JP6899629B2 - 耐熱性多孔層形成用組成物、耐熱性多孔層を含む分離膜、分離膜を用いた電気化学電池、および分離膜の製造方法 - Google Patents
耐熱性多孔層形成用組成物、耐熱性多孔層を含む分離膜、分離膜を用いた電気化学電池、および分離膜の製造方法 Download PDFInfo
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- JP6899629B2 JP6899629B2 JP2015257082A JP2015257082A JP6899629B2 JP 6899629 B2 JP6899629 B2 JP 6899629B2 JP 2015257082 A JP2015257082 A JP 2015257082A JP 2015257082 A JP2015257082 A JP 2015257082A JP 6899629 B2 JP6899629 B2 JP 6899629B2
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- separation membrane
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- porous layer
- electrochemical battery
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Description
ポリビニリデンフルオリド系ホモポリマー(ソレフ(登録商標)5120、ソルベイスペシャルティポリマーズ社製)7重量%、およびジメチルアセトアミド(DMAc、デジュンケミカルズ&メタルズ社製)93重量%を混合し、これを40℃で3時間撹拌して第1の溶液を製造した。
ポリビニリデンフルオリド系コポリマー(KF9300、クレハ社製)7重量%、およびジメチルアセトアミド(DMAc、デジュンケミカルズ&メタルズ社製)93重量%を混合し、これを40℃で3時間撹拌して第2の溶液を製造した。
ポリメチルメタクリレート10重量%、およびアセトン90重量%を混合し、これを40℃で1時間撹拌して第3の溶液を製造した。
平均粒径D50500nmのアルミナ(LS235、日本軽金属社製)をアセトンに25重量%で添加後、25℃で2時間ビーズミルを用いて分散してアルミナ分散液を製造した。
エトキシ化ペンタエリスリトールテトラアクリレート(PE―044、ハノンケミカルズ社製)0.7重量%、ベンゾイルパーオキシド0.035重量%、製造例1で製造した第1の溶液6.6重量%、製造例4で製造したアルミナ分散液55.4重量%、およびアセトン37.265重量%を混合して耐熱性多孔層組成液を製造した。厚さが7μmのポリエチレン素材(SKI)の両面に組成液をそれぞれ2μm厚さでコーティングした後、80℃で約30秒間乾燥した。ここで、100℃で24時間、熱硬化させ、総厚さ11μm程度の分離膜を作製した。
実施例1の第1の溶液6.6重量%の代わりに、製造例2で製造した第2の溶液6.6重量%を用いたことを除いては、実施例1と同一の方法で分離膜を作製した。
エトキシ化ペンタエリスリトールテトラアクリレート、ベンゾイルパーオキシドを用いず、第1の溶液33.6重量%および第3の溶液10.3重量%、アルミナ分散液38.4重量%およびアセトン17.7重量%を用いたことを除いては、実施例1と同一の方法で分離膜を作製した。
エトキシ化ペンタエリスリトールテトラアクリレート、ベンゾイルパーオキシドを用いず、第2の溶液33.6重量%および第3の溶液10.3重量%、アルミナ分散液38.4重量%およびアセトン17.7重量%を用いたことを除いては、実施例2と同一の方法で分離膜を作製した。
エトキシ化ペンタエリスリトールテトラアクリレート、ベンゾイルパーオキシドを用いず、第1の溶液10.3重量%および第3の溶液33.6重量%、アルミナ分散液38.4重量%およびアセトン17.7重量%を用いたことを除いては、実施例1と同一の方法で分離膜を作製した。
エトキシ化ペンタエリスリトールテトラアクリレート、ベンゾイルパーオキシドを用いず、第2の溶液10.3重量%および第3の溶液33.6重量%、アルミナ分散液38.4重量%およびアセトン17.7重量%を用いたことを除いては、実施例2と同一の方法で分離膜を作製した。
Claims (12)
- 多孔性基材と、
前記多孔性基材の一面あるいは両面に形成された耐熱性多孔層と、を含み、
