JP2014112539A - 蓄電装置用電極及び蓄電装置、並びに蓄電装置用電極の作製方法 - Google Patents
蓄電装置用電極及び蓄電装置、並びに蓄電装置用電極の作製方法 Download PDFInfo
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- 239000004642 Polyimide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000002391 graphite-based active material Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000012905 input function Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- ACFSQHQYDZIPRL-UHFFFAOYSA-N lithium;bis(1,1,2,2,2-pentafluoroethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)C(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)C(F)(F)F ACFSQHQYDZIPRL-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
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- 230000036961 partial effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
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- 229920001721 polyimide Polymers 0.000 description 1
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- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002296 pyrolytic carbon Substances 0.000 description 1
- 235000011835 quiches Nutrition 0.000 description 1
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- 230000000979 retarding effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
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- 239000000779 smoke Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000008053 sultones Chemical class 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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
- H01G11/22—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
- H01G11/32—Carbon-based
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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
- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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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- 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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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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
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Abstract
【解決手段】蓄電装置用電極は、集電体と、集電体上に設けられた活物質層と、を有し、活物質層は、複数の粒状の活物質と、酸化ケイ素と、を有し、粒状の活物質はその表面において、他の粒状の活物質と接触する領域を有し、領域を除いた粒状の活物質の表面は、その一部または全部が酸化ケイ素によって被覆されている。
【選択図】図1
Description
本実施の形態では、本発明の一態様に係る蓄電装置用電極について、図1を用いて説明する。
本実施の形態では、蓄電装置用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、蓄電装置用電極を有する蓄電装置およびその作製方法について、図3乃至図7を参照して説明する。
図5(A)は、コイン型(単層偏平型)の二次電池の外観図であり、図5(B)は、その断面図である。
次に、ラミネート型の二次電池の一例について、図6を参照して説明する。
次に、円筒型の二次電池の一例について、図7を参照して説明する。円筒型のリチウムイオン電池500は図7(A)に示すように、上面に正極キャップ(電池蓋)501を有し、側面及び底面に電池缶(外装缶)502を有している。これら正極キャップと電池缶(外装缶)502とは、ガスケット(絶縁パッキン)510によって絶縁されている。
本実施の形態では、蓄電装置としてリチウムイオンキャパシタについて説明する。
本発明の一態様に係る蓄電装置は、電力により駆動する様々な電気機器の電源として用いることができる。
次に、電気機器の一例である携帯情報端末について、図9を用いて説明する。
さらに、電気機器の一例である移動体の例について、図10を用いて説明する。
はじめに、本実施例で用いた電極の作製方法について説明する。
次に、電極A、比較電極B、及び比較電極Cに含まれる黒鉛ついて、ラマン分光法により、ラマンスペクトルを測定した結果について説明する。測定には、(株)堀場製作所の顕微PL装置LabRAMを用い、電極A、比較電極B、比較電極Cのそれぞれについて、3点測定した。
次に、電極A、比較電極B、比較電極Cを用いたハーフセルを形成し、初回不可逆容量を測定した結果について説明する。
次に、電極Aを負極として用い、電解液、及び正極を有するフルセルを組み立てた後、1回充放電してリチウムイオン二次電池Aを作製した。次に、二次電池のサイクル特性を測定した。また、比較電極B及び比較電極Cも同様にして負極として用い、電解液、及び正極を有するフルセルを組み立てた後、1回充放電してリチウムイオン二次電池B、リチウムイオン二次電池Cを作製した。
図14に、電極AについてのSEM(Scanning Electron Microscope)観察像を示す。図14(A)、図14(B)は、一部に酸化ケイ素膜が形成された黒鉛を観察したSEM像である。図14(B)は、図14(A)に示すSEM観察像の一部を拡大したSEM観察像である。観察条件は、加速電圧0.1kV、トップ検出器を用い、リターディング法による低加速電圧の観察を行った。図14に示すように、酸化ケイ素の形成領域は濃いグレー、黒鉛表面は薄いグレー又は白く現れた。
以上のことから、本発明の一態様に係る電極をリチウムイオン電池に適用することにより、リチウムイオン電池の初回不可逆容量が低減することができた。また、リチウムイオン電池の充放電の繰り返しにおいて、充放電の副反応として生じる電解液等の分解反応を最小限に抑制することで、リチウムイオン電池のサイクル特性を向上させることができた。
また、図16に、比較電極E4及び比較電極F4についてのSEM観察像を示す。図16(A)に、比較電極E4のSEM観察像を示し、図16(B)に、比較電極F4についてのSEM観察像を示す。なお、図16(A)に示すSEM観察像と、図16(B)に示すSEM観察像は、同じ倍率で観察したものである。
102 集電体
103 活物質層
111 活物質
112 被膜
113 バインダ
114 空隙
200 負極
201 負極集電体
202 負極活物質層
211 負極活物質
212 被膜
213 バインダ
215 グラフェン
250 正極
251 正極集電体
252 正極活物質層
261 正極活物質
262 被膜
263 バインダ
265 グラフェン
300 リチウムイオン電池
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
400 リチウムイオン電池
401 正極集電体
402 正極活物質層
403 正極
404 負極集電体
405 負極活物質層
406 負極
407 セパレータ
408 電解液
409 外装体
500 リチウムイオン電池
501 正極キャップ
502 電池缶
503 正極端子
504 正極
505 セパレータ
506 負極
507 負極端子
508 絶縁板
509 絶縁板
511 PTC素子
512 安全弁機構
600 表示装置
601 筐体
602 表示部
603 スピーカ部
604 蓄電装置
610 照明装置
611 筐体
612 光源
613 蓄電装置
614 天井
615 側壁
616 床
617 窓
620 室内機
621 筐体
622 送風口
623 蓄電装置
624 室外機
630 電気冷凍冷蔵庫
631 筐体
632 冷蔵室用扉
633 冷凍室用扉
634 蓄電装置
650 タブレット型端末
651 筐体
652 表示部
652a 表示部
652b 表示部
653 スイッチ
654 電源スイッチ
655 スイッチ
656 操作スイッチ
657a 領域
657b 領域
658 操作キー
659 ボタン
660 太陽電池
670 充放電制御回路
671 バッテリー
672 DCDCコンバータ
673 コンバータ
680 電気自動車
681 バッテリー
682 制御回路
683 駆動装置
684 処理装置
701 曲線
702 曲線
703 曲線
751 黒鉛
752 酸化ケイ素膜
Claims (6)
- 集電体と、
前記集電体上に設けられた活物質層と、を有し、
前記活物質層は、複数の粒状の活物質と、酸化ケイ素と、を有し、
前記粒状の活物質はその表面において、他の粒状の活物質と接触する領域を有し、
前記領域を除いた前記粒状の活物質の表面は、その一部または全部が前記酸化ケイ素によって被覆されていることを特徴とする蓄電装置用電極。 - 請求項1において、
前記活物質は、ラマン分光法により観測されるラマンスペクトルのラマンシフトが1360cm−1のピーク強度I1360とラマンシフトが1580cm−1のピーク強度I1580との比I1360/I1580が0.4以下である炭素材料であることを特徴とする蓄電装置用電極。 - 請求項1又は2のいずれか一に記載された蓄電装置用電極を用いた蓄電装置。
- 複数の粒状の活物質とバインダとを含むスラリーを形成し、
集電体上に、前記スラリーを塗布した後、乾燥させることで活物質層を形成し、
前記活物質層を、溶媒と有機ケイ素化合物と触媒とを含む処理液に含浸させることで、前記複数の粒状の活物質の表面に、前記処理液を付着させ、
前記複数の粒状の活物質の表面に付着した前記処理液の溶媒を蒸発させ、前記有機ケイ素化合物を加水分解及び縮合反応させることにより、前記複数の粒状の活物質の表面に酸化ケイ素を被覆することを特徴とする蓄電装置用電極の作製方法。 - 請求項4において、
前記有機ケイ素化合物は、エチルポリシリケート、メチルポリシリケート、プロピルポリシリケート、ブチルポリシリケート、テトラメトキシシラン、テトラエトキシシラン、テトラブトキシシラン、又はテトラプロポキシシランのいずれかであることを特徴とする蓄電装置用電極の作製方法。 - 請求項4又は5において、
前記処理液は、酸化ケイ素が、0.1wt%以上40wt%以下の濃度で含まれることを特徴とする蓄電装置用電極の作製方法。
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- 2013-10-28 WO PCT/JP2013/079658 patent/WO2014073461A1/en active Application Filing
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Also Published As
Publication number | Publication date |
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WO2014073461A1 (en) | 2014-05-15 |
TW201436349A (zh) | 2014-09-16 |
US20190326069A1 (en) | 2019-10-24 |
KR102195511B1 (ko) | 2020-12-28 |
CN104781954B (zh) | 2017-08-08 |
DE112013005307T5 (de) | 2015-07-23 |
TWI664775B (zh) | 2019-07-01 |
US20140127567A1 (en) | 2014-05-08 |
US10388467B2 (en) | 2019-08-20 |
CN104781954A (zh) | 2015-07-15 |
KR20150082556A (ko) | 2015-07-15 |
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