JP6713693B2 - 炭素電極を用いたアクチュエータ素子 - Google Patents
炭素電極を用いたアクチュエータ素子 Download PDFInfo
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- JP6713693B2 JP6713693B2 JP2018189452A JP2018189452A JP6713693B2 JP 6713693 B2 JP6713693 B2 JP 6713693B2 JP 2018189452 A JP2018189452 A JP 2018189452A JP 2018189452 A JP2018189452 A JP 2018189452A JP 6713693 B2 JP6713693 B2 JP 6713693B2
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- conductive thin
- thin film
- actuator element
- polymer
- ionic liquid
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 47
- 229910052799 carbon Inorganic materials 0.000 title description 7
- 239000010409 thin film Substances 0.000 claims description 95
- 239000002608 ionic liquid Substances 0.000 claims description 62
- 229920000642 polymer Polymers 0.000 claims description 58
- 239000003792 electrolyte Substances 0.000 claims description 51
- 239000002904 solvent Substances 0.000 claims description 51
- 239000000463 material Substances 0.000 claims description 40
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 40
- 239000002041 carbon nanotube Substances 0.000 claims description 38
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 38
- 239000012528 membrane Substances 0.000 claims description 34
- 230000002209 hydrophobic effect Effects 0.000 claims description 13
- -1 phosphonium ion Chemical class 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002482 conductive additive Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 5
- 239000002109 single walled nanotube Substances 0.000 claims description 5
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 3
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- 229920000128 polypyrrole Polymers 0.000 claims description 3
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- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 claims description 2
- 239000002048 multi walled nanotube Substances 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 claims 1
- PCCVSPMFGIFTHU-UHFFFAOYSA-N tetracyanoquinodimethane Chemical compound N#CC(C#N)=C1C=CC(=C(C#N)C#N)C=C1 PCCVSPMFGIFTHU-UHFFFAOYSA-N 0.000 description 28
- 238000006073 displacement reaction Methods 0.000 description 26
- 230000000052 comparative effect Effects 0.000 description 16
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- 229910052794 bromium Inorganic materials 0.000 description 11
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- 238000000034 method Methods 0.000 description 9
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- 238000011156 evaluation Methods 0.000 description 8
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- 150000002500 ions Chemical class 0.000 description 7
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
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- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 4
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- 101710161969 Alkaline phosphatase, tissue-nonspecific isozyme Proteins 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229920006370 Kynar Polymers 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000001879 gelation Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- UGNWTBMOAKPKBL-UHFFFAOYSA-N tetrachloro-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(Cl)=C(Cl)C1=O UGNWTBMOAKPKBL-UHFFFAOYSA-N 0.000 description 3
