JP2015159107A - 電極、蓄電装置および電子機器 - Google Patents
電極、蓄電装置および電子機器 Download PDFInfo
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- JP2015159107A JP2015159107A JP2015006326A JP2015006326A JP2015159107A JP 2015159107 A JP2015159107 A JP 2015159107A JP 2015006326 A JP2015006326 A JP 2015006326A JP 2015006326 A JP2015006326 A JP 2015006326A JP 2015159107 A JP2015159107 A JP 2015159107A
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- electrode
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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Abstract
【解決手段】活物質、第1のバインダーおよび第2のバインダーを有する電極であって、活物質の比表面積をS[m2/g]とし、電極に含まれる活物質の重量、電極に含まれる第1のバインダーの重量、および、電極に含まれる第2のバインダーの重量をそれぞれa、bおよびcとし、{(b+c)/(a+b+c)}×100÷Sが0.3以上であることを特徴とする電極である。
【選択図】なし
Description
本実施の形態では、本発明の一態様に係る電極およびその作製方法について説明する。
図1(A)は電極100を俯瞰した図であり、図1(B)は図1(A)の破線で囲んだ部分の断面を示す図である。電極100は、集電体101上に活物質層102が設けられた構造である。なお、図では集電体101の両面に活物質層102が設けられているが、集電体101の片面のみに活物質層102が設けられていてもよい。また、活物質層102は、活物質を有する。
次に、本発明の一態様である電極100の作製方法について説明する。
本実施の形態では、本発明の一態様である電極を用いた蓄電装置の一例を示す。
図2(A)に、蓄電装置の一例として、薄型の蓄電池について示す。薄型の蓄電池は、可撓性を有する構成とすれば、可撓性を有する部位を少なくとも一部有する電子機器に実装すれば、電子機器の変形に合わせて蓄電池も曲げることもできる。
次に蓄電装置の一例として、コイン型の蓄電池の一例を図10を用いて説明する。図10(A)はコイン型(単層偏平型)の蓄電池の外観図であり、図10(B)は、その断面図である。
[円筒型蓄電池]
次に蓄電装置の一例として、円筒型の蓄電池を示す。円筒型の蓄電池について、図11を参照して説明する。円筒型の蓄電池600は図11(A)に示すように、上面に正極キャップ(電池蓋)601を有し、側面及び底面に電池缶(外装缶)602を有している。これら正極キャップと電池缶(外装缶)602とは、ガスケット(絶縁パッキン)610によって絶縁されている。
図12乃至図13に、薄型の蓄電池の構成例を示す。図12(A)に示す捲回体993は、負極994と、正極995と、セパレータ996と、を有する。
また、蓄電システムの構造例について、図14、図15、図16を用いて説明する。ここで蓄電システムとは、例えば、蓄電装置を搭載した機器を指す。
本実施の形態では、可撓性を有する蓄電装置を電子機器に実装する例について説明する。
本実施の形態では、蓄電装置を搭載することのできる電子機器の一例を示す。
本実施の形態では、車両に蓄電装置を搭載する例を示す。
黒鉛を活物質に用いて電極を作製した。用いた黒鉛の比表面積の測定値、および平均粒径を表1に示す。
次に、作製した電極のうち、電極A−1および電極C−1について、飛行時間型二次イオン質量分析法(ToF−SIMS)による分析を行った。図21に、Naイオン、Na2C2HOイオンおよびC6H5イオンのマッピング測定の結果を示す。電極A−1の分析結果を図21(A)に、電極C−1の分析結果を図21(B)に示す。観察領域は19.5μm角である。
次に、電極A−1について、FIB(Focused Ion Beam System:集束イオンビーム加工観察装置)を用いて薄片化加工した後、透過型電子顕微鏡(TEM:Transmission Electron Microscope)により断面の観察を行った。TEM観察結果を図34に示す。図34(A)は、電極の断面の一部を観察した結果であり、図34(B)はさらに高い倍率で観察を行った結果である。図34(B)の結果より、黒鉛151をバインダー152が覆っている様子がわかる。また、その厚さはおおよそ4nm以上13nm以下と見積もられた。なお観察をしやすくするため、保護膜153を電極の表面に形成している。
実施例1で作製した電極に、対極としてリチウム金属を組み合わせてハーフセルを作製した。特性の評価にはCR2032タイプ(直径20mm高さ3.2mm)のコイン型の蓄電池を用いた。セパレータにはポリプロピレンとWhatman社製のガラス繊維濾紙であるGF/Cを積層して用いた。また電解液には、エチレンカーボネート(EC)とジエチルカーボネート(DEC)とを体積比で3:7の割合で混合した混合溶液中へ六フッ化リン酸リチウム(LiPF6)を1モル/リットルの濃度で溶解したものを用いた。正極缶及び負極缶として、ステンレス(SUS)で形成されているものを用いた。
