JP6338179B2 - イオン伝導性複合体 - Google Patents
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- 239000002131 composite material Substances 0.000 title claims description 48
- 239000000126 substance Substances 0.000 claims description 114
- 239000011148 porous material Substances 0.000 claims description 79
- 150000002500 ions Chemical class 0.000 claims description 67
- 239000002245 particle Substances 0.000 claims description 64
- 239000012071 phase Substances 0.000 claims description 57
- 239000004033 plastic Substances 0.000 claims description 50
- 239000004020 conductor Substances 0.000 claims description 13
- 239000005373 porous glass Substances 0.000 claims description 10
- 238000000113 differential scanning calorimetry Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-O Pyrrolidinium ion Chemical compound C1CC[NH2+]C1 RWRDLPDLKQPQOW-UHFFFAOYSA-O 0.000 claims description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 3
- 239000007790 solid phase Substances 0.000 claims description 2
- 230000007704 transition Effects 0.000 description 29
- 239000013078 crystal Substances 0.000 description 18
- 239000013259 porous coordination polymer Substances 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 14
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 239000007772 electrode material Substances 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 230000001747 exhibiting effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 239000013206 MIL-53 Substances 0.000 description 7
- 239000005289 controlled pore glass Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- -1 piperidinium ion Chemical class 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 239000003960 organic solvent Substances 0.000 description 6
- 229920006254 polymer film Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OYFRNYNHAZOYNF-UHFFFAOYSA-N H2dhybdc Natural products OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 description 5
- 239000003990 capacitor Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
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- 239000013207 UiO-66 Substances 0.000 description 3
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- 238000004458 analytical method Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CDOWNLMZVKJRSC-UHFFFAOYSA-N 2-hydroxyterephthalic acid Chemical group OC(=O)C1=CC=C(C(O)=O)C(O)=C1 CDOWNLMZVKJRSC-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 239000013178 MIL-101(Cr) Substances 0.000 description 2
- 239000013118 MOF-74-type framework Substances 0.000 description 2
- 239000013115 Zn-MOF-74 Substances 0.000 description 2
- 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 description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 159000000003 magnesium salts Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 159000000000 sodium salts Chemical class 0.000 description 2
- 239000012453 solvate Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 2
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910020366 ClO 4 Inorganic materials 0.000 description 1
- 239000013148 Cu-BTC MOF Substances 0.000 description 1
- 239000013147 Cu3(BTC)2 Substances 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- BRVHCCPVIILNPA-UHFFFAOYSA-N bis(trifluoromethylsulfonyl)azanide;1-ethyl-1-methylpyrrolidin-1-ium Chemical compound CC[N+]1(C)CCCC1.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F BRVHCCPVIILNPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 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 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000005486 organic electrolyte Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007569 slipcasting Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010345 tape casting Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 238000003826 uniaxial pressing Methods 0.000 description 1