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- SDDBCEWUYXVGCQ-UHFFFAOYSA-N 1,5-dimethylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1C SDDBCEWUYXVGCQ-UHFFFAOYSA-N 0.000 description 2
- WCZNKVPCIFMXEQ-UHFFFAOYSA-N 2,3,5,6-tetramethylbenzene-1,4-diamine Chemical compound CC1=C(C)C(N)=C(C)C(C)=C1N WCZNKVPCIFMXEQ-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- VHQGURIJMFPBKS-UHFFFAOYSA-N 2,4,7-trinitrofluoren-9-one Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=O)C2=C1 VHQGURIJMFPBKS-UHFFFAOYSA-N 0.000 description 2
- OVIRUXIWCFZJQC-UHFFFAOYSA-N 2-(1,3-benzodithiol-2-ylidene)-1,3-benzodithiole Chemical compound S1C2=CC=CC=C2SC1=C1SC2=CC=CC=C2S1 OVIRUXIWCFZJQC-UHFFFAOYSA-N 0.000 description 2
- UFPVYWYEZPMUQL-UHFFFAOYSA-N 2-(1,3-diselenol-2-ylidene)-1,3-diselenole Chemical compound [Se]1C=C[Se]C1=C1[Se]C=C[Se]1 UFPVYWYEZPMUQL-UHFFFAOYSA-N 0.000 description 2
- POJAQDYLPYBBPG-UHFFFAOYSA-N 2-(2,4,7-trinitrofluoren-9-ylidene)propanedinitrile Chemical compound [O-][N+](=O)C1=CC([N+]([O-])=O)=C2C3=CC=C([N+](=O)[O-])C=C3C(=C(C#N)C#N)C2=C1 POJAQDYLPYBBPG-UHFFFAOYSA-N 0.000 description 2
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- HGOTVGUTJPNVDR-UHFFFAOYSA-N 2-(4,5-dimethyl-1,3-dithiol-2-ylidene)-4,5-dimethyl-1,3-dithiole Chemical compound S1C(C)=C(C)SC1=C1SC(C)=C(C)S1 HGOTVGUTJPNVDR-UHFFFAOYSA-N 0.000 description 2
- VRSXBMGXAHSMFB-UHFFFAOYSA-N 2-(5,6-dihydro-4h-cyclopenta[d][1,3]diselenol-2-ylidene)-5,6-dihydro-4h-cyclopenta[d][1,3]diselenole Chemical compound C1CCC([Se]2)=C1[Se]C2=C([Se]1)[Se]C2=C1CCC2 VRSXBMGXAHSMFB-UHFFFAOYSA-N 0.000 description 2
- DTJPUCUJANTIIU-UHFFFAOYSA-N 2-(5,6-dihydro-4h-cyclopenta[d][1,3]dithiol-2-ylidene)-5,6-dihydro-4h-cyclopenta[d][1,3]dithiole Chemical compound C1CCC(S2)=C1SC2=C(S1)SC2=C1CCC2 DTJPUCUJANTIIU-UHFFFAOYSA-N 0.000 description 2
- VRGCYEIGVVTZCC-UHFFFAOYSA-N 3,4,5,6-tetrachlorocyclohexa-3,5-diene-1,2-dione Chemical compound ClC1=C(Cl)C(=O)C(=O)C(Cl)=C1Cl VRGCYEIGVVTZCC-UHFFFAOYSA-N 0.000 description 2
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
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- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
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- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
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- BXPLEMMFZOKIHP-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-3-fluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=CC(=C(C#N)C#N)C=CC1=C(C#N)C#N BXPLEMMFZOKIHP-UHFFFAOYSA-N 0.000 description 1
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Description
本出願は、2012年3月30日に出願された、日本国特許出願第2012−79763号明細書(その開示全体が参照により本明細書中に援用される)に基づく優先権を主張する。
なお、導電性微粒子は、ナノ粒子として用いる場合には、平均粒径がナノサイズである必要があるが、他の炭素含有導電性ナノ材料と組み合わせる場合には、サブミクロン或いはミクロンサイズの導電性微粒子を使用してもよい。
ナノカーボン材料:
5〜90重量%、好ましくは10〜70重量%、より好ましくは15〜50重量%;
イオン液体:
5〜80重量%、好ましくは15〜73.4重量%、より好ましくは20〜69重量%;
ポリマー:
4〜70重量%、好ましくは10〜68.4重量%、より好ましくは11〜64重量%;である。
[導電性薄膜層形成用分散液の調製]
DMAC溶媒中に、カーボンナノチューブ(SWCNT)とイオン液体(IL)、ポリマー[粉末状PVDF(HFP)]、有機分子を分散させて、マグネチックスターラーにて撹拌、その後、超音波による分散を行うことにより導電性薄膜層形成用分散液を調製する。
イオン液体(IL)とポリマー[粉末状PVDF(HFP)]を、上記導電性薄膜層形成用分散液の調製と同様にして、溶媒に溶解させることにより、電解質膜形成用溶液を調製する。
導電性薄膜、電解質膜は、それぞれ上記のように調製した分散液および溶液を、別々にキャストし、室温で一昼夜溶媒を乾燥させ、次いで、真空乾燥を行うことにより得る。
