JP4497456B2 - ゲル状電解質およびそれを用いた電気化学素子 - Google Patents
ゲル状電解質およびそれを用いた電気化学素子 Download PDFInfo
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- JP4497456B2 JP4497456B2 JP2004123232A JP2004123232A JP4497456B2 JP 4497456 B2 JP4497456 B2 JP 4497456B2 JP 2004123232 A JP2004123232 A JP 2004123232A JP 2004123232 A JP2004123232 A JP 2004123232A JP 4497456 B2 JP4497456 B2 JP 4497456B2
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- 239000003792 electrolyte Substances 0.000 claims description 35
- 150000001875 compounds Chemical class 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 25
- 125000003566 oxetanyl group Chemical group 0.000 claims description 24
- 238000004132 cross linking Methods 0.000 claims description 21
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
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- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
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- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
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- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
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- 150000002596 lactones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical class [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
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- RQAKESSLMFZVMC-UHFFFAOYSA-N n-ethenylacetamide Chemical compound CC(=O)NC=C RQAKESSLMFZVMC-UHFFFAOYSA-N 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
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- 229910052697 platinum Inorganic materials 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- 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
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Conductive Materials (AREA)
- Secondary Cells (AREA)
- Hybrid Cells (AREA)
Description
本発明のゲル状電解質の実施の形態を説明するにあたり、先ず、このゲル状電解質を構成する樹脂組成物の説明を行う。本発明のゲル状電解質に用いる樹脂組成物の一例は、後述する溶媒および溶質を保持するために、化学架橋可能な官能基を含む架橋性高分子化合物を架橋してなる重合体(A)と、物理架橋可能な重合体(B)とを含んでいる。
で示されるモノマーであることが好ましい。式(1)に示した重合性モノマーは、ヨウ素やヨウ素化合物などの活性成分の存在下でも充分な速度でカチオン重合(架橋)するからである。
で示されるモノマーであることが好ましい。式(2)に示した重合性モノマーもまた、ヨウ素やヨウ素化合物などの活性成分の存在下でも充分な速度でカチオン重合(架橋)するからである。
で示されるモノマーであることが好ましい。式(3)に示した重合性モノマーは、ヨウ素やヨウ素化合物などの活性成分の存在下でも充分な速度でカチオン重合(架橋)するからである。
上記オキセタン基および脂環式エポキシ基から選ばれる少なくとも1種の官能基を含む重合性モノマーは2種以上であってもよく、また、他の重合性モノマーについても2種以上であってもよい。