前記耐熱性多孔層は、下記化学式2または3のモノマー、オリゴマーまたはポリマーからなる群より選ばれる単独またはこれらの混合物で形成される架橋型バインダー、ポリビニリデンフルオリド系ポリマー、ポリメチルメタクリレート、ポリアクリロニトリル、ポリビニルピロリドン、ポリビニルアセテート、ポリエチレンオキシド、セルロースアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート、シアノエチルプルラン、シアノエチルポリビニルアルコール、シアノエチルセルロース、シアノエチルスクロース、プルラン、カルボキシメチルセルロース、およびアクリロニトリル−ブタジエン−スチレン共重合体からなる群より選ばれる単独またはそれらの混合物であるバインダー樹脂、および無機粒子を含み、
前記多孔性基材の厚さは5μm〜15μmであり、
前記耐熱性多孔層の厚さは2μm〜8μmである、電気化学電池分離膜。
化学式2において、a 5 ないしa 8 はそれぞれ独立した1ないし10の整数であり、化学式3において、R 5 は炭素数1ないし10のアルキル基であり、n 5 ないしn 7 はそれぞれ独立した1ないし5の整数であり、a 9 ないしa 12 はそれぞれ独立した1ないし10の整数である。 - 前記無機粒子は、前記耐熱性多孔層の全重量を基準として50重量%ないし95重量%である、請求項1に記載の電気化学電池分離膜。
- 前記バインダー樹脂は、ポリビニリデンフルオリド系ポリマーであり、
前記ポリビニリデンフルオリド系ポリマーは、ポリビニリデンフルオリドホモポリマーおよびポリビニリデンフルオリド―ヘキサフルオロプロピレン系コポリマーの中から選ばれる単独またはそれらの混合物である、請求項1に記載の電気化学電池分離膜。 - 前記モノマー、オリゴマーまたはポリマーと、前記バインダー樹脂との重量比は8:2ないし2:8である、請求項1に記載の電気化学電池分離膜。
- 多孔性基材と、
前記多孔性基材の一面あるいは両面に形成された耐熱性多孔層と、を含み、
前記耐熱性多孔層は、下記化学式2または3のモノマー、オリゴマーまたはポリマーで形成される架橋型バインダー、ポリビニリデンフルオリド系ポリマー、ポリメチルメタクリレート、ポリアクリロニトリル、ポリビニルピロリドン、ポリビニルアセテート、ポリエチレンオキシド、セルロースアセテート、セルロースアセテートブチレート、セルロースアセテートプロピオネート、シアノエチルプルラン、シアノエチルポリビニルアルコール、シアノエチルセルロース、シアノエチルスクロース、プルラン、カルボキシメチルセルロース、およびアクリロニトリル−ブタジエン−スチレン共重合体からなる群より選ばれる単独またはそれらの混合物であるバインダー樹脂、および無機粒子を含み、
前記多孔性基材の厚さは5μm〜15μmであり、
前記耐熱性多孔層の厚さは2μm〜8μmであり、
200℃で10分間放置した後の引張強度が50kgf/cm2ないし350kgf/cm2である電気化学電池分離膜。
化学式2において、a 5 ないしa 8 はそれぞれ独立した1ないし10の整数であり、化学式3において、R 5 は炭素数1ないし10のアルキル基であり、n 5 ないしn 7 はそれぞれ独立した1ないし5の整数であり、a 9 ないしa 12 はそれぞれ独立した1ないし10の整数である。
- 前記電気化学電池分離膜は200℃で10分間放置時、破断しないことを特徴とする、請求項5に記載の電気化学電池分離膜。
- 前記無機粒子が前記耐熱性多孔層の全重量を基準として50重量%ないし95重量%である、請求項5に記載の電気化学電池分離膜。
- 前記バインダー樹脂はポリビニリデンフルオリド系ポリマーであり、
前記ポリビニリデンフルオリド系ポリマーは、ポリビニリデンフルオリドホモポリマーおよびポリビニリデンフルオリド―ヘキサフルオロプロピレン系コポリマーから選ばれる単独またはそれらの混合物である、請求項5に記載の電気化学電池分離膜。 - 通気性が、300sec/100cc以下である、請求項5に記載の電気化学電池分離膜。
- 150℃で60分間放置後、機械方向および横断方向の熱収縮率が、それぞれ10%以下である、請求項5に記載の電気化学電池分離膜。
- 陽極、陰極、分離膜および電解質を含む電気化学電池であって、前記分離膜は、請求項1ないし10のいずれか1つに記載の電気化学電池分離膜を用いた電気化学電池。
- 前記電気化学電池は、リチウム二次電池である、請求項11に記載の電気化学電池。
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KR101551757B1 (ko) | 2014-12-30 | 2015-09-10 | 삼성에스디아이 주식회사 | 다공성 내열층 조성물, 다공성 내열층을 포함하는 분리막, 상기 분리막을 이용한 전기 화학 전지, 및 상기 분리막의 제조 방법 |
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