JP2019179631A - 電池電極用組成物の製造方法 - Google Patents
電池電極用組成物の製造方法 Download PDFInfo
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- JP2019179631A JP2019179631A JP2018067219A JP2018067219A JP2019179631A JP 2019179631 A JP2019179631 A JP 2019179631A JP 2018067219 A JP2018067219 A JP 2018067219A JP 2018067219 A JP2018067219 A JP 2018067219A JP 2019179631 A JP2019179631 A JP 2019179631A
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
水溶性高分子の残りについては、第二工程において粒子状バインダーと同時に添加してもよいし、第三工程として、粒子状バインダーを添加終了後に添加してもよい。
活物質100重量部(固形分)に対して、粒子状バインダーを0.1〜10重量部(固形分)含有することが好ましく、0.3〜7重量部含有することがより好ましい。0.1重量部未満では、結着力が劣る傾向にあり、10重量部を超えると電池として組み立てた際に過電圧が著しく上昇しサイクル特性が劣る傾向にある。
活物質100重量部(固形分)に対して、水溶性高分子を、活物質100重量部(固形分)に対して0.05〜5重量部(固形分)含有することが好ましく、0.5〜4重量部(固形分)含有することがより好ましい。0.05重量部未満であると結着力が劣る傾向にあり、4重量部を超えるとサイクル特性が劣る傾向にある。
上述の共重合体としては、電池電極用組成物の分散性や結着力の観点から、エチレン性不飽和カルボン酸単量体に由来する構造単位を含有することが好ましい。このような共重合体は、エチレン性不飽和カルボン酸単量体と、エチレン性不飽和カルボン酸単量体と共重合可能な他の単量体と共重合することによって得られる。中でもエチレン性不飽和カルボン酸単量体由来の構造単位を5質量%以上35質量%以下含有する共重合体を使用することで、さらに活物質への被覆性を向上させることができる。
本発明の電池電極用組成物を集電体に塗布する方法としては、リバースロール法、コンマバー法、グラビヤ法、エアーナイフ法など任意のコーターヘッドを用いることができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できる。
A:カルボキシ変性スチレン−ブタジエンラテックス:イタコン酸由来の構造単位を1質量%含有
B:カルボキシ変性スチレン−ブタジエンラテックス:イタコン酸由来の構造単位を2質量%及びアクリル酸由来の構造単位を4質量%含有
(実施例1)
負極活物質として平均粒子径が20μmの天然黒鉛を使用し、天然黒鉛100重量部(固形分)に対して、第一工程として、水溶性高分子としてカルボキシメチルセルロースナトリウム(第一工業製薬株式会社製セロゲンEP、以下CMC)の水溶液を0.1重量部(固形分)添加し、組成物の固形分が65%となるように適量の水を添加して、混練した。十分混練した後、粒子状バインダーAを2.0重量部(固形分)添加して混練した。続いて、CMC水溶液を0.9重量部(固形分)と全固形分が40%となるように適量の水を加えて混練し、負極用組成物を調製した。負極用組成物を集電体となる厚さ20μmの銅箔に塗布し、130℃で5分間乾燥し、塗工層の厚みが60μmの負極シートを得た。
CMC水溶液の添加量及び粒子状バインダーの種類と添加量を表1に示す通りに変更した以外は、実施例1と同様の方法で負極シートを得た。比較例2については、電池電極用組成物の分散性が悪く、一部凝集した部分が認められた。
粒子状バインダーが活物質の表面をより多く被覆することにより、充放電を繰り返した際のサイクル特性が向上することから、上記の方法で得られた各負極シートにおいて、下記の方法により共重合体ラテックスの活物質への被覆性を評価した。すなわち、上記で得られた各負極シート(圧延前のもの) を1cm四方に切り、四酸化オスミウム雰囲気下で染色した後、走査型電子顕微鏡(日本電子製、商品名: JSM−6510LA)を用いて、5000倍にて観察した。SEM観察画像において、活物質の面積に対し、活物質上に粒子状バインダーが付着している面積を目視で確認し、下記のとおり評価した。なお、SEM観察画像8画面のうち、最も平均的な画像を選び、相対評価を行った。結果を表1に示す。
比較例1の活物質表面の粒子状バインダーによる被覆度合を基準として、
A : 被覆度合が3割以上向上した。
B : 被覆度合が2割以上3割未満向上した。
C : 被覆度合が1割以上2割未満向上した。
D : 被覆度合がほぼ同等もしくは低下していた。
Claims (2)
- 活物質、粒子状バインダー、及び水溶性高分子を含有する電池電極用組成物を製造するにあたり、該粒子状バインダーを組成物に添加する前までに水溶性高分子の全量を添加しないことを特徴とする電池電極用組成物の製造方法。
- 全使用量の3質量%以上60質量%以下の水溶性高分子を組成物中に添加した後に、粒子状バインダーを添加することを特徴とする、請求項1に記載の電池電極用組成物の製造方法。
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Citations (4)
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WO2011001665A1 (ja) * | 2009-06-30 | 2011-01-06 | パナソニック株式会社 | 非水電解質二次電池用負極及びその製造方法並びに非水電解質二次電池 |
JP2013229163A (ja) * | 2012-04-25 | 2013-11-07 | Shin Etsu Chem Co Ltd | 非水電解質二次電池用負極及び非水電解質二次電池 |
JP2015013658A (ja) * | 2013-07-03 | 2015-01-22 | アサヒビール株式会社 | 充填設備 |
JP2015138658A (ja) * | 2014-01-22 | 2015-07-30 | トヨタ自動車株式会社 | リチウム二次電池用電極の製造方法および造粒物 |
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WO2011001665A1 (ja) * | 2009-06-30 | 2011-01-06 | パナソニック株式会社 | 非水電解質二次電池用負極及びその製造方法並びに非水電解質二次電池 |
JP2013229163A (ja) * | 2012-04-25 | 2013-11-07 | Shin Etsu Chem Co Ltd | 非水電解質二次電池用負極及び非水電解質二次電池 |
JP2015013658A (ja) * | 2013-07-03 | 2015-01-22 | アサヒビール株式会社 | 充填設備 |
JP2015138658A (ja) * | 2014-01-22 | 2015-07-30 | トヨタ自動車株式会社 | リチウム二次電池用電極の製造方法および造粒物 |
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