- 238000012982 x-ray structure analysis Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Description
しかし、この構成では、電極材10と多孔性高分子膜100の接触点が少ないため、イオンがほとんど伝達されず、電気化学デバイスとして機能しない。
(1)絶縁性の多孔性ガラスの粒子によって構成された構造体と、前記粒子の細孔内に保持されたイオン性物質と、を備え、前記イオン性物質が、細孔内で固相であるプラスチッククリスタル相であるとともに、前記イオン性物質のカチオンが、ピロリジニウムイオンまたは4級アンモニウムイオンであり、前記イオン性物質のアニオンが、TFSIであり、前記粒子の細孔の直径が、25nm以下であることを特徴とするイオン伝導性複合体。
(2)前記細孔内の前記イオン性物質が、示差走査熱量分析において50℃以上および5℃以下に吸熱ピークを有することを特徴とする前記(1)に記載のイオン伝導性複合体。
(3)前記構造体が、膜状またはシート状であることを特徴とする前記(1)または(2)に記載のイオン伝導性複合体。
(4)前記構造体が、複数の前記粒子によって構成された成形体であることを特徴とする前記(1)〜(3)のいずれかに記載のイオン伝導性複合体。
(5)前記成形体が、前記粒子間に設けられた複数の間隙を有することを特徴とする前記(4)に記載のイオン伝導性複合体。
(6)前記複数の間隙のうち少なくとも一部の間隙に、イオン伝導性物質を有していることを特徴とする前記(5)に記載のイオン伝導性複合体。
(7)前記イオン伝導性物質が、前記イオン性物質と同一であることを特徴とする前記(6)に記載のイオン伝導性複合体。
Zn(MeIM)2(以下、ZIF−8と記載する。)
Al(OH)(BDC)(以下、Al−MIL−53と記載する。)
Cr(OH)(BDC)(以下、Cr−MIL−53と記載する。)
Fe(OH)(BDC)(以下、Fe−MIL−53と記載する。)
VO(BDC)(以下、V−MIL−47と記載する。)
Zn2(DOBDC)(以下、Zn−MOF−74と記載する。)
Mg2(DOBDC)(以下、Mg−MOF−74と記載する。)
Al(OH)(1,4−NDC)
Cr3O(F,OH)(BDC)3(以下、Cr−MIL−101と記載する。)
Al8(OH)15(BTC)3(以下、Al−MIL−110と記載する。)
Cu3(BTC)2(以下、HKUST−1と記載する。)
Zr6O4(OH)4(BDC)6またはZr6O6(BDC)6(以下、UiO−66と記載する。)
Zr6O4(OH)4(BPDC)6またはZr6O6(BPDC)6(以下、UiO−67と記載する。)
Zr6O4(OH)4(TPDC)6またはZr6O6(TPDC)6(以下、UiO−68と記載する。)
ZrO(BDC)(以下、MIL−140と記載する。)
などが挙げられる。
H(MeIM):2−メチルイミダゾール
H2(BDC):テレフタル酸
H4(DOBDC):2,5−ジヒドロキシテレフタル酸
H2(1,4−NDC):1,4−ナフタレンジカルボン酸
H3(BTC):1,3,5−ベンゼントリカルボン酸
H2(BPDC):4,4’−ビフェニルジカルボン酸
H2(TPDC):4,4’’−p−テルフェニルジカルボン酸
においてH+が解離した残基を表わす。
ZIF−8:多孔性配位高分子であるSIGMA−ALDRICH社のBasolite(登録商標)Z1200(細孔径1.2nm)
CPG120:多孔性ガラスであるSIGMA−ALDRICH社のControlled Pore Glass(細孔径12nm、80−120メッシュ)
1a 細孔
2 イオン性物質
3 イオン伝導性複合体
4 成形体
5 間隙
6 イオン伝導性物質
10 電極材
20 電極
100 多孔性高分子膜
Claims (7)
- 絶縁性の多孔性ガラスの粒子によって構成された構造体と、前記粒子の細孔内に保持されたイオン性物質と、を備え、
前記イオン性物質が、細孔内で固相であるプラスチッククリスタル相であるとともに、
前記イオン性物質のカチオンが、ピロリジニウムイオンまたは4級アンモニウムイオンであり、
前記イオン性物質のアニオンが、TFSIであり、
前記粒子の細孔の直径が、25nm以下であることを特徴とするイオン伝導性複合体。 - 前記細孔内の前記イオン性物質が、示差走査熱量分析において50℃以上および5℃以下に吸熱ピークを有することを特徴とする請求項1に記載のイオン伝導性複合体。
- 前記構造体が、膜状またはシート状であることを特徴とする請求項1または2に記載のイオン伝導性複合体。
- 前記構造体が、複数の前記粒子によって構成された成形体であることを特徴とする請求項1〜3のいずれかに記載のイオン伝導性複合体。
- 前記成形体が、前記粒子間に設けられた複数の間隙を有することを特徴とする請求項4に記載のイオン伝導性複合体。
- 前記複数の間隙のうち少なくとも一部の間隙に、イオン伝導性物質を有していることを特徴とする請求項5に記載のイオン伝導性複合体。
- 前記イオン伝導性物質が、前記イオン性物質と同一であることを特徴とする請求項6に記載のイオン伝導性複合体。
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JP6338179B2 true JP6338179B2 (ja) | 2018-06-06 |
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Families Citing this family (3)
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DK3673531T3 (da) | 2017-08-24 | 2021-07-12 | Fraunhofer Ges Forschung | Solid-state-batteri baseret på en ionledende matrix af kamfer eller 2-adamantanon |
CN115443568A (zh) * | 2020-06-23 | 2022-12-06 | 株式会社村田制作所 | 电化学装置 |
CN113410523B (zh) * | 2021-06-21 | 2022-08-02 | 中原工学院 | 一种柔性金属有机框架基塑晶电解质及其制备方法和应用 |
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JP4997465B2 (ja) * | 2005-03-31 | 2012-08-08 | 独立行政法人産業技術総合研究所 | ナノ細孔を用いたイオン性液体の制御方法 |
WO2008081811A1 (ja) * | 2006-12-28 | 2008-07-10 | National Institute Of Advanced Industrial Science And Technology | プラスティッククリスタル |
WO2013161452A1 (ja) * | 2012-04-23 | 2013-10-31 | 国立大学法人京都大学 | 多孔性配位高分子-イオン液体複合体 |
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