製造したアクチュエータ素子の変位応答性の評価は、図2に示した装置を用いて行った。アクチュエータ素子を、幅1mm×長さ10mmの短冊状に切断し、端3mmの部分を電極付きホルダーでつかんで、空気中で電圧を加え、レーザ変位計を用いて、固定端から5mmの位置での変位を測定して行った。
製造した導電性薄膜の導電率は四端子法により求めた。また、ヤング率は応力−ひずみ測定により求めた。
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子供与性有機分子(TTF)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/TTF=50.7mg/80.1mg/120.8mg/50.7mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子吸引性有機分子(TCNQ)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/TCNQ=50.2mg/80.2mg/120.8mg/50.6mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び有機分子(TTF、TCNQ)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/TTF/TCNQ=50.7mg/80.1mg/120.1mg/25.1mg/25.0mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子供与性有機分子(フェノチアジン)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/フェノチアジン=50.4mg/80.2mg/120.1mg/50.1mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子吸引性有機分子(TCNQ)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/TCNQ=50.2mg/80.2mg/120.8mg/25.0mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子吸引性有機分子(クロラニル)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/クロラニル=50.2mg/80.2mg/120.8mg/50.0mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子吸引性有機分子(ブロマニル)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/ブロマニル=50.2mg/80.2mg/120.8mg/50.1mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)及び電子吸引性有機分子(PMDA)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4/PMDA=50.2mg/80.2mg/120.8mg/50.3mg
電解質:kynar2801/EMIBF4=101.8mg/114.3mg
以下に、用いた有機分子の構造を示す。
以下の比率で、カーボンナノチューブ(CNT)、イオン液体(EMIBF4)、ポリマー(kynar2801)を使用して、導電性薄膜層(電極)−電解質膜−導電性薄膜層(電極)からなる、3層構造のフィルム状のアクチュエータ素子を製造した。
電極 :CNT/kynar2801/EMIBF4=50.2mg/80.0mg/125.6mg
電解質:kynar2801/EMIBF4=206.2mg/208.3mg
実施例1〜8および比較例1で得られたアクチュエータ素子の電圧に対する応答性、耐久性、電極膜の特性の評価を行った。得られた結果を、図3〜図7及び表1〜表3に示す。
2 導電性薄膜層
3 導電層
Claims (14)
- イオン液体およびポリマーから構成される電解質膜と、
前記電解質膜の一方の表面に形成された第1の導電性薄膜層と、
前記電解質膜の前記一方の面と反対側の他方の表面に形成された第2の導電性薄膜層とを備え、
前記第1および第2の導電性薄膜層の各々は、電子供与性有機分子及び電子吸引性有機分子からなる群から選ばれる少なくとも1種の有機分子、カーボンナノチューブ、カーボンナノホーンおよびカーボンナノファイバーの少なくとも1つからなるナノカーボン材料、イオン液体およびポリマーを溶媒に混合して得られる組成物から形成される高分子ゲルから構成される導電性薄膜を含み、
前記第1の導電性薄膜層、前記第2の導電性薄膜層および前記電解質膜に含まれる前記イオン液体のアニオンは、BF4 −、(CF3SO2)2N−、CF3SO3 −および(CN)2N−の少なくとも1つである、アクチュエータ素子。 - 前記第1の導電性薄膜層、前記第2の導電性薄膜層および前記電解質膜に含まれる前記イオン液体のカチオンは、イミダゾリウムイオン、第4級アンモニウムイオン、ピリジニウムイオンおよびホスホニウムイオンの少なくとも1つである、請求項1に記載のアクチュエータ素子。
- 前記第1および第2の導電性薄膜層の前記導電性薄膜に含まれる前記ポリマーは、前記電解質膜に含まれる前記ポリマーと同一である、請求項1または請求項2に記載のアクチュエータ素子。
- 前記第1および第2の導電性薄膜層の前記導電性薄膜は、導電添加剤を更に含み、
前記導電添加剤は、カーボンブラック、ポリアニリン、ポリチオフェンおよびポリピロールの少なくとも1つである、請求項1から請求項3のいずれか1項に記載のアクチュエータ素子。 - 前記ナノカーボン材料50重量部に対して、前記有機分子は、20〜100重量部含まれる、請求項1から請求項4のいずれか1項に記載のアクチュエータ素子。
- 前記第1および第2の導電性薄膜層の前記導電性薄膜は、2種の有機分子を含み、
前記2種の有機分子の配合割合は、1:3〜3:1である、請求項1から請求項5のいずれか1項に記載のアクチュエータ素子。 - 前記電解質膜の厚さは、5〜200μmである、請求項1から請求項6のいずれか1項 に記載のアクチュエータ素子。
- 前記第1および第2の導電性薄膜層の各々の厚さは、10〜500μmである、請求項1から請求項7のいずれか1項に記載のアクチュエータ素子。
- 前記第1および第2の導電性薄膜層の前記導電性薄膜は、前記少なくとも1種の有機分子、前記ナノカーボン材料、前記イオ ン液体および前記ポリマーを、親水性溶媒と疎水性溶媒との混合溶媒、または親水性溶媒、または疎水性溶媒に混合して得られる組成物から形成される高分子ゲルから構成される、請求項1から請求項8のいずれか1項に記載のアクチュエータ素子。
- 前記導電性薄膜において、前記有機分子、前記ナノカーボン材料および前記イオン液体と前記ポリマーとの配合比は、(前記有機分子、前記ナノカーボン材料および前記イオン液体):前記ポリマー=1:2〜5:1である、請求項1から請求項9のいずれか1項に記載のアクチュエータ素子。
- 前記ナノカーボン材料は、単層カーボンナノチューブまたは多層カーボンナノチューブである、請求項1から請求項10のいずれか1項に記載のアクチュエータ素子。
- 請求項1から請求項11のいずれか1項に記載のアクチュエータ素子を備えるアクチュエータ。
- 請求項12に記載のアクチュエータを備えるロボット。
- 請求項12に記載のアクチュエータを備えるマイクロマニピュレータ。
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