JP5499827B2 - 有機電解液電池用シール剤組成物及び有機電解液電池 - Google Patents
有機電解液電池用シール剤組成物及び有機電解液電池 Download PDFInfo
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- JP5499827B2 JP5499827B2 JP2010074616A JP2010074616A JP5499827B2 JP 5499827 B2 JP5499827 B2 JP 5499827B2 JP 2010074616 A JP2010074616 A JP 2010074616A JP 2010074616 A JP2010074616 A JP 2010074616A JP 5499827 B2 JP5499827 B2 JP 5499827B2
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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
- Sealing Battery Cases Or Jackets (AREA)
- Secondary Cells (AREA)
Description
(1) 1,3−ブタジエン重合体(ポリマーA)と、共役ジエン系モノマーブロックを含むブロック共重合体(ポリマーB)と、前記1,3−ブタジエン重合体(ポリマーA)100重量部に対して0.001〜3重量部の老化防止剤とを含み、前記老化防止剤が、フェノール系老化防止剤とチオエーテル系老化防止剤との組み合わせ、又は、フェノール系老化防止剤と亜リン酸エステル系老化防止剤との組み合わせである、有機電解液電池用シール剤組成物、
(2) 前記1,3−ブタジエン重合体(ポリマーA)の重量平均分子量は20,000〜800,000であることを特徴とする(1)記載の有機電解液電池用シール剤組成物、
(3) さらに炭素数5〜15の有機溶媒を含んでなる(1)または(2)に記載のシール剤組成物、
(4) 発電要素を収納した金属容器の開口部に装着された絶縁ガスケットと金属容器との間、および/又は絶縁ガスケットと封口体との間に(1)〜(3)の何れかに記載の有機電解液電池用シール剤組成物を用いたシール剤層が設けられている有機電解液電池、
(5) 有機電解液電池がリチウム二次電池であることを特徴とする(4)記載の電池
が提供される。
本発明に係る有機電解液電池用シール剤組成物は、1,3−ブタジエン重合体(ポリマーA)と、共役ジエン系モノマーブロックを含むブロック共重合体(ポリマーB)と、1,3−ブタジエン重合体(ポリマーA)100重量部に対して0.001重量部〜3重量部の老化防止剤とを含み、前記老化防止剤が、フェノール系老化防止剤とチオエーテル系老化防止剤との組み合わせ、又は、フェノール系老化防止剤と亜リン酸エステル系老化防止剤との組み合わせであることを特徴とする。
ポリマーAとしては、1,3−ブタジエンモノマーを重合することによって得られる1,3−ブタジエン単独重合体を用いる。重合方法は、溶液重合や乳化重合など公知の方法を用いることができる。1,3−ブタジエン重合体は、シス−1・4結合が多く含まれる高シスブタジエン重合体であっても、トランス−1・4結合が多く含まれる低シスブタジエン重合体であってもよい。例えば溶液重合において用いる触媒によって所望のシス−1・4結合の割合を有する1,3−ブタジエン重合体を得ることができる。このとき、触媒としては、チーグラー系触媒、リチウム系触媒などを挙げることができる。
本発明のシール剤に用いられるブロック共重合体は、共役ジエン系モノマーの重合体ブロック(以下、ジエン系ブロックということがある)と共役ジエン系モノマー以外のモノマーの重合体ブロック(以下、その他のブロックということがある)を少なくとも含むジブロックまたはマルチブロックポリマーである。また、その形状は線状であっても分岐状であってもよい。本発明において用いられるこのようなブロックポリマーは、必ずしも完全なブロックポリマーであることを必要とせず、部分的に不完全なブロックやランダム重合部分を含んでいてもよく、ポリマーとしてブロックが全体の60重量%以上、好ましくは70重量%以上、より好ましくは80重量%以上含んでいればよい。本発明で用いるブロックポリマーを構成する各ブロックは、実質的にそのモノマーの重合によって得られるブロックであればよい。
1,3−ブタジエン重合体(ポリマーA)は、二重結合を主鎖に含むためポリエチレンやポリプロピレン等の二重結合を含まないポリマーと比較して耐オゾン性に劣ることが知られている。また、有機溶媒とポリマーを含んでなるシール剤組成物を塗布乾燥して形成するシール剤層の一部は電解液と接触するため電池性能に悪影響を及ぼす材料を添加すると電池性能が低下するおそれがある。
