JP2017027935A - 電極、蓄電池、蓄電装置、及び電子機器 - Google Patents
電極、蓄電池、蓄電装置、及び電子機器 Download PDFInfo
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- JP2017027935A JP2017027935A JP2016133258A JP2016133258A JP2017027935A JP 2017027935 A JP2017027935 A JP 2017027935A JP 2016133258 A JP2016133258 A JP 2016133258A JP 2016133258 A JP2016133258 A JP 2016133258A JP 2017027935 A JP2017027935 A JP 2017027935A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
- H01G11/28—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features arranged or disposed on a current collector; Layers or phases between electrodes and current collectors, e.g. adhesives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
【解決手段】第1の電極と、第2の電極と、を有する蓄電装置であり、第1の電極は、第1の集電体と、第1の活物質層と、を有し、第1の活物質層は、粒子状の活物質と、粒子状の活物質の周囲に設けた空隙と、グラフェンと、結着材と、を有し、粒子状の活物質はシリコンであり、活物質と当該空隙は、グラフェンと結着材により覆われている蓄電装置である。
【選択図】図1
Description
本実施の形態では、本発明の一態様の電極について説明する。
ここで、図1(A)は負極101の断面図を示す。負極101において、負極活物質層107は負極集電体109に接して形成される。図1(B)は図1(A)において破線で囲む領域の拡大図を示す。
また、図2には、上記で説明した負極の構造とは一部の構造が異なる負極の構造について説明する。図2(A)は負極101の断面図を示し、図2(B)は図2(A)において破線で囲む領域の拡大図を示す。
負極活物質121としては、例えばシリコン(Si)など、キャリアイオンとの合金化及び脱合金化が可能な材料が用いられる。シリコンは、黒鉛に比べ、重量あたり約10倍のキャリアイオンと合金化することが可能であるため、理論容量が大きく、蓄電装置の大容量化という点において優れている。
空隙は、グラフェン化合物123と結着材122によって、その形状が維持されている。空隙としては、充電に伴い負極活物質121が膨張する際、その前後の体積の差分を有していれば良い。また空隙は、図1(B)の空隙124に示すように負極活物質を覆うように設ければ良い。具体的には、例えばシリコンを負極活物質として用いた場合、充電に伴う膨張によって、膨張前のシリコンの体積に比べ理論上、2倍以上、場合によっては4倍以上の体積に膨張する。従って、図1(B)における空隙124としては、充電に伴うシリコン粒子の体積の膨張で生じる応力を緩和するために、空隙の体積をシリコン粒子の体積の4倍以上とすることが好ましい。一方で、空隙は負極活物質において電極反応には関与しないため、空隙の体積が大き過ぎると、負極活物質の体積当たりの容量が低下する。そのため、空隙の体積はシリコン粒子の体積の5倍以下であることがさらに好ましい。また、図1(B)の空隙125については、シリコン粒子の体積より小さい体積を有していても良い。また、図2(B)または図2(C)に示すように、負極活物質121の周囲に複数個の空隙を設けても良い。ここで、空隙の体積とは、例えば、空隙の直径から空隙の体積を算出すればよい。または、例えば空隙の断面を観察し、その面積を円に換算し、その直径から体積を算出すればよい。なお、空隙の直径は、SEM(走査型電子顕微鏡)またはTEMによる観察によって測定することができる。
結着材としては、ポリイミド、ポリ塩化ビニル、ポリテトラフルオロエチレン、ポリエチレン、ポリプロピレン、イソブチレン、ポリエチレンテレフタレート、ナイロン、ポリフッ化ビニリデン(PVdF)、ポリアクリロニトリル(PAN)、ポリビニルクロライド、エチレンプロピレンジエンポリマー、ポリ酢酸ビニル、ニトロセルロース、ポリスチレン、ポリアクリル酸メチル、ポリメタクリル酸メチル(ポリメチルメタクリレートPMMA)、ポリアクリル酸ナトリウム、ポリビニルアルコール(PVA)、ポリエチレンオキシド(PEO)、ポリプロピレンオキシド等の材料を用いることが好ましい。また、結着材として、スチレン−ブタジエンゴム(SBR)、スチレン・イソプレン・スチレンゴム、アクリロニトリル・ブタジエンゴム、ブタジエンゴム、エチレン・プロピレン・ジエン共重合体などのジエン系のゴム材料、フッ素ゴムを用いることができる。
本実施の形態では、導電性を有するグラフェン化合物を導電助剤として用いる。また、導電助剤としては、例えば繊維状の炭素材料、金属材料、又は導電性セラミックス材料等を用いることができる。負極活物質層107の総量に対する導電助剤の含有量は、5wt%以上40wt%以下が好ましく、10wt%以上20wt%以下がより好ましい。
