JP3070796B2 - Manufacturing method of polarized electrode - Google Patents
Manufacturing method of polarized electrodeInfo
- Publication number
- JP3070796B2 JP3070796B2 JP4244853A JP24485392A JP3070796B2 JP 3070796 B2 JP3070796 B2 JP 3070796B2 JP 4244853 A JP4244853 A JP 4244853A JP 24485392 A JP24485392 A JP 24485392A JP 3070796 B2 JP3070796 B2 JP 3070796B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- binder
- polarizable electrode
- electrode
- double layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
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
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
- Carbon And Carbon Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、電気二重層キャパシタ
や電池あるいはエレクトロクロミックディスプレイなど
に用いる活性炭からなる分極性電極およびその製造法に
関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polarizable electrode made of activated carbon for use in electric double layer capacitors, batteries, electrochromic displays, and the like, and a method for producing the same.
【０００２】[0002]
【従来の技術】従来の技術を電気二重層キャパシタを例
にとり説明する。2. Description of the Related Art The prior art will be described by taking an electric double layer capacitor as an example.
【０００３】電気二重層キャパシタは分極性電極として
活性炭粉末もしくは活性炭繊維を用い、活性炭と電解液
との界面に生じる電気二重層を利用した大容量コンデン
サである。電気二重層キャパシタは小型で大容量の充電
可能なコンデンサとして、マイコン、メモリ、タイマー
のバックアップ用に広く用いられている。An electric double layer capacitor is a large-capacity capacitor using an activated carbon powder or an activated carbon fiber as a polarizable electrode and utilizing an electric double layer generated at an interface between activated carbon and an electrolyte. Electric double layer capacitors are widely used as backup capacitors for microcomputers, memories, and timers as small, large-capacity rechargeable capacitors.
【０００４】このような電気二重層キャパシタには従来
大別して次の２種類が存在する。すなわち、硫酸水溶液
のような水溶液系電解液を用いたものと、プロピレンカ
ーボネートのような有機溶媒に電解質を添加した有機溶
液系電解液を用いたものである。Conventionally, the following two types of such electric double layer capacitors are roughly classified. That is, a solution using an aqueous solution electrolyte such as a sulfuric acid aqueous solution, and a solution using an organic solution electrolyte obtained by adding an electrolyte to an organic solvent such as propylene carbonate.
【０００５】粉末状活性炭を用いる場合は一般に電解質
としての希硫酸を混合し、スラリー状のペーストにして
キャパシタに組み込んでいる。この場合、活性炭の充填
密度を上げ、また活性炭どうしの接触抵抗を良好にする
ために、分極性電極を加圧して密封する必要があり、そ
のため大きなケースが必要になる、製造プロセスが複雑
になる、ハンドリング性が悪いなどの課題があった。[0005] When powdered activated carbon is used, dilute sulfuric acid as an electrolyte is generally mixed, and a slurry paste is incorporated into a capacitor. In this case, in order to increase the packing density of the activated carbon and improve the contact resistance between the activated carbons, it is necessary to pressurize and seal the polarizable electrode, which requires a large case and complicates the manufacturing process. And poor handling properties.
【０００６】繊維状活性炭を用いる場合は、粉末状活性
炭よりもさらに充填密度が低く、接触抵抗も大きいとい
う課題がある。When fibrous activated carbon is used, there are problems that the packing density is lower and the contact resistance is higher than that of powdered activated carbon.
【０００７】そこで、構造が簡単でエネルギー密度が高
く、電極加圧手段を不要とするような分極性電極とし
て、固形状の活性炭電極の開発が提案されている。Therefore, the development of a solid activated carbon electrode has been proposed as a polarizable electrode having a simple structure, a high energy density and not requiring an electrode pressing means.
【０００８】図３は、活性炭粉末あるいは活性炭繊維と
結合剤との乾式混合物を加圧、成型した後、不活性ガス
雰囲気下で加熱し結合剤を炭化することにより得られた
活性炭粉末あるいは活性炭繊維と炭素から構成される固
形状活性炭電極（例、特開昭６３−２２６０１９号公報
参照）の断面を示している。活性炭微粒子１は結合剤２
によって接着され、結合剤２を炭化することにより結合
している。各粒子間には空孔３がある。FIG. 3 shows activated carbon powder or activated carbon fiber obtained by pressurizing and molding a dry mixture of activated carbon powder or activated carbon fiber and a binder, and then heating in an inert gas atmosphere to carbonize the binder. 1 shows a cross section of a solid activated carbon electrode composed of carbon and carbon (for example, see JP-A-63-226019). Activated carbon fine particles 1 are binder 2
And are bonded by carbonizing the binder 2. There are holes 3 between each particle.
【０００９】[0009]
【発明が解決しようとする課題】しかし、活性炭１と結
合剤２を乾式混合して製造した固形状活性炭電極の場
合、活性炭１および結合剤２がそれぞれ独立して分散す
るため活性炭１と結合剤２の接触面積が小さく、固形化
する際に活性炭電極の強度を上げようとすると多量の結
合剤２が必要となる。その結果活性炭１の含有率が少な
くなり、電気二重層キャパシタを構成した場合、容量密
度は小さくなり、内部抵抗は大きくなってしまうという
課題がある。However, in the case of a solid activated carbon electrode produced by dry-mixing the activated carbon 1 and the binder 2, the activated carbon 1 and the binder 2 are dispersed independently, so that the activated carbon 1 and the binder 2 are dispersed independently. 2 has a small contact area, and a large amount of binder 2 is required to increase the strength of the activated carbon electrode during solidification. As a result, when the content of the activated carbon 1 is reduced and an electric double layer capacitor is formed, there is a problem that the capacitance density is reduced and the internal resistance is increased.
【００１０】そこで本発明は上記の従来の固形状活性炭
電極の課題を解消し、かつ電気二重層キャパシタを構成
した場合、飛躍的に改善された容量密度および内部抵抗
をもつ固形状分極性電極を提供することを目的とする。Accordingly, the present invention solves the above-mentioned problems of the conventional solid activated carbon electrode and, when an electric double layer capacitor is formed, provides a solid polarizable electrode having a dramatically improved capacity density and internal resistance. The purpose is to provide.
【００１１】[0011]
【課題を解決するための手段】本発明は、結合剤を溶剤
に溶解して得られた溶液に活性炭を分散して得られた溶
液から前記溶剤を除去して得られた活性炭と結合剤混合
品を、加圧、成型、炭化して形成することを特徴とする
分極性電極の製造法である。 SUMMARY OF THE INVENTION The present invention relates to a method for preparing a binder by using a solvent.
Solution obtained by dispersing activated carbon in the solution
Activated carbon obtained by removing the solvent from the liquid and binder mixture
The product is formed by pressing, molding and carbonizing
This is a method for manufacturing a polarizable electrode.
【００１２】[0012]
【００１３】[0013]
【作用】本発明では、活性炭の一部が結合剤で被覆され
ることにより活性炭と結合剤の親和性が高まり、活性炭
と結合剤が強固に結合することによって電極の強度が増
し、また活性炭間の接触抵抗が低減されることによって
内部抵抗が低くなり、急速充電および大電流放電に適し
た信頼性の高い分極性電極を実現することができる。In the present invention, the affinity between the activated carbon and the binder is increased by coating a part of the activated carbon with the binder, and the strength of the electrode is increased by the strong binding between the activated carbon and the binder. , The internal resistance is reduced by reducing the contact resistance, and a highly reliable polarizable electrode suitable for quick charge and large current discharge can be realized.
【００１４】[0014]
【実施例】以下、本発明の実施例について図面を参照し
て説明する。Embodiments of the present invention will be described below with reference to the drawings.
