JPH0770448B2 - Method of manufacturing polarizable electrodes - Google Patents
Method of manufacturing polarizable electrodesInfo
- Publication number
- JPH0770448B2 JPH0770448B2 JP62059366A JP5936687A JPH0770448B2 JP H0770448 B2 JPH0770448 B2 JP H0770448B2 JP 62059366 A JP62059366 A JP 62059366A JP 5936687 A JP5936687 A JP 5936687A JP H0770448 B2 JPH0770448 B2 JP H0770448B2
- Authority
- JP
- Japan
- Prior art keywords
- activated carbon
- polarizable electrode
- electric double
- carbon fiber
- 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
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 239000003990 capacitor Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical group CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 238000007750 plasma spraying Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
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
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
Description
【発明の詳細な説明】 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に用いる分極性電極の製造
法に関する。TECHNICAL FIELD The present invention relates to a method for producing a polarizable electrode used in an electric double layer capacitor, a battery or an electrochromic display.
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。ペーパ状の分極性電極としては特開昭59−93216号
公報にしめされているものがある。図に示すように、こ
のものは活性炭繊維とバインダーとから構成されたペー
パ状の分極性電極１の片面にアルミニウム，ニッケル等
の導電層２を形成し、セパレータ３を介し相対向させ、
これらを電解液とともに金属ケース４と封口板５および
両者を絶縁するガスケット６によって密封したものであ
る。2. Description of the Related Art Conventional technology will be described by taking an electric double layer capacitor as an example. As a paper-like polarizable electrode, there is one described in JP-A-59-93216. As shown in the figure, this one has a conductive layer 2 made of aluminum, nickel or the like formed on one surface of a paper-like polarizable electrode 1 composed of activated carbon fibers and a binder, and made to face each other via a separator 3,
These are sealed together with an electrolytic solution by a metal case 4, a sealing plate 5, and a gasket 6 that insulates both.
また活性炭繊維布を分極性電極に用いるものは比表面積
が2500m2/gと大きくでき、また不純物も少なく電気二重
層キャパシタに適しているが活性炭粉末と比較すると大
変高価であり、加圧しないと空隙率が90％以上占めてお
り（加圧しても60％以上占める）空間部分のロスが大き
い。以上のように空間部分が多いため、繊維一体どうし
の接触が少なく、接触抵抗が大きくなる。In addition, the one using activated carbon fiber cloth for the polarizable electrode has a large specific surface area of 2500 m 2 / g, and it is suitable for electric double layer capacitors with few impurities, but it is very expensive compared to activated carbon powder and must be pressurized. Porosity occupies 90% or more (occupies 60% or more even when pressurized) and the loss in the space is large. Since there are many space portions as described above, there is less contact between the fibers and the contact resistance increases.
さらに活性炭粉末をフッ素樹脂で結合させ集電体に保持
させ分極性電極としたものがある。Further, there is a polarizable electrode in which activated carbon powder is bound with a fluororesin and held on a current collector.
発明が解決しようとする問題点 上記のような構成の分極性電極はペーパ状の場合強度を
高めるためにバインダーの含有量を多くなり、抵抗値が
大きいためインピーダンスも高くなりまた純度が低く使
用電圧を高くできない。また、活性炭繊維布の場合空間
効率が低く高価である。活性炭粉末を用いた場合でもバ
インダーの含有量が多くなり抵抗値が大きくなる。Problems to be Solved by the Invention In the case of a paper-like polarizable electrode having the above-described structure, the content of the binder is increased to increase the strength, the resistance is large, the impedance is also high, and the purity is low and the operating voltage is low. Can't be high Further, the activated carbon fiber cloth has a low space efficiency and is expensive. Even when activated carbon powder is used, the content of the binder increases and the resistance value increases.
問題点を解決するための手段 本発明は、上記問題点を解決するため、活性炭粉末ある
いは活性炭繊維とフェノール樹脂との混合物を不活性雰
囲気下で加熱しフェノール樹脂を炭化し活性炭粉末ある
いは活性炭繊維と炭素とから分極性電極を製造したもの
である。Means for Solving Problems The present invention, in order to solve the above problems, a mixture of activated carbon powder or activated carbon fiber and a phenol resin is heated under an inert atmosphere to carbonize the phenol resin and activated carbon powder or activated carbon fiber. It is a polarizable electrode manufactured from carbon.
作用 上記の構成により、分極性電極の活性炭繊維密度を高め
抵抗を低減しエネルギー密度を高くするとともに、急速
充電に適し、信頼性の高い分極性電極を実現することが
できる。Action With the above configuration, it is possible to realize a highly reliable polarizable electrode suitable for rapid charging, while increasing the activated carbon fiber density of the polarizable electrode to reduce the resistance and increase the energy density.