正極として、正極A乃至正極Dの4条件を用いた。正極Aは、カーボンコートを施したLiFePO4(以下C/LiFePO4)、酸化グラフェンおよびPVDFを、C/LiFePO4:酸化グラフェン:PVDF=94.2:0.8:5.0(weight%)の配合とし、溶媒としてNMPを用いて電極用のスラリーを作製した。用いたC/LiFePO4の比表面積は約25m2/gであった。正極Bは、LiFePO4、酸化グラフェンおよびPVDFを、LiFePO4:酸化グラフェン:PVDF=94.4:0.6:5.0(weight%)の配合とし、溶媒としてNMPを用いて電極用のスラリーを作製した。用いたLiFePO4の比表面積は約9m2/gであった。正極Cは、平均粒径が6.8μmのLiCoO2と、ABおよびPVDFを、LiCoO2:AB:PVDF=85.0:8.0:7.0(weight%)の配合とし、溶媒としてNMPを用いて電極用のスラリーを作製した。
次に、作製した正極および負極を用いて、単層の薄型蓄電池を作製した。外装体として熱溶着樹脂で覆われたアルミのフィルムを用いた。電極面積は、正極が20.5cm2、負極が23.8cm2であった。また、セパレータには25μm厚のポリプロピレン(PP)を用いた。
ここで、セルR’について691サイクルの充放電を行った後に解体を行い、電極のTEM観察を行った。691回目の放電容量は128.4mAh/gであった。なお、セルの解体、FIB装置への導入およびTEM装置への導入は、不活性雰囲気下で行った。
次に、実施例1で記載した電極A−2−2の条件を用いた負極と、実施例3で記載した正極を組み合わせて蓄電池を作製し、温度特性およびレート特性を評価した。正極として、実施例3で記載した正極Aを用いた蓄電池をセルVとし、正極として、平均粒径が6.8μmのLiCoO2と、ABおよびPVDFを、LiCoO2:AB:PVDF=90.0:5.0:5.0weight%の配合とした正極Eを用いた蓄電池をセルWとする。セルVおよびセルWに用いた電解液、正極還元条件および容量比は表6に示す。電解液の条件および還元条件については実施例3の記載を参照する。
まず負極を作製した。活物質として表1に示す黒鉛Aを用いた。それぞれの電極において、黒鉛、VGCF−H、CMC−NaおよびSBRの割合は黒鉛:VGCF−H:CMC−Na:SBR=96:1:1:2(重量比)とした。
次に、活物質をLiFePO4として、正極を作製した。
次に、作製した各負極と、各正極と、を用い、表7に記載のセル1乃至8を作製した。単層の薄型蓄電池を作製した。ここで単層とは、セパレータを介して向かい合う正極と負極を一組有することを指す。
次に、作製した蓄電池のサイクル特性の評価を行った。初回充放電は、0.2Cのレートで定電流充放電した。その後、0.5Cのレートで定電流充放電を繰り返すサイクル試験をおこなった。充放電の上限電圧を4.0V、下限電圧は2Vとした。また、測定温度は60℃で行った。202サイクル目、およびその後200サイクル毎に0.2Cのレートで充放電を行った。
表9に示す負極1および負極2を作製した。いずれの負極も、黒鉛として表1に示す黒鉛Aを用いた。負極1を作製するためのスラリーは、黒鉛、VGCF−H、CMC−Na、SBR、および水を用いて作製した。負極1において、黒鉛、VGCF−H、CMC−NaおよびSBRの割合は黒鉛:VGCF−H:CMC−Na:SBR=96:1:1:2(重量比)とした。また、負極2を作製するためのスラリーは、黒鉛、CMC−Na、SBR、および水を用いて作製した。負極2において、黒鉛、CMC−NaおよびSBRの割合は黒鉛:CMC−Na:SBR=97:1:2(重量比)とした。
次に、活物質をLiFePO4として、正極を作製した。
次に、作製した各負極と、各正極と、を用い、積層型の薄型蓄電池として表7に記載のセル1乃至8を作製した。セパレータを介して正極と負極とが10組、向かい合うように正極および負極を配置した。
次に、作製した蓄電池の曲げ伸ばし試験を行った。曲げ試験前、および1000回、3000回、6000回、10000回の曲げを行った後に充放電を行った。得られた放電容量を図39に示す。図39の横軸は、曲げ回数を示す。
101 集電体
102 活物質層
151 黒鉛
152 バインダー
153 保護膜
154 保護膜
203 正極活物質
300 蓄電池
301 正極缶
302 負極缶
303 ガスケット
304 正極
305 正極集電体
306 正極活物質層
307 負極
308 負極集電体
309 負極活物質層
310 セパレータ
500 蓄電池
501 正極集電体
502 正極活物質層
503 正極
504 負極集電体
505 負極活物質層
506 負極
507 セパレータ
508 電解液
509 外装体
510 正極リード電極
511 負極リード電極
512 溶接領域
513 湾曲部
514 封止部
521 グラフェン
522 正極活物質
600 蓄電池
601 正極キャップ
602 電池缶
603 正極端子
604 正極
605 セパレータ
606 負極
607 負極端子
608 絶縁板
609 絶縁板
610 ガスケット