負極集電体109には、銅、ステンレス、金、白金、アルミニウム、チタン等の金属、及びこれらの合金など、導電性が高い材料を用いることができる。また負極集電体109に用いる集電体材料としては、リチウム等のキャリアイオンと合金化しない材料が好ましい。また、シリコン、チタン、ネオジム、スカンジウム、モリブデンなどの耐熱性を向上させる元素が添加されたアルミニウム合金を用いることができる。また、シリコンと反応してシリサイドを形成する金属元素で形成してもよい。シリコンと反応してシリサイドを形成する金属元素としては、ジルコニウム、チタン、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、コバルト、ニッケル等がある。負極集電体109は、箔状、板状(シート状)、網状、パンチングメタル状、エキスパンドメタル状等の形状を適宜用いることができる。負極集電体109は、厚さが5μm以上30μm以下のものを用いるとよい。
本発明の一態様に係る負極の作製方法について、図3を用いて以下に説明する。
ステップS101として、シリコンウェハを粉砕して、負極活物質となるシリコン粒子を作製する。
ステップS101の粉砕処理により得たシリコン粒子を加熱処理して、シリコン粒子の表面にシリコン酸化膜を形成する。
次いで、酸化グラフェン、結着材、及びS102で得られたシリコン粒子を混合し、混合物Aを作製する。
ステップS103において作製した混合物Aに含まれる、シリコン粒子表面に形成したシリコン酸化膜をエッチング処理により除去して混合物Bを作製する。その後、混合物Bの洗浄と乾燥を行い、加熱処理を行う。
ステップS104で得られた混合物Bを用いて、スラリーを作製する。
ステップS105において作製したスラリーを用いて、負極集電体109上にスラリーを塗工する。
次いで、スラリーが塗布された負極集電体109の加熱処理を行う。
以上述べた作製工程にて、負極集電体109上に形成された負極活物質層107を有する負極101を形成する。
図4は、図2に示す負極の作製方法のフロー図である。
シリコンウェハを粉砕して、負極活物質となるシリコン粒子を作製する。なお、ステップS201は、ステップS101に記載した工程と同様である。
次いで、S201で作製したシリコン粒子、酸化シリコン粒子、グラフェン化合物、及び結着材を混合し、混合物Aを作製する。
ステップS202において作製した混合物Aに含まれる、酸化シリコン粒子をエッチング処理により除去して混合物Bを作製する。その後、混合物Bの洗浄と乾燥を行い、加熱処理を行う。
ステップS203で得られた混合物Bを用いて、スラリーを作製する。スラリーの作成工程については、ステップS105で記載した工程と同様である。
ステップS204において作製したスラリーを用いて、負極集電体109上にスラリーを塗工する。スラリーの塗工工程については、ステップS106に記載した工程と同様である。
次いで、スラリーが塗布された負極集電体109の加熱処理を行う。加熱処理工程については、ステップS107に記載した工程と同様である。
以上述べた作製工程にて、負極集電体109上に形成された負極活物質層107を有する負極101を形成する。
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5に、蓄電装置の一例として、薄型の蓄電池について示す。図5は、薄型の蓄電池の一例を示す。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。
正極集電体501には、ステンレス、金、白金、アルミニウム、チタン等の金属、及びこれらの合金など、導電性が高く、正極の電位で溶出しない材料を用いることができる。また、シリコン、チタン、ネオジム、スカンジウム、モリブデンなどの耐熱性を向上させる元素が添加されたアルミニウム合金を用いることができる。また、シリコンと反応してシリサイドを形成する金属元素で形成してもよい。シリコンと反応してシリサイドを形成する金属元素としては、ジルコニウム、チタン、ハフニウム、バナジウム、ニオブ、タンタル、クロム、モリブデン、タングステン、コバルト、ニッケル等がある。正極集電体501は、箔状、板状(シート状)、網状、パンチングメタル状、エキスパンドメタル状等の形状を適宜用いることができる。正極集電体501は、厚さが5μm以上30μm以下のものを用いるとよい。また、正極集電体501の表面に、グラファイトなどを用いてアンダーコート層を設けてもよい。
正極活物質層502は、正極活物質の他、正極活物質の密着性を高めるための結着材(バインダ)、正極活物質層502の導電性を高めるための導電助剤等を有してもよい。
導電助剤としては、例えば炭素材料、金属材料、又は導電性セラミックス材料等を用いることができる。また、導電助剤として繊維状の材料を用いてもよい。正極活物質層502の総量に対する導電助剤の含有量は、1wt%以上10wt%以下が好ましく、1wt%以上5wt%以下がより好ましい。
電解液508の溶媒としては、非プロトン性有機溶媒が好ましく、例えば、エチレンカーボネート(EC)、プロピレンカーボネート(PC)、ブチレンカーボネート、クロロエチレンカーボネート、ビニレンカーボネート、γ−ブチロラクトン、γ−バレロラクトン、ジメチルカーボネート(DMC)、ジエチルカーボネート(DEC)、エチルメチルカーボネート(EMC)、ギ酸メチル、酢酸メチル、酪酸メチル、1,3−ジオキサン、1,4−ジオキサン、ジメトキシエタン(DME)、ジメチルスルホキシド、ジエチルエーテル、メチルジグライム、アセトニトリル、ベンゾニトリル、テトラヒドロフラン、スルホラン、スルトン等の1種、又はこれらのうちの2種以上を任意の組み合わせおよび比率で用いることができる。