実施例 実施例以下本発明の実施例を説明する。なお、本発明の
実施例の製法になる分極性電極を図に示す構造の電気二
重層キャパシタを構成し諸特性を比較している。EXAMPLES Examples Examples of the present invention will be described below. In addition, the polarizable electrodes according to the manufacturing method of the embodiment of the present invention are used to construct an electric double layer capacitor having the structure shown in FIG.
（実施例１） 比表面積2000m2/gの活性炭繊維（フェノール系）とレゾ
ール型フェノール樹脂とを第１表に示す比率で混合した
ものを100℃で１時間硬化後窒素ガス雰囲気下昇温速度4
0℃/hrで900℃まで加熱しフェノール樹脂を炭化した。
尚、900℃では５時間保持した。上記成型体は厚みが0.6
mm,直径6mmである。表にはそれぞれの組成混合物の熱処
理後の収率，気孔率を付記しておく。このようにして得
られた分極性電極の片面にアルミニウム層をプラズマ溶
射法を用い200μｍ形成した。このものを用い図に示し
たコイン型キャパシタを構成した。なお、第２図と同一
名称のものには同一番号を付している。セパレータに
は、直径10mmのポリプロピレン製多孔膜を用いた。この
セパレータを介し上記分極性電極を相対向させた後、テ
トラエチルアンモニウムのホウフッ化塩（Et4NBF4）を
電解質とした１モル/1のプロピレンカーボネート有機電
解液として注入後封口ケーシングし、コイン型の電気二
重層キャパシタを作成した。このキャパシタを2.4Vで充
電後1mAで定電流放電し第１表に示した容量、インピー
ダンスを得た。また70℃の雰囲気下で常時2.4Vを印加し
たところ初期容量に対する1000時間後の容量減少率も同
表にしめした。同表のN0.5,6は従来の活性炭繊維布およ
びペーパ状活性炭繊維を分極性電極に用いたキャパシタ
の特性をしめしている。本発明のものは特にインピーダ
ンス（1KHz）の面で従来のものに比べ特に優れている。Example 1 A mixture of activated carbon fibers (phenolic) having a specific surface area of 2000 m 2 / g and a resole type phenolic resin in a ratio shown in Table 1 was cured at 100 ° C. for 1 hour and then heated in a nitrogen gas atmosphere at a heating rate. Four
The phenol resin was carbonized by heating at 0 ° C / hr to 900 ° C.
The temperature was held at 900 ° C for 5 hours. The above molded body has a thickness of 0.6
mm, diameter 6 mm. The table also shows the yield and porosity of each composition mixture after heat treatment. An aluminum layer having a thickness of 200 μm was formed on one surface of the thus obtained polarizable electrode by plasma spraying. Using this one, the coin type capacitor shown in the figure was constructed. The same names as those in FIG. 2 are given the same numbers. A polypropylene porous membrane having a diameter of 10 mm was used as the separator. After the polarizable electrodes were opposed to each other through this separator, tetraethylammonium borofluoride salt (Et 4 NBF 4 ) was used as an electrolyte and injected as a 1 mol / 1 propylene carbonate organic electrolytic solution, which was then sealed to form a coin shape. The electric double layer capacitor was prepared. This capacitor was charged at 2.4 V and then discharged at a constant current of 1 mA to obtain the capacitance and impedance shown in Table 1. Further, when 2.4 V was constantly applied in the atmosphere of 70 ° C, the capacity reduction rate after 1000 hours with respect to the initial capacity is also shown in the same table. N0.5 and 6 in the table show the characteristics of the conventional activated carbon fiber cloth and the capacitor using the paper-like activated carbon fiber as the polarizable electrode. The present invention is particularly superior to the conventional one in terms of impedance (1 KHz).
（実施例２） 比表面積950m2/gの活性炭粉末とを実施例１の表中NO.1
と同様な組成、方法で分極性電極を作成し、図に示す電
気二重層キャパシタ（実施例１と同様）を作成したとこ
ろを容量0.11F、インピーダンス16Ωを得た。 (Example 2) Activated carbon powder having a specific surface area of 950 m 2 / g was used as NO. 1 in the table of Example 1.
A polarizable electrode was prepared by the same composition and method as described in (1), and an electric double layer capacitor (similar to Example 1) shown in the figure was prepared to obtain a capacitance of 0.11 F and an impedance of 16Ω.
