JP6764860B2 - プラズマ重合による、ゲル高分子電解質の高分子マトリックスの製造方法 - Google Patents
プラズマ重合による、ゲル高分子電解質の高分子マトリックスの製造方法 Download PDFInfo
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- 229920000642 polymer Polymers 0.000 title claims description 119
- 239000005518 polymer electrolyte Substances 0.000 title claims description 34
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- 238000004519 manufacturing process Methods 0.000 title claims description 18
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- 229920000053 polysorbate 80 Polymers 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 206010040844 Skin exfoliation Diseases 0.000 claims 1
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- 238000000034 method Methods 0.000 description 12
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 11
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- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
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- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 description 1
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100021202 Desmocollin-1 Human genes 0.000 description 1
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- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
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- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
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- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
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- 230000009477 glass transition Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- WFKAJVHLWXSISD-UHFFFAOYSA-N isobutyramide Chemical compound CC(C)C(N)=O WFKAJVHLWXSISD-UHFFFAOYSA-N 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
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- FCZYGJBVLGLYQU-UHFFFAOYSA-M sodium;2-[2-[2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]ethoxy]ethoxy]ethanesulfonate Chemical compound [Na+].CC(C)(C)CC(C)(C)C1=CC=C(OCCOCCOCCS([O-])(=O)=O)C=C1 FCZYGJBVLGLYQU-UHFFFAOYSA-M 0.000 description 1
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- 229920003002 synthetic resin Polymers 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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Description
1)ポリエチレンオキサイドとイオン性物質のプラズマ高分子薄膜の製造
[BMIM]BF4(1−butyl−3−methylimidazolium tetrafluoroborate、 Sigma−Aldrich、 USA)にTritonX−100(Sigma−Aldrich、 USA)の最終濃度が6M%になるように添加した後ボルテックスミキサー(Vortex Mixer−KMC−1300V)を使用して、5分間攪拌した。製造された溶液0.5mLをspin−coater(SPIN−1200D、MIDAS)を使用して20X20mmガラス板の上に5000rpmで15秒間スピンコーティングした。以後常圧プラズマシステム(Ar、150W、3lpm)を使用して、10分間重合した。プラズマ電極とスピンコーティングされた薄膜の距離は2mmであった。プラズマ処理されたガラス板は、エタノール中に浸漬してガラス板から薄膜を分離し、アセトンと蒸留水で順次洗浄した後、60℃で1時間乾燥した。
反応時間を1〜30分に調節したことを除いては、1)と同様の方法でTritonX−100と[BMIM]BF4をプラズマ重合した後、高分子薄膜を分離して、断面を走査電子顕微鏡(SEM、JEOL、JSM−7000F、USA)で観察し、その結果を図2に示した。図2のa)〜d)は、それぞれ1、2、6、10分間プラズマ重合反応して生成された高分子薄膜の断面のSEM画像であり、e)は、反応時間に伴う薄膜の厚さを示したグラフである。
TritonX−100のM%を0.3〜48M%に調節したことを除いては、1)と同様の方法でTritonX−100と[BMIM]BF4を6分間プラズマ重合した後(このとき、Ar flowは5lpm)、高分子薄膜を分離して、断面を走査電子顕微鏡(SEM)で観察し、その結果を図3に示した。図3のa)〜g)は、それぞれ0.3、0.7、1.5、3、6、12、および24M%のTritonX−100を使用して、6分間プラズマ重合反応して生成された高分子薄膜の断面の SEM 画像であり、e)は、TritonX−100の割合に対する薄膜の厚さを示したグラフである。図3からイオン性液体とポリエチレンオキシドのモル比は、薄膜の厚さに影響を与えることがわかる。図4は、TritonX−100の含有量が0〜3M%である区間を拡大したグラフで TritonX−100の含有量が1.5M%と非常に低い場合に最も厚いフィルムを製造することができることを示している。
実施例1で製造したプラズマ高分子薄膜の構造をsolid−NMR(Agilent 400MH 54mm NMR DD2、USA)、IR(Nicolet 670、USA)およびXPS(Thermo Scientific MultiLab 2000)を使用して分析し、熱重量分析器(TGA/DSC1、Mettler−Toledo Inc.)を使用して熱特性を分析した。下記の実施例では、TritonX−100と[BMIM]BF4のプラズマ高分子を試料に分析し、特別な記載がない限り6M%のTritonX−100と[BMIM]BF4を用いて実施例1の1)の記載の方法に基づいて10分間プラズマ重合した高分子を試料として使用して分析した結果を示す。分析に使用した機器は、次のとおりである。
図5は、高分子薄膜のa)13C MAS−NMR、b)1H MAS−NMR(15kHz)およびFTIRスペクトルを示す。IRスペクトルからプラズマ高分子でイミダゾリウム環のC−Hのピークが弱くなって、C=CおよびC=O結合が生成されたことを確認できた。
図7のa)は代表的な高分子薄膜のXPSスペクトルであり、b)は、XPSスペクトルから計算したTritonX−100のM%による高分子薄膜中の元素の比を示すグラフである。また、TritonX−100のM%によるプラズマ重合された高分子で元素の%とその割合をそれぞれ表3と表4に示した。
プラズマ重合された高分子薄膜を熱重量分析装置を使用して分析した。図10は、高分子薄膜を10℃/minの速度で25℃から1000℃に加熱して得られたDSCとTGAスペクトルであり、高分子の分解温度が200℃以上で熱的に非常に安定であることを確認できた。また、DSCスペクトルから測定したTgとTmは、それぞれ3.11℃と279.50℃であった。
実施例1で製造したプラズマ高分子薄膜の電気的特性を測定するために、ニケル電極に挟んで薄膜電池を作製した。電解質として1MのLiPF6/DMCを0.5mL添加し、密封された試料を150℃で3秒間安定化させた後使用した。電池をリード線を使用してpotentiostat(IVIUMSTAT、Ivium Technologies)に接続し、交流インピーダンス法により試料の抵抗値を測定した。図11は、測定されたインピーダンスの値を示すグラフであり、前記グラフから計算された試料の抵抗値(Rb)と厚さ(l)と高分子電解質の面積(A)からイオン伝導度(σ)を下記数式1により算出し、その結果を図12に示した。
Claims (3)
- プラズマ重合による、ゲル高分子電解質の高分子マトリックスの製造方法において、
イオン性液体とポリエチレンオキシドの混合物である液状の高分子モノマーと気体の界面にプラズマを加えて重合し、
前記ポリエチレンオキシドは、下記化1の式、または、Tween80であり、
前記ポリエチレンオキシドの含有量は6モル%以下であり、
前記イオン性液体は、陽イオンが置換または非置換された1−R−1-メチルピロリジウム(1−R−1−methylpyrrolidium)または置換または非置換された1−R−3−メチルイミダゾリウム(1−R−3−methylimidazolium)で、RはC3〜C16のアルキル基であり、陰イオンがBF 4 − 、F − 、Cl − 、Br − またはI − で構成される塩であることを特徴とするゲル高分子電解質の高分子マトリックスの製造方法。 - 前記液状の高分子モノマーは、基板上にコーティングされた状態で、
(A) 基板上に高分子モノマーをコーティングする段階;
(B) コーティングされた高分子モノマーと気体の界面にプラズマを加えて重合する段階;、および、
(C) 基板からプラズマ重合された高分子を剥離する段階;
を含むことを特徴とする請求項1に記載のゲル高分子電解質の高分子マトリックスの製造方法。 - 前記ポリエチレンオキシドは、分子量が200〜2000であることを特徴とする請求項1に記載のゲル高分子電解質の高分子マトリックスの製造方法。
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