次に蓄電装置の一例として、コイン型の蓄電池の一例について、図17を参照して説明する。図17(A)はコイン型(単層偏平型)の蓄電池の外観図であり、図17(B)は、その断面図である。
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18を参照して説明する。円筒型の蓄電池600は、図18(A)に示すように、上面に正極キャップ(電池蓋)601を有し、側面および底面に電池缶(外装缶)602を有している。これら正極キャップ601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19および図20に、薄型の蓄電池の構成例を示す。図19(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21乃至図23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池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。
本参考例の負極における負極活物質層は、負極活物質としてシリコンウェハを粉砕したシリコン粒子を用いるが、本発明の一態様で設けたシリコン粒子の周囲に存在する空隙を設けない。
107 負極活物質層
109 負極集電体
111 正極
111a 正極
115 負極
115a 負極
121 負極活物質
122 結着材
123 グラフェン化合物
124 空隙
125 空隙
126 シリコン酸化膜
127 グラフェン
128 ポリイミド
130 電極組立体
131 電極組立体
151 正極集電体
152 正極活物質層
153 セパレータ
155 負極集電体
156 負極活物質層
157 外装体
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
322 正極活物質
323 結着材
331 第1の領域
332 第2の領域
333 第3の領域
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
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
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
992 外装体
993 捲回体
994 負極
995 正極
996 セパレータ
997 リード電極
998 リード電極
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
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
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
8406 電気モーター
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 (9)
- 負極と、正極と、を有し、
前記負極は、集電体と活物質層と、を有し、
前記活物質層は、活物質粒子と、前記活物質粒子の周囲を覆うグラフェン化合物及び結着材と、を有し、
かつ前記活物質粒子と、前記グラフェン化合物と、前記結着材とに接する空隙を有することを特徴とする蓄電装置。 - 負極と、正極と、を有し、
前記負極は、集電体と活物質層と、を有し、
前記活物質層は、活物質粒子と、前記活物質粒子の周囲を覆うグラフェン化合物および結着材と、を有し、
かつ前記活物質粒子と、前記グラフェン化合物と、前記結着材とに接する第1の空隙を有し、
かつ前記グラフェン化合物と、前記結着材とに接する第2の空隙を有することを特徴とする蓄電装置。 - 負極と、正極と、を有し、
前記負極は、集電体と活物質層と、を有し、
前記活物質層は、活物質粒子と、前記活物質粒子の周囲を覆うグラフェン化合物及び結着材と、を有し、
かつ前記活物質粒子と、前記グラフェン化合物と、前記結着材とに接する複数の空隙を有することを特徴とする蓄電装置。 - 請求項1乃至請求項3のいずれか一において、
前記グラフェン化合物は、2層以上100層以下の還元した酸化グラフェンを含み、
前記還元した酸化グラフェンの層間距離は0.335nm以上0.7nm以下であることを特徴とする蓄電装置。 - 請求項1乃至請求項3のいずれか一において、
前記活物質粒子はシリコンである蓄電装置。 - 請求項1乃至請求項3のいずれか一において、
前記結着材は、ポリイミドであることを特徴とする蓄電装置。 - 請求項1乃至請求項3のいずれか一において、
前記活物質粒子は、平均粒子径が0.5μm以上1.5μm以下であることを特徴とする蓄電装置。 - 請求項1乃至請求項3のいずれか一において、
前記活物質粒子は、シリコンウェハを粉砕して作製されることを特徴とする蓄電装置。 - 請求項1乃至請求項8のいずれか一に記載の蓄電装置と、操作ボタンと、表示装置と、を有する電子機器。
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