（実施例３） 表中N0.3を300℃までは80℃/hr,1000℃までは30℃/hrで
窒素気流中で昇温した。このような条件で作成した分極
性電極を用いて実施例１と同様なコイン型キャパシタを
作成し次の特性を得た。容量0.18F,インピーダンス12Ω
を得た。(Example 3) In the table, N0.3 was heated up to 300 ° C at 80 ° C / hr and up to 1000 ° C at 30 ° C / hr in a nitrogen stream. A coin-type capacitor similar to that of Example 1 was prepared using the polarizable electrode prepared under such conditions, and the following characteristics were obtained. Capacity 0.18F, impedance 12Ω
Got
（実施例４） 正極側分極性電極として表中N0.3と同様な電極を用い、
負極としてSnとCdの比が85:15の合金（ウッド合金）に
リチウムを吸蔵させた非分極性電極を用いて図に示す電
気二重層キャパシタを作成した。本実施例においても他
の構成材料は実施例１と同様である。このキャパシタは
3Vの電圧、0.14Fの容量を示した。(Example 4) An electrode similar to N0.3 in the table was used as the positive electrode side polarizable electrode,
The electric double layer capacitor shown in the figure was prepared using a non-polarizable electrode in which lithium was occluded in an alloy (Wood alloy) having a Sn: Cd ratio of 85:15 as the negative electrode. Also in this embodiment, the other constituent materials are the same as in the first embodiment. This capacitor
It showed a voltage of 3V and a capacity of 0.14F.
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や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 in the electric double layer capacitor as described above but also in batteries, electrochromic displays and the like.
発明の効果 以上のように、本発明によれば従来よりエネルギー密度
の高い、低抵抗でしかも均一な分極性電極が得られる。EFFECTS OF THE INVENTION As described above, according to the present invention, it is possible to obtain a uniform polarizable electrode having a higher energy density, lower resistance, and lower resistance.
図は本発明の一実施例の分極性電極の特性を調べるため
の電気二重層キャパシタの構成図である。 １……分極性電極、２……集電体、３……セパレータ、
４……ガスケット、５……封口板、６……ケース、７…
…ウッド合金。FIG. 1 is a configuration diagram of an electric double layer capacitor for investigating the characteristics of a polarizable electrode according to an embodiment of the present invention. 1 ... Polarizable electrode, 2 ... Current collector, 3 ... Separator,
4 ... Gasket, 5 ... Seal plate, 6 ... Case, 7 ...
… Wood alloy.
Claims (1)
ル樹脂との混合物を不活性ガス雰囲気下で加熱しフェノ
ール樹脂を炭化し活性炭粉末あるいは活性炭繊維と、炭
素とから構成される分極性電極の製造法。1. A method for producing a polarizable electrode composed of activated carbon powder or activated carbon fiber and carbon by heating activated carbon powder or a mixture of activated carbon fiber and phenol resin in an inert gas atmosphere to carbonize the phenol resin.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62059366A JPH0770448B2 (en) | 1987-03-13 | 1987-03-13 | Method of manufacturing polarizable electrodes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62059366A JPH0770448B2 (en) | 1987-03-13 | 1987-03-13 | Method of manufacturing polarizable electrodes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63226019A JPS63226019A (en) | 1988-09-20 |
| JPH0770448B2 true JPH0770448B2 (en) | 1995-07-31 |
Family
ID=13111196
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62059366A Expired - Fee Related JPH0770448B2 (en) | 1987-03-13 | 1987-03-13 | Method of manufacturing polarizable electrodes |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0770448B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05211111A (en) * | 1991-11-20 | 1993-08-20 | Nec Corp | Electric double layer capacitor |
| JP3364968B2 (en) * | 1992-09-01 | 2003-01-08 | 株式会社デンソー | Battery |
| JP2998401B2 (en) * | 1992-02-26 | 2000-01-11 | 日本電気株式会社 | Electric double layer capacitor and method of manufacturing the same |
| JP2993343B2 (en) * | 1993-12-28 | 1999-12-20 | 日本電気株式会社 | Polarizing electrode and method of manufacturing the same |
| JPH11121300A (en) | 1997-10-17 | 1999-04-30 | Nec Corp | Polarizing electrode and method of manufacturing the same |
| JP4497622B2 (en) * | 2000-02-17 | 2010-07-07 | 株式会社Kri | Anode material for lithium secondary battery |
| JP2001250742A (en) | 2000-03-07 | 2001-09-14 | Nec Corp | Electric double layer capacitor and its manufacturing method |
| WO2010150534A1 (en) * | 2009-06-23 | 2010-12-29 | クラレケミカル株式会社 | Flow-through capacitor, method for producing deionized water, and device for producing deionized water |
-
1987
- 1987-03-13 JP JP62059366A patent/JPH0770448B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63226019A (en) | 1988-09-20 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |