JP2003309046A - High energy density electric double layer capacitor - Google Patents
High energy density electric double layer capacitorInfo
- Publication number
- JP2003309046A JP2003309046A JP2002153134A JP2002153134A JP2003309046A JP 2003309046 A JP2003309046 A JP 2003309046A JP 2002153134 A JP2002153134 A JP 2002153134A JP 2002153134 A JP2002153134 A JP 2002153134A JP 2003309046 A JP2003309046 A JP 2003309046A
- Authority
- JP
- Japan
- Prior art keywords
- double layer
- electric double
- activated carbon
- layer capacitor
- electrode
- 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.)
- Pending
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
- Y02E60/13—Energy storage using capacitors
Abstract
Description
【０００１】［発明の属する技術分野］本発明は、電気
二重層キャパシタ電極用材料、それらにより形成される
電極およびそれらの電極による構成されるキャパシタ。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for an electric double layer capacitor electrode, an electrode formed by them and a capacitor constituted by those electrodes.
【０００２】［従来の技術及び問題点］近年、電子機器
の進展はめざましく、携帯用電子機器の小型化、軽量化
が急速に進行している。これらの電源となるリチウムイ
オン電池などが小型、軽量である高エネルギー密度電池
として重要が急速にのびている。 電気二重層キャパシ
タはこれらの電池と従来からのキャパシタ（コンデンサ
ー）の中間に値する新規な電源として注目されている。
すなわちこれらのリチウムイオン電池などが３００回な
いし５００回の充放電が可能なことに対して、電気二重
層キャパシタは１００００回ないし１０００００回の充
放電が可能なこと、電池に比較すると１０倍以上の高電
流で電力貯蔵あるいは充放電可能なことなど電池には求
めることができない高性能を有している。 したがって
停電用電源あるいは電気自動車などの補助電源として、
あるいは回生エネルギー回収用電源として大きな用途が
考えられている。従来、電気二重層キャパシタ電極材料
としては活性炭やカーボンナノチューブなどの炭素材料
が用いられているが、価格が安価な点などから活性炭が
広く使用されている。活性炭は比表面積が大きく、電気
二重層キャパシタ用の電極材料としては最適である。そ
の合成法は、通常活性炭を水蒸気賦活法あるいはＫＯＨ
賦活法によっている。しかしながら、ＫＯＨ賦活法では
活性炭の数倍のＫＯＨを混合して、焼成しているが、か
なり危険で爆発などの現象が起こるため、性能はよい
が、コストが高価になる。そのため大量生産法は主とし
て水蒸気雰囲気下での焼成によっている。またこれらの
活性炭を用いて作成される電気二重層キャパシタは水溶
液系と、有機溶媒系電解液からなっている。水溶液系電
気二重層キャパシタは電圧が低いため、大型電気二重層
キャパシタには３Ｖ近い電圧を示す、有機溶媒系電解液
からなる電気二重層キャパシタが適している。しかしな
がら電気二重層キャパシタの容量は、電池に比較すると
非常に小さく、容量の上昇が急務となっている。これま
で種々の方法を用いて、活性炭を用いる電気二重層キャ
パシタの容量増加がおこなわれてきたが、ほとんど成功
していなかった。[Prior Art and Problems] In recent years, electronic devices have been remarkably developed, and portable electronic devices have been rapidly reduced in size and weight. Lithium-ion batteries, etc., which are the power sources of these, are rapidly gaining importance as high energy density batteries that are small and lightweight. The electric double layer capacitor is attracting attention as a new power source that is intermediate between these batteries and conventional capacitors.
That is, while these lithium-ion batteries can be charged and discharged 300 to 500 times, the electric double layer capacitor can be charged and discharged 10,000 to 100,000 times, which is more than 10 times that of batteries. It has high performance that cannot be demanded from a battery, such as the ability to store or charge electricity at high current. Therefore, as a power source for blackouts or as an auxiliary power source for electric vehicles,
Alternatively, it is considered to have a large use as a power source for regenerative energy recovery. Conventionally, carbon materials such as activated carbon and carbon nanotubes have been used as the electric double layer capacitor electrode material, but activated carbon is widely used because of its low price. Activated carbon has a large specific surface area and is optimal as an electrode material for electric double layer capacitors. The synthesis method is usually activated carbon by steam activation method or KOH.
It depends on the activation method. However, in the KOH activation method, KOH which is several times as much as the activated carbon is mixed and fired, but since it is quite dangerous and phenomena such as explosion occur, the performance is good, but the cost becomes expensive. Therefore, the mass production method is mainly performed by firing in a steam atmosphere. An electric double layer capacitor made by using these activated carbons is composed of an aqueous solution type and an organic solvent type electrolytic solution. Since an aqueous solution type electric double layer capacitor has a low voltage, an electric double layer capacitor composed of an organic solvent type electrolytic solution showing a voltage of about 3 V is suitable for a large size electric double layer capacitor. However, the capacity of the electric double layer capacitor is much smaller than that of the battery, and there is an urgent need to increase the capacity. Up to now, the capacity of an electric double layer capacitor using activated carbon has been increased by using various methods, but it has hardly succeeded.
【０００３】［発明が解決しようとする問題点］前述の
如く、電気二重層キャパシタ用活性炭の容量は、水蒸気
賦活法やＫＯＨ賦活法によりかなり上昇してきたが、実
用的にはまだ不十分である。電気二重層キャパシタのエ
ネルギー密度を上げることが急務である。[Problems to be Solved by the Invention] As described above, the capacity of activated carbon for electric double layer capacitors has been considerably increased by the steam activation method or the KOH activation method, but it is still insufficient in practical use. . There is an urgent need to increase the energy density of electric double layer capacitors.
【０００４】［発明が解決しようとする課題］本発明
は、かかる間題点を解決し、電気二重層キャパシタとし
て使用できる水蒸気賦活法やＫＯＨ賦活法により合成さ
れた活性炭の容量、ひいてはエネルギー密度を増大さ
せ、さらには導電剤を加えずとも使用できる電気二重層
キャパシタ電極用活性炭の提供を目的とする。[Problems to be Solved by the Invention] The present invention solves the above-mentioned problems and improves the capacity, and thus the energy density, of activated carbon synthesized by a steam activation method or a KOH activation method that can be used as an electric double layer capacitor. It is an object of the present invention to provide activated carbon for an electric double layer capacitor electrode, which can be increased and used without adding a conductive agent.
【０００５】［問題点を解決するための手段］本発明
は、通常用いられている電気二重層キャパシタ用活性炭
を、単独であるいは金属塩共存下水蒸気雰囲気あるいは
炭酸ガス雰囲気中７００〜１０００℃で加熱して改質す
ることを特徴とする。これらの改質活性炭は、未改質の
活性炭に比較して電気二重層キャパシタの容量を増加さ
せる。さらに導電性を上げる効果もあり、電極合剤に導
電剤を加えずとも使用できるため、さらに高電圧までの
充電が可能となる。これらにより高容量、高エネルギー
密度の電気二重層キャパシタの供給が可能である。[Means for Solving the Problems] The present invention heats a commonly used activated carbon for an electric double layer capacitor at 700 to 1