lithium-sulfur secondary battery in which the porous carbon structure prepared in Example 8 was applied to a positive electrode, respectively, and it can be seen that the performance is excellent.
이상에서 본 발명은 비록 한정된 실시예와 도면에 의해 설명되었으나, 본 발명은 이것에 의해 한정되지 않으며, 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 본 발명의 기술사상과 아래에 기재될 특허청구범위의 균등범위 내에서 다양한 수정 및 변형이 가능함은 물론이다.In the above, although the present invention has been described by limited embodiments and drawings, the present invention is not limited thereto, and the technical idea of the present invention and the following description by those of ordinary skill in the art to which the present invention pertains. It goes without saying that various modifications and variations are possible within the equivalent range of the claims to be made.
Claims (14)
상기 아연과 유기 리간드의 몰 비율은 1:3 내지 1:6 인, 금속 유기 골격체.The method of claim 1,
The molar ratio of the zinc and the organic ligand is 1:3 to 1:6, metal organic framework.
(S2) 상기 혼합 용액을 가열하는 단계; 및
(S3) 상기 가열된 혼합 용액에서 상층액을 버린 후, 합성된 금속 유기 골격체를 세척하는 단계;
를 포함하는, 금속 유기 골격체의 제조방법.(S1) preparing a mixed solution by dissolving a zinc precursor and a precursor of an organic ligand in a mixed solvent of an organic solvent and an aqueous solvent;
(S2) heating the mixed solution; And
(S3) after discarding the supernatant from the heated mixed solution, washing the synthesized metal organic skeleton;
Containing, a method for producing a metal organic skeleton.
상기 아연 전구체는 아연나이트레이트·6수화물 (Zn(NO3)2·6H2O), 아연아세테이트·2수화물 (Zn(CH3CO2)2·2H2O) 및 아연설페이트·6수화물 (ZnSO4·6H2O)로 이루어진 군에서 선택되는 1종 이상인, 금속 유기 골격체의 제조방법.The method of claim 3,
The zinc precursor is zinc nitrate hexahydrate (Zn(NO 3 ) 2 6H 2 O), zinc acetate dihydrate (Zn(CH 3 CO 2 ) 2 2H 2 O) and zinc sulfate hexahydrate (ZnSO 4 · 6H 2 O) at least one selected from the group consisting of, a method for producing a metal organic skeleton.
상기 유기 리간드의 전구체는 벤젠-1,4-디카르복실산(benzene-1,4-dicarboxylic acid), 벤젠-1,3,5-트리카르복실산(benzene-1,3,5-tricarboxylic acid), 2-메틸이미다졸(2-methylimidazole), 에탄디오산(ethanedioic acid), 프로판디오산(propanedioic acid), 부탄디오산(butanedioic acid), 펜탄디오산(pentanedioic acid), o-프탈산(o-phthalic acid), m-프탈산(m-phthalic acid), p-프탈산(p-phthalic acid), 2-히드록시-1,2,3-프로판트리카르복실산(2-hydroxy-1,2,3-propanetricarboxylic acid), 1H-1,2,3-트리아졸(1H-1,2,3-triazole), 1H-1,2,4-트리아졸(1H-1,2,4-triazole) 및 3,4-디히드록시-3-사이클로부텐-1,2-디온(3,4-dihydroxy-3-cyclobutene-1,2-dione)로 이루어진 군에서 선택되는 1종 이상인, 금속 유기 골격체의 제조방법.The method of claim 3,
The precursor of the organic ligand is benzene-1,4-dicarboxylic acid, benzene-1,3,5-tricarboxylic acid ), 2-methylimidazole, ethanedioic acid, propanedioic acid, butanedioic acid, pentanedioic acid, o-phthalic acid ( o-phthalic acid), m-phthalic acid, p-phthalic acid, 2-hydroxy-1,2,3-propanetricarboxylic acid (2-hydroxy-1,2 ,3-propanetricarboxylic acid), 1H-1,2,3-triazole (1H-1,2,3-triazole), 1H-1,2,4-triazole (1H-1,2,4-triazole) And 3,4-dihydroxy-3-cyclobutene-1,2-dione (3,4-dihydroxy-3-cyclobutene-1,2-dione) at least one selected from the group consisting of, a metal organic skeleton Method of manufacturing.
상기 아연 전구체와 유기 리간드의 전구체의 몰 비율(Molar ratio)은 1:3 내지 1:6 인, 금속 유기 골격체의 제조방법.The method of claim 3,
Molar ratio of the zinc precursor and the precursor of the organic ligand (Molar ratio) is 1:3 to 1:6, the method for producing a metal organic skeleton.
상기 유기 용매는 디메틸 카보네이트, 디메틸 포름아미드, N-메틸 포름아미드, 술폴란(테트라히드로티오펜-1,1-디옥사이드), 3-메틸술폴란, N-부틸 술폰, 디메틸 설폭사이드, 피로리디논(HEP), 디메틸피페리돈(DMPD), N-메틸 피롤리디논(NMP), N-메틸 아세트아미드, 디메틸 아세트아미드(DMAc), 디메틸포름아미드(DMF), 디에틸아세트아마이드(DEAc) 디프로필아세트 아마이드(DPAc), 에탄올, 프로판올, 부탄올, 헥산올, 에틸렌글리콜, 테트라클로로에틸렌, 프로필렌글리콜, 톨루엔, 트르펜틴, 메틸 아세테이트, 에틸 아세테이트, 페트롤 에테르, 아세톤, 크레졸 및 글리세롤로 이루어진 군에서 선택된 1종 이상인, 금속 유기 골격체의 제조방법.The method of claim 3,
The organic solvent is dimethyl carbonate, dimethyl formamide, N-methyl formamide, sulfolane (tetrahydrothiophene-1,1-dioxide), 3-methylsulfolane, N-butyl sulfone, dimethyl sulfoxide, pyloridinone (HEP), dimethylpiperidone (DMPD), N-methylpyrrolidinone (NMP), N-methyl acetamide, dimethyl acetamide (DMAc), dimethylformamide (DMF), diethylacetamide (DEAc) dipropyl 1 selected from the group consisting of acetamide (DPAc), ethanol, propanol, butanol, hexanol, ethylene glycol, tetrachloroethylene, propylene glycol, toluene, trpentine, methyl acetate, ethyl acetate, petroleum ether, acetone, cresol and glycerol More than a species, a method for producing a metal organic skeleton.
상기 수계 용매는 물인, 금속 유기 골격체의 제조방법.The method of claim 3,
The aqueous solvent is water, a method for producing a metal organic skeleton.
상기 유기 용매와 수계 용매의 부피비는 4~11:1인, 금속 유기 골격체의 제조방법.The method of claim 3,
The volume ratio of the organic solvent and the aqueous solvent is 4 to 11: 1, the method for producing a metal organic skeleton.
상기 혼합 용액의 농도는 고형분 함량을 기준으로 1 내지 10%인, 금속 유기 골격체의 제조방법.The method of claim 3,
The concentration of the mixed solution is 1 to 10% based on the solid content, the method for producing a metal organic skeleton.
상기 가열은 20 내지 40 시간 동안 80 내지 150℃에서 수행되는 것인, 금속 유기 골격체의 제조방법.The method of claim 3,
The heating is carried out at 80 to 150 ℃ for 20 to 40 hours, the method for producing a metal organic skeleton.
상기 탄화는 불활성 분위기 하에서 500 내지 1500 ℃의 온도로 3 내지 10 시간 동안 실시하는 것인, 다공성 탄소 구조체의 제조방법.
The method of claim 13,
The carbonization is carried out for 3 to 10 hours at a temperature of 500 to 1500 ℃ in an inert atmosphere, the method of manufacturing a porous carbon structure.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113072058A (en) * | 2021-03-25 | 2021-07-06 | 电子科技大学 | Preparation method and application of nano carbon material with porous structure |
| CN113072056A (en) * | 2021-03-25 | 2021-07-06 | 电子科技大学 | Preparation method of metal organic framework derived carbon with high specific surface area |
| CN113402727A (en) * | 2021-06-30 | 2021-09-17 | 云南师范大学 | Terbium (III) loaded zinc-based metal organic framework and preparation and application thereof |
| CN114050261A (en) * | 2021-11-04 | 2022-02-15 | 浙江工业大学 | Preparation method of zinc-based battery negative electrode material |
| WO2022164213A1 (en) * | 2021-01-27 | 2022-08-04 | 주식회사 엘지에너지솔루션 | Porous carbon structure, manufacturing method therefor, and lithium secondary battery comprising same |
| CN115050938A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery |
| CN116536092A (en) * | 2023-03-30 | 2023-08-04 | 西北工业大学 | Carbon sphere@copper-based metal organic framework nano lubricant and preparation method thereof |
| WO2023244050A1 (en) * | 2022-06-17 | 2023-12-21 | 경상국립대학교산학협력단 | Method for controlling size of metal-organic framework |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267145A (en) | 2018-08-30 | 2019-01-25 | 济南大学 | A kind of four acid anhydrides Zn-MOF crystalline material of naphthalene and its preparation method and application |
-
2019
- 2019-06-28 KR KR1020190078068A patent/KR20210001662A/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109267145A (en) | 2018-08-30 | 2019-01-25 | 济南大学 | A kind of four acid anhydrides Zn-MOF crystalline material of naphthalene and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| RSC Adv., Vol. 6, Issue. 97, pp. 94629-94635 |
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| CN113072058A (en) * | 2021-03-25 | 2021-07-06 | 电子科技大学 | Preparation method and application of nano carbon material with porous structure |
| CN113072056A (en) * | 2021-03-25 | 2021-07-06 | 电子科技大学 | Preparation method of metal organic framework derived carbon with high specific surface area |
| CN113402727A (en) * | 2021-06-30 | 2021-09-17 | 云南师范大学 | Terbium (III) loaded zinc-based metal organic framework and preparation and application thereof |
| CN113402727B (en) * | 2021-06-30 | 2022-07-12 | 云南师范大学 | Terbium (III) loaded zinc-based metal organic framework and preparation and application thereof |
| CN114050261A (en) * | 2021-11-04 | 2022-02-15 | 浙江工业大学 | Preparation method of zinc-based battery negative electrode material |
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| CN115050938A (en) * | 2022-06-18 | 2022-09-13 | 福州大学 | Preparation method of heteroatom-doped hollow carbon material and application of heteroatom-doped hollow carbon material in lithium-sulfur battery |
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