JP6664184B2 - 電極、及び電極の作製方法 - Google Patents
電極、及び電極の作製方法 Download PDFInfo
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- JP6664184B2 JP6664184B2 JP2015201154A JP2015201154A JP6664184B2 JP 6664184 B2 JP6664184 B2 JP 6664184B2 JP 2015201154 A JP2015201154 A JP 2015201154A JP 2015201154 A JP2015201154 A JP 2015201154A JP 6664184 B2 JP6664184 B2 JP 6664184B2
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- active material
- power storage
- positive electrode
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- electrode
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- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000004772 tellurides Chemical class 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(II) oxide Inorganic materials [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01G11/30—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
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
-
- 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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- 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
- Y02E60/13—Energy storage using capacitors
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Description
本実施の形態では、本発明の一態様に係る電極について、図1を用いて説明する。
本実施の形態では、電極の作製方法の一例について、図2を参照して説明する。本実施の形態では、スプレードライヤを用いて、活物質の表面に被膜を形成する。
電極の作製フローを図2(B)に示す。
作製方法1では、活物質、シリコーン、及び第1の溶媒を含む混合液をスプレードライヤに取り込んで、活物質の表面に被膜を形成する例を説明したが、当該混合液に導電助剤を加えてもよい。以下に、電極の作製方法の他の一例について説明する。なお、混合液の構成以外は、作製方法1を参照することができるので、重複する説明は省略する。
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4に、蓄電装置の一例として、薄型(ラミネート型とも呼ぶ)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し、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6を用いて説明する。図6(A)はコイン型(単層偏平型)の蓄電池の外観図であり、図6(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7を参照して説明する。円筒型の蓄電池600は図7(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8および図9に、薄型の蓄電池の構成例を示す。図8(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10、図11、および図12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。
実施例Aは、被膜を有する活物質を用いて作製した電極である。まず、人造黒鉛MCMBと、KR−400(信越化学工業株式会社製)と、97%エタノール水溶液とを用いて、混合液を形成した。実施の形態2で説明したとおり、混合液を用意する段階で、黒鉛に対するKR−400の割合が1wt%となるように、KR−400の量を決定した。当該混合液をスプレードライヤに取り込み、スプレーシリンダ内の温度を100℃、窒素雰囲気として、噴射された混合液中の溶媒を瞬時に蒸発させ、被膜を有する黒鉛の粉末を得た。
実施例Bは、KR−9218(信越化学工業株式会社製)を用いて、被膜を有する黒鉛を形成し、作製した。使用したシリコーンを除き、実施例Bの構成及び作製方法は、実施例Aと同じであるので、ここでは説明を省略する。
KR−9218を用いて形成した被膜を有する黒鉛を、減圧雰囲気下、300℃で10時間加熱した。実施例B´は、該被膜を有する黒鉛を用い、実施例Bの作製方法と同様にして作製した。
実施例Cは、黒鉛に対するKR−400の割合が、実施例Aと異なる。具体的には、実施例Cでは、混合液を用意する段階で、黒鉛に対するKR−400の割合が0.5wt%となるように、KR−400の量を決定した。KR−400の割合を除き、実施例Cの構成及び作製方法は、実施例Aと同じであるので、ここでは説明を省略する。