次に、本発明の電気化学素子の一例であるリチウムイオン電池の実施の形態について説明する。本実施形態のリチウムイオン電池は、リチウムイオンを吸蔵・放出することができる材料を含む正極と、リチウムイオンを吸蔵・放出することができる炭素材料、金属リチウム、およびリチウムと合金を形成することができる金属から選ばれる少なくとも1種の材料を含む負極と、実施形態1で説明したゲル状電解質とを備えている。
(参考例1)
(参考例2)
(参考例3)
(参考例4)
前述の式(1)においてR1がCH3、R2がC2H5で表されるオキセタン基を含む重合性モノマーmモルと、前述の式(3)においてR4がCH3、R5がCH3で表される他の重合性モノマーnモルとを、モル比m/nが1/3で共重合して重量平均分子量が5×103の架橋性高分子化合物Eを作製した。次に、架橋性高分子化合物Eを用いたこと以外は、参考例1と同様にしてゲル状電解質前駆体Eを作製した。このゲル状電解質前駆体Eを参考例1と同様にして75℃で2時間加熱したところ、白濁も硬化も起らなかった。
フッ化ビニリデン−ヘキサフルオロプロピレン共重合体を用いず、98重量部の電解液Aと、重合開始剤として2重量部のトリクレジルボレートとを混合したこと以外は、参考例1と同様にしてゲル状電解質前駆体Gを作製した。その後、参考例1と同様にしてゲル状電解質膜Gを作製した。このゲル状電解質膜Gを室温(20℃)で観察したところ、軟質なゼリー状であり、キャストした基板から剥がし取ったり、打ち抜いたりすることができず、膜としての形状を維持するのに充分な機械的強度を有していなかった。
オキセタン基を含む架橋性高分子化合物を用いず、20重量部のフッ化ビニリデン−ヘキサフルオロプロピレン共重合体“Power Flex LGB1”と、参考例1で作製した80重量部の電解液Aとを混合したこと以外は、参考例1と同様にしてゲル状電解質前駆体Hを作製した。その後、参考例1と同様にしてゲル状電解質膜Hを作製した。このゲル状電解質膜Hを室温(20℃)で観察したところ、膜としての形状を維持するのに充分な機械的強度を有していた。しかし、このゲル状電解質膜Hを密閉状態において80℃で10分間加熱したところ、液状に融解し、80℃における形状安定性は不良であった。
オキセタン基を含む架橋性高分子化合物を用いず、20重量部のフッ化ビニリデン−ヘキサフルオロプロピレン共重合体“Power Flex LGB1”と、実施例1で作製した80重量部の電解液Iとを混合したこと以外は、実施例1と同様にしてゲル状電解質前駆体Jを作製した。その後、実施例1と同様にしてゲル状電解質膜Jを作製した。このゲル状電解質膜Jを室温(20℃)で観察したところ、膜としての形状を維持するのに充分な機械的強度を有していた。しかし、このゲル状電解質膜Jを密閉状態において80℃で10分間加熱したところ、液状に融解し、80℃における形状安定性は不良であった。
Claims (8)
- オキセタン基および脂環式エポキシ基から選ばれる少なくとも1種の官能基を含む架橋性高分子化合物を架橋してなる重合体(A)と、フッ化ビニリデンをモノマー成分として含む重合体(B)と、溶媒およびリチウム塩とを含み、
前記架橋性高分子化合物の重量平均分子量が1×104〜5×106であり、
前記架橋性高分子化合物は、オキセタン基および脂環式エポキシ基から選ばれる少なくとも1種の官能基を含む重合性モノマーmモルと、ビニル系モノマーnモルとを、モル比m/nが1/20〜2/1の範囲で共重合してなり、
前記ビニル系モノマーのQ値が0〜1.5であり、そのホモポリマーの溶解度パラメータが17〜30であることを特徴とするゲル状電解質。 - オキセタン基および脂環式エポキシ基から選ばれる少なくとも1種の官能基を含む架橋性高分子化合物を架橋してなる重合体(A)と、フッ化ビニリデンをモノマー成分として含む重合体(B)と、溶媒およびリチウム塩とを含み、
前記架橋性高分子化合物の重量平均分子量が1×104〜5×106であり、
前記架橋性高分子化合物は、オキセタン基および脂環式エポキシ基から選ばれる少なくとも1種の官能基を含む重合性モノマーmモルと、他の重合性モノマーnモルとを、モル比m/nが1/20〜2/1の範囲で共重合してなり、
前記他の重合性モノマーが、式(3):
で示されるモノマーであることを特徴とするゲル状電解質。 - 前記フッ化ビニリデンをモノマー成分として含む重合体が、フッ化ビニリデン−ヘキサフルオロプロピレン共重合体である請求項1〜4のいずれかに記載のゲル状電解質。
- ゲル状電解質の全体の重量に対して、前記重合体(A)の重量割合が0.5重量%以上10重量%以下であり、前記重合体(B)の重量割合が5重量%以上30重量%以下である請求項1〜5のいずれかに記載のゲル状電解質。
- 前記溶媒が、環状エステル、環状カーボネート、鎖状カーボネート、環状エーテル、鎖状エーテル、およびニトリル類から選ばれる少なくとも1種の溶媒を含む請求項1〜6のいずれかに記載のゲル状電解質。
- リチウムイオンを吸蔵・放出することができる材料を含む正極と、リチウムイオンを吸蔵・放出することができる材料、金属リチウム、およびリチウムと合金を形成することができる金属材料から選ばれる少なくとも1種の材料を含む負極と、電解質とを備えた電気化学素子であって、
前記電解質が、請求項1〜7のいずれかに記載のゲル状電解質であることを特徴とする電気化学素子。
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