611 PTC素子
612 安全弁機構
900 回路基板
910 ラベル
911 端子
912 回路
913 蓄電池
914 アンテナ
915 アンテナ
916 層
917 層
918 アンテナ
919 端子
920 表示装置
921 センサ
922 端子
951 端子
952 端子
981 フィルム
982 フィルム
990 蓄電池
991 外装体
994 負極
995 正極
996 セパレータ
997 リード電極
998 リード電極
1101 リチウムイオン二次電池
1102 充電器
1103 負荷
1700 曲面
1701 平面
1702 曲線
1703 曲率半径
1704 曲率中心
1800 曲率中心
1801 フィルム
1802 曲率半径
1803 フィルム
1804 曲率半径
1805 電極・電解液などを含む内容物
2103 活物質
2104 バインダー
2105 カチオン
2106 溶媒分子
2107 被膜
7100 携帯表示装置
7101 筐体
7102 表示部
7103 操作ボタン
7104 蓄電装置
7200 携帯情報端末
7201 筐体
7202 表示部
7203 バンド
7204 バックル
7205 操作ボタン
7206 入出力端子
7207 アイコン
7300 表示装置
7304 表示部
7400 携帯電話機
7401 筐体
7402 表示部
7403 操作ボタン
7404 外部接続ポート
7405 スピーカ
7406 マイク
7407 蓄電装置
7408 リード電極
7409 集電体
8000 表示装置
8001 筐体
8002 表示部
8003 スピーカ部
8004 蓄電装置
8021 充電装置
8022 ケーブル
8024 蓄電装置
8100 照明装置
8101 筐体
8102 光源
8103 蓄電装置
8104 天井
8105 側壁
8106 床
8107 窓
8200 室内機
8201 筐体
8202 送風口
8203 蓄電装置
8204 室外機
8206 モーター
8300 電気冷凍冷蔵庫
8301 筐体
8302 冷蔵室用扉
8303 冷凍室用扉
8304 蓄電装置
8400 自動車
8401 ヘッドライト
8500 自動車
9600 タブレット型端末
9625 スイッチ
9626 スイッチ
9627 電源スイッチ
9628 操作スイッチ
9629 留め具
9630 筐体
9630a 筐体
9630b 筐体
9631 表示部
9631a 表示部
9631b 表示部
9632a 領域
9632b 領域
9633 太陽電池
9634 充放電制御回路
9635 蓄電体
9636 DCDCコンバータ
9637 コンバータ
9638 操作キー
9639 ボタン
9640 可動部
Claims (14)
- 集電体、活物質、第1のバインダーおよび第2のバインダーを有する電極であって、
前記活物質の比表面積をS[m2/g]とし、
前記電極に含まれる前記活物質の重量、前記電極に含まれる前記第1のバインダーの重量、および、前記電極に含まれる前記第2のバインダーの重量をそれぞれa、bおよびcとし、
下記数式(1)で定義されるAが0.3以上であることを特徴とする電極。
- 請求項1において、
前記電極は、前記活物質と接する第1の膜を有し、
前記第1の膜は、前記活物質と接する領域を有し、
前記第1の膜は、2nm以上20nm以下の厚さである領域を有し、
前記第1の膜は、水溶性高分子を有することを特徴とする電極。 - 請求項1または2において、
前記活物質は、粒子状の形状を有し、
前記活物質の比表面積Sは0.2m2/g以上7.0m2/g以下であることを特徴とする電極。 - 請求項1乃至請求項3のいずれか一項において、
前記第1のバインダーは、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、または、ジアセチルセルロースを有することを特徴とする電極。 - 請求項1乃至請求項4のいずれか一項において、
前記第2のバインダーは、スチレンモノマーまたはブタジエンモノマーを有することを特徴とする電極。 - 請求項2乃至請求項5のいずれか一項において、
前記活物質は黒鉛を有することを特徴とする電極。 - 請求項1乃至請求項6のいずれか一項に記載の電極と、
第2の電極と、
を有する蓄電装置であって、
前記電極は、正極または負極の一方として動作させることができる機能を有し、
前記第2の電極は、正極または負極の他方として動作させることができる機能を有することを特徴とする蓄電装置。 - 第1の電極および電解液を有する蓄電装置であって、
前記第1の電極は、集電体および活物質層を有し、
前記活物質層は、活物質、第1の膜および第2の膜を有し、
前記第1の膜は、前記活物質と接する領域を有し、
前記第2の膜は、第1の膜と接する領域を有し、
前記第1の膜は、水溶性高分子を有し、
前記第2の膜は、リチウム、フッ素、酸素および炭素を有し、
前記電解液は、リチウム、フッ素、酸素および炭素を有することを特徴とする蓄電装置。 - 請求項8において、
前記活物質は、粒子状の形状を有し、
前記活物質の比表面積Sは0.2m2/g以上7.0m2/g以下であることを特徴とする蓄電装置。 - 請求項8または請求項9において、
前記水溶性高分子は、カルボキシメチルセルロース、メチルセルロース、エチルセルロース、ヒドロキシプロピルセルロース、または、ジアセチルセルロースを有することを特徴とする蓄電装置。 - 請求項8乃至請求項10のいずれか一項において、