本発明のシール剤組成物には、上述の1,3−ブタジエン重合体(ポリマーA)、ブロック共重合体(ポリマーB)及び老化防止剤の他に、さらに分散剤、紫外線吸収剤等の成分が含まれていてもよい。これらは後述の絶縁ガスケットの性能を劣化させず、電解液と反応せず、また、電解液に溶解しないものでなければ特に限られない。
有機溶媒としては、1,3−ブタジエン重合体(ポリマーA)及びブロック共重合体(ポリマーB)が溶解可能なものであれば特に制限されないが、揮発性と乾燥しやすさを考慮して、炭素数5〜15の有機溶媒が好ましく、炭素数6〜12の有機溶媒がより好ましい。
本発明の有機電解液電池は、発電要素を収納した金属容器の開口部に装着された絶縁ガスケットと金属容器との間、および/又は絶縁ガスケットと封口体との間に、前記シール剤組成物で形成されたシール剤層が設けられてなる。有機電解液電池に用いる金属容器の素材、発電要素、絶縁ガスケットは、一般に使用されているものでよい。この有機電解液電池は、その発電要素を金属容器に収納され密閉されたものである。
10リットルの攪拌機付きオートクレーブにトルエン5000g、ブタジエン810gを加え、十分攪拌した後、ジエチルアルミニウムクロライド0.27mol、塩化クロム・ピリジン錯体0.6mmolを加え、60℃で3時間攪拌しながら重合した。その後、メタノール100mlを加えて重合を停止した。重合停止後、室温まで冷却した後、重合液を取り出した。得られた重合液を水蒸気凝固した後、60℃で48時間真空乾燥して固体状のポリマー780gを得た。得られたポリマーのMwは390,000であった。
10リットルの攪拌機付きオートクレーブに、n−ブタン/シクロヘキサン=30/70の割合の混合溶剤3750gを入れ、ジブチルエーテル200mmol、n−ブチルリチウム100mmolを存在させ、30℃で1時間、先ずスチレン560gを加えて重合し、続いてイソプレン340gを添加し、反応温度が50℃から60℃の間となるように還流冷却により温度制御しながら1時間30分重合した。続いてジメチルジクロロシラン50mmolを添加し、カップリング反応を行った。その後、メタノール100mlを加えて重合を停止した。重合停止後、室温まで冷却した後、重合液を取り出した。得られた重合液を水蒸気凝固した後、60℃で48時間真空乾燥してブロック共重合体750gを得た。得られたポリマーのMwは190,000であった。
ポリマーA 100重量部、ポリマーB 10重量部、カーボン8重量部を、二軸混錬機を用いて150℃10分間混錬した後、キシレン800重量部に溶解し、さらに表1の組成で老化防止剤を加えて、固形分濃度13重量%のシール剤組成物を得た。
変色:シール剤組成物をガラス板にキャストし、常温で1時間乾燥したのち、80℃で1時間真空乾燥して厚さ50μmにフィルムを得た。該フィルムを電解液(EC+PC+DEC 1:1:1モル比、LiPF6 1モル/L)に60℃で100時間浸漬した。評価基準は、液が透明の場合変色なしとして「◎」、わずかに変色していた場合を「△」、褐色に変色していた場合を「×」とし、表1に示す。フィルムからの溶出物が、電解液のアニオン種と反応して変色をおこしていると考えられるため、変色がないものの方が電池性能を保っていることを示す。
Claims (5)
- 1,3−ブタジエン重合体(ポリマーA)と、共役ジエン系モノマーブロックを含むブ
ロック共重合体(ポリマーB)と、前記1,3−ブタジエン重合体(ポリマーA)100
重量部に対して0.001〜3重量部の老化防止剤とを含み、
前記老化防止剤が、フェノール系老化防止剤とチオエーテル系老化防止剤との組み合わせ、又は、フェノール系老化防止剤と亜リン酸エステル系老化防止剤との組み合わせである、
有機電解液電池用シール剤組成物。 - 前記1,3−ブタジエン重合体(ポリマーA)の重量平均分子量は20,000〜800,000であることを特徴とする請求項1記載の有機電解液電池用シール剤組成物。
- さらに炭素数5〜15の有機溶媒を含んでなる請求項1または2に記載のシール剤組成物。
- 発電要素を収納した金属容器の開口部に装着された絶縁ガスケットと金属容器との間、および/又は絶縁ガスケットと封口体との間に請求項1〜3の何れか一項に記載の有機電解液電池用シール剤組成物を用いたシール剤層が設けられている有機電解液電池。
- 有機電解液電池がリチウム二次電池であることを特徴とする請求項4記載の電池。
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