実施例Dは、黒鉛に対するKR−9218の割合が、実施例Bと異なる。具体的には、実施例Dでは、混合液を用意する段階で、黒鉛に対するKR−9218の割合が0.5wt%となるように、KR−9218の量を決定した。KR−9218の割合を除き、実施例Dの構成及び作製方法は、実施例Bと同じであるので、ここでは説明を省略する。
実施例A〜Dが、被膜を有する黒鉛を用いて作製された電極であるのに対し、比較例Eは、被膜を有さない黒鉛を用いて作製した電極である。比較例Eでは、活物質として人造黒鉛MCMB、導電助剤としてVGCF(登録商標)、バインダとしてCMC−Na及びSBRを用いて、黒鉛、VGCF(登録商標)、CMC−Na、及びSBRの重量比が、96:1:1:2となるようにペーストを形成した。ペーストの溶媒としては、純水を用いた。
実施例A及び実施例Bの作製に用いた、スプレードライ工程により得た被膜を有する黒鉛を、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、断面観察を行った。断面観察は、高分解能透過電子顕微鏡(TEM、日立製作所製「H9000−NAR」)を用いて、加速電圧を200kVとして行った。
次に、ToF−SIMS分析により、実施例Aの作製に用いた、被膜を有する黒鉛の表面の構造解析を行い、被膜に用いたシリコーンの構成要素(二次イオンであるSiCH3O2イオン)の分布を評価した。
次に、実施例A、実施例B’及び比較例Eに対して、集電体から活物質層を剥離する際に必要な力(剥離に要する力)の測定を行った。
初回充放電効率の測定を行うため、実施例C、実施例D、比較例Eを正極として組み込んだハーフセルを作製した。なお、ハーフセルとは、正極にLi金属以外の活物質を用い、負極にLi金属を用いたリチウムイオン電池のセルを示す。負極にはリチウム金属を用い、電解液はECと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。セパレータには、PP(ポリプロピレン)及びGF/C(ガラス繊維ろ紙)を用いた。ここで便宜上、実施例Cを組み込んだハーフセルを、ハーフセルCと呼ぶこととする。また、実施例Dを組み込んだハーフセルをハーフセルDと呼ぶこととする。また、比較例Eを組み込んだハーフセルをハーフセルEと呼ぶこととする。
次に、実施例Aを負極として用い、電解液、セパレータ、及び正極を有するフルセルを組み立てた後、1回充放電して二次電池Aを作製し、二次電池のサイクル試験を行った。また、実施例Bについても、同様に負極として用い、電解液、セパレータ、及び正極を有するフルセルを組み立てた後、1回充放電して二次電池Bを作製し、サイクル試験を行った。また、二次電池Aおよび二次電池Bと同様に、比較例Eを用いた二次電池Eを作製し、サイクル試験を行った。
実施例Fは、KR−251を用いて、実施例Cまたは実施例Dと同様の方法で作製した電極である。
実施例Fについて評価するため、実施例1と同様の条件で、実施例Fを組み込んだハーフセルを作製した。実施例Fを組み込んだハーフセルの放電曲線および実施例Dまたは比較例Eを組み込んだハーフセルの放電曲線を図22に示す。また、実施例F、実施例Dおよび比較例Eの、作製条件を表2にまとめる。
102 集電体
103 活物質層
111 活物質
112 被膜
113 バインダ
114 導電助剤
115 空隙
121 二流体ノズル
122 加熱手段
123 スプレーシリンダ
124 サイクロン
125 容器
126 エアフィルタ
127 排気装置
141 活物質
142 被膜
143 バインダ
144 導電助剤
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 リチウムイオン電池
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
521 正極活物質
522 被膜
523 バインダ
524 導電助剤
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
980 蓄電池
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
1000 電極
1001 集電体
1002 活物質層
1003 粘着テープ
1004 端部
1005 端部
1401 黒鉛
1402 被膜
1403 膜
1404 膜
1405 被膜
1406 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
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
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 (2)
- 集電体と、活物質層と、を有し、
前記活物質層は、粒状の形状を有する複数の活物質と、シリコーンを含む膜と、導電助剤と、バインダと、を有し、
前記複数の活物質のいずれか一の活物質は、他の活物質と接触する領域と、前記導電助剤と接触する領域と、前記バインダと接触する領域と、を有し、
前記シリコーンを含む膜は、前記一の活物質を被覆する領域を有し、
前記シリコーンは、メトキシ基、メチル基又はフェニル基の少なくともいずれか一を含むことを特徴とする電極。 - 活物質と、シリコーンと、第1の溶媒と、を有する混合液を形成する工程と、
前記混合液を噴射して前記第1の溶媒を蒸発させることにより、被膜を有する活物質を形成する工程と、
前記被膜を有する活物質、導電助剤、バインダ、及び第2の溶媒を有するペーストを形成する工程と、
集電体上に前記ペーストを塗布し、前記第2の溶媒を蒸発させることで活物質層を形成する工程と、を有し、
前記シリコーンは、メトキシ基、メチル基又はフェニル基の少なくともいずれか一を含むことを特徴とする電極の作製方法。
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