前記第1の膜はスチレンモノマーまたはブタジエンモノマーを有することを特徴とする蓄電装置。 - 請求項8乃至請求項11のいずれか一項において、
前記活物質は黒鉛を有することを特徴とする蓄電装置。 - 請求項8乃至請求項12のいずれか一項において、
前記蓄電装置は第2の電極を有し、
前記第1の電極は負極として動作させることができる機能を有し、
前記第2の電極は正極として動作させることができる機能を有し、
下記数式(2)で定義されるRは20以上90以下であることを特徴とする蓄電装置。
- 請求項7乃至請求項13のいずれか一項に記載の蓄電装置と、
表示装置と、
を有することを特徴とする電子機器。
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- 2015-01-19 KR KR1020150008588A patent/KR20150088191A/ko not_active Application Discontinuation
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- 2021-10-14 US US17/501,462 patent/US11735736B2/en active Active
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JP2003157849A (ja) * | 2001-11-21 | 2003-05-30 | Toyota Central Res & Dev Lab Inc | リチウム二次電池用負極およびそれを用いたリチウム二次電池 |
WO2013146766A1 (ja) * | 2012-03-30 | 2013-10-03 | 日本電気株式会社 | リチウムイオン二次電池 |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2017112102A (ja) * | 2015-12-10 | 2017-06-22 | 株式会社半導体エネルギー研究所 | 蓄電装置、蓄電装置の作製方法及び電子機器 |
US11264648B2 (en) | 2015-12-10 | 2022-03-01 | Semiconductor Laboratory Energy Co., Ltd. | Power storage device, method for manufacturing power storage device, and electronic device |
US11942602B2 (en) | 2015-12-10 | 2024-03-26 | Semiconductor Energy Laboratory Co., Ltd. | Power storage device, method for manufacturing power storage device, and electronic device |
CN107026270A (zh) * | 2016-01-29 | 2017-08-08 | 株式会社半导体能源研究所 | 蓄电池、电池管理单元和电子设备 |
JP2017139224A (ja) * | 2016-01-29 | 2017-08-10 | 株式会社半導体エネルギー研究所 | 蓄電池、電池制御ユニット、および電子機器 |
JP2021170538A (ja) * | 2016-01-29 | 2021-10-28 | 株式会社半導体エネルギー研究所 | 蓄電池、電池制御ユニットおよび電子機器 |
CN107026270B (zh) * | 2016-01-29 | 2022-02-11 | 株式会社半导体能源研究所 | 蓄电池、电池管理单元和电子设备 |
JP7284215B2 (ja) | 2016-01-29 | 2023-05-30 | 株式会社半導体エネルギー研究所 | 蓄電池、電池制御ユニットおよび電子機器 |
Also Published As
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US10529990B2 (en) | 2020-01-07 |
US20200144621A1 (en) | 2020-05-07 |
US20220037666A1 (en) | 2022-02-03 |
JP2022037103A (ja) | 2022-03-08 |
US11735736B2 (en) | 2023-08-22 |
US9735430B2 (en) | 2017-08-15 |
KR20210137979A (ko) | 2021-11-18 |
US20170338491A1 (en) | 2017-11-23 |
JP2023103453A (ja) | 2023-07-26 |
KR20150088191A (ko) | 2015-07-31 |
JP2020129546A (ja) | 2020-08-27 |
US11152622B2 (en) | 2021-10-19 |
US20150207148A1 (en) | 2015-07-23 |
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