【００１５】図１に、本発明の一実施例に掛かる分極性
電極の断面図を示した。活性炭微粒子１は結合剤２によ
って表面が薄く被覆されており、結合剤２どうしが互い
に結合することにより活性炭微粒子１が密に結合してい
る。結合剤２を炭化することにより活性炭微粒子１およ
び結合剤２は強固に結合し高い電気伝導性も保たれる。
各粒子間には空孔３がある。 （実施例１）結合剤としてのフェノール樹脂をエタノー
ルに溶解して得られた溶液に、フェノール樹脂に対して
重量比で４倍量のフェノール系活性炭粉末を混合し分散
させて得られた溶液から、前記エタノールを除去して活
性炭と結合剤の高分散混合品を得た。前記混合品を、プ
レス圧１２０kg/cm2、プレス温度１８０℃の条件下でプ
レス成形して分極性電極の材料を形成し、不活性ガス雰
囲気下で８００℃で加熱しフェノール樹脂を炭化するこ
とによって分極性電極を得た。FIG. 1 is a sectional view of a polarizable electrode according to an embodiment of the present invention. The surface of the activated carbon fine particles 1 is thinly covered with a binder 2, and the activated carbon fine particles 1 are tightly bound by binding of the binders 2 to each other. By carbonizing the binder 2, the activated carbon fine particles 1 and the binder 2 are firmly bound and high electric conductivity is maintained.
There are holes 3 between each particle. (Example 1) A solution obtained by dissolving a phenolic resin as a binder in ethanol and mixing and dispersing a phenolic activated carbon powder in a weight ratio of 4 times the amount of the phenolic resin to a solution obtained by dissolving the solution in the ethanol. Then, the ethanol was removed to obtain a highly dispersed mixture of activated carbon and a binder. The mixture is press-molded under the conditions of a press pressure of 120 kg / cm 2 and a press temperature of 180 ° C. to form a polarizable electrode material, and heated at 800 ° C. in an inert gas atmosphere to carbonize the phenol resin. Thus, a polarizable electrode was obtained.
【００１６】本実施例で製造した分極性電極について、
曲げ強度、および比抵抗を測定し（表１）に示した。With respect to the polarizable electrode manufactured in this embodiment,
The bending strength and the specific resistance were measured (Table 1).
【００１７】また、電気二重層キャパシタの電極として
の特性を測るため、図２に示した電気二重層キャパシタ
の試験セルを試作して、静電容量、内部抵抗を測定し、
（表１）に示した。本実施例で製造した分極性電極を直
径２０mm、厚さ１．５mmの円柱状に切り出した１対の分
極性電極４に電解液として３０wt%硫酸水溶液を含浸
し、ポリエチレン製のセパレータ６を介して対向させ、
集電体５と絶縁性ガスケット７を用いて電気二重層キャ
パシタを形成した。Further, in order to measure the characteristics of the electric double layer capacitor as an electrode, a test cell of the electric double layer capacitor shown in FIG. 2 was prototyped, and the capacitance and internal resistance were measured.
The results are shown in (Table 1). A pair of polarizable electrodes 4 obtained by cutting out the polarizable electrode manufactured in this example into a cylindrical shape having a diameter of 20 mm and a thickness of 1.5 mm is impregnated with a 30 wt% sulfuric acid aqueous solution as an electrolytic solution, and is interposed through a polyethylene separator 6. To face each other,
An electric double layer capacitor was formed using the current collector 5 and the insulating gasket 7.
【００１８】従来例との比較のため、以下に示した比較
例により製造した分極性電極についても同様に、曲げ強
度、比抵抗、および電気二重層キャパシタの電極として
静電容量、内部抵抗を測定し（表１）に示した。 （比較例１）フェノール系の活性炭粉末に、結合剤とし
てのフェノール樹脂と、フェノール樹脂に対して重量比
で４倍量のフェノール系活性炭粉末を乾式混合して得ら
れた活性炭と結合剤の混合品を、プレス圧１２０kg/c
m2、プレス温度１８０℃の条件下でプレス成形して分極
性電極の材料を形成し、不活性ガス雰囲気下で８００℃
で加熱しフェノール樹脂を炭化することによって分極性
電極を得た。For comparison with the conventional example, the bending strength, the specific resistance, and the capacitance and the internal resistance of the electrodes of the electric double layer capacitor were measured for the polarizable electrodes manufactured in the following comparative examples. (Table 1). (Comparative Example 1) Mixing of activated carbon and binder obtained by dry-mixing phenolic activated carbon powder with phenolic resin as a binder and phenolic activated carbon powder in a weight ratio of 4 times the phenolic resin to the phenolic resin The product is pressed at 120kg / c
m 2 , press molding under the condition of a pressing temperature of 180 ° C. to form a material for the polarizable electrode,
To obtain a polarizable electrode by carbonizing the phenol resin.
【００１９】[0019]
【表１】 [Table 1]
【００２０】（表１）から明らかなように、本実施例の
分極性電極は従来例に比較して、曲げ強度が大きく比抵
抗が小さくなっていることがわかる。また、電気二重層
キャパシタの分極性電極として用いた場合、本実施例の
分極性電極は従来例に比較して静電容量が大きく内部抵
抗が小さくなることがわかる。As is clear from Table 1, the polarizable electrode of the present embodiment has a higher bending strength and lower specific resistance than the conventional example. Also, when used as a polarizable electrode of an electric double layer capacitor, it can be seen that the polarizable electrode of this embodiment has a larger capacitance and a lower internal resistance than the conventional example.
【００２１】なお、上記実施例では、活性炭が粉末状の
場合について説明したが、活性炭が粒状、繊維状の場合
についても同様の効果が得られる。In the above embodiment, the case where the activated carbon is in the form of powder has been described. However, the same effect can be obtained when the activated carbon is in the form of granules or fibers.
【００２２】また、上記実施例では、集電体材料および
分極性電極材料として粉末状の材料を用いたが、これに
限定されるものではなく、顆粒状，繊維状でも良い。In the above embodiment, a powdery material is used as the current collector material and the polarizable electrode material. However, the present invention is not limited to this, and may be granular or fibrous.
【００２３】また、上記実施例では、分極性電極材料と
してフェノール樹脂系の活性炭を用いたが、活性炭であ
ればこれに限定されるものではなく、フェノール樹脂に
ついても、硬化温度以下で溶融する熱硬化型のバインダ
であればこれに限定されるものではない。In the above embodiment, phenolic resin-based activated carbon was used as the polarizable electrode material. However, the activated carbon is not limited to this. It is not limited to this as long as it is a curable binder.
【００２４】また、上記実施例では、電解液として３０
ｗｔ％の硫酸水溶液を用いたが、これに限定されるもの
ではなく、有機系の電解液でも良い。Further, in the above embodiment, 30% is used as the electrolytic solution.
Although the aqueous solution of sulfuric acid of wt% was used, the present invention is not limited to this, and an organic electrolytic solution may be used.
【００２５】また、上記実施例では、セパレータとして
ポリエチレンの多孔膜を用いたが、非電子電導性で、イ
オン透過性であればこれに限定されるものではない。In the above embodiment, a polyethylene porous film is used as the separator. However, the separator is not limited to this as long as it is non-electroconductive and ion-permeable.
【００２６】また、本発明の分極性電極は、上記のよう
な電気二重層キャパシタのみならず、電池あるいはエレ
クトロクロミックディスプレイ等に広く使用できる。The polarizable electrode of the present invention can be widely used not only for the electric double layer capacitor as described above, but also for a battery or an electrochromic display.
【００２７】[0027]
【発明の効果】以上述べたところから明らかなように、
本発明では、活性炭の一部が結合剤で被覆されることに
より活性炭と結合剤の親和性が高まり、活性炭と結合剤
が強固に結合することによって電極の強度が増し、また
活性炭間の接触抵抗が低減されることによって内部抵抗
が低くなり、急速充電および大電流放電に適した信頼性
の高い分極性電極を実現することができる。As is apparent from the above description,
In the present invention, a part of the activated carbon is coated with the binder to increase the affinity between the activated carbon and the binder, and the activated carbon and the binder are firmly bonded to each other, thereby increasing the strength of the electrode, and the contact resistance between the activated carbons Is reduced, the internal resistance is reduced, and a highly reliable polarizable electrode suitable for quick charge and large current discharge can be realized.
【図１】本発明の一実施例によるプロセスを経て形成さ
れた分極性電極の断面図である。FIG. 1 is a cross-sectional view of a polarizable electrode formed through a process according to one embodiment of the present invention.
【図２】電気二重層キャパシタ試験セルの断面図であ
る。FIG. 2 is a sectional view of an electric double layer capacitor test cell.
【図３】比較例によるプロセスを経て形成された分極性
電極の断面図である。FIG. 3 is a cross-sectional view of a polarizable electrode formed through a process according to a comparative example.
１ 活性炭微粒子 ２ 結合剤 ３ 空孔 ４ 分極性電極 ５ 集電体 ６ セパレータ ７ ガスケット DESCRIPTION OF SYMBOLS 1 Activated carbon fine particles 2 Binder 3 Void 4 Polarized electrode 5 Current collector 6 Separator 7 Gasket
フロントページの続き (72)発明者 吉田 昭彦 大阪府門真市大字門真1006番地 松下電 器産業株式会社内 (56)参考文献 特開 昭63−226019（ＪＰ，Ａ) 特開 昭63−107011（ＪＰ，Ａ) 特開 平３−80165（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) H01G 9/058 G02F 1/155 H01M 4/04 Continuation of front page (72) Inventor Akihiko Yoshida 1006 Kadoma, Kazuma, Osaka Prefecture Inside Matsushita Electric Industrial Co., Ltd. (56) References JP-A-62-226019 (JP, A) JP-A-63-107011 (JP) (A) JP-A-3-80165 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB name) H01G 9/058 G02F 1/155 H01M 4/04
Claims (1)
性炭を分散して得られた溶液から前記溶剤を除去して得
られた活性炭と結合剤混合品を、加圧、成型、炭化して
形成することを特徴とする分極性電極の製造法。1. A solution obtained by dissolving a binder in a solvent.
Removing the solvent from the solution obtained by dispersing
Pressurized, molded and carbonized the activated carbon and binder mixture
A method for producing a polarizable electrode, comprising:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4244853A JP3070796B2 (en) | 1992-09-14 | 1992-09-14 | Manufacturing method of polarized electrode |
| US08/064,933 US5381303A (en) | 1992-05-20 | 1993-05-20 | Electric double layer capacitor and method for manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4244853A JP3070796B2 (en) | 1992-09-14 | 1992-09-14 | Manufacturing method of polarized electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0697004A JPH0697004A (en) | 1994-04-08 |
| JP3070796B2 true JP3070796B2 (en) | 2000-07-31 |
Family
ID=17124959
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4244853A Expired - Fee Related JP3070796B2 (en) | 1992-05-20 | 1992-09-14 | Manufacturing method of polarized electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3070796B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4288465B2 (en) | 2000-11-17 | 2009-07-01 | 株式会社Ｋｒｉ | Non-aqueous lithium secondary battery |
| KR20110109810A (en) * | 2009-01-28 | 2011-10-06 | 도요 알루미늄 가부시키가이샤 | Carbon-coated aluminum member and method for producing the same |
-
1992
- 1992-09-14 JP JP4244853A patent/JP3070796B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0697004A (en) | 1994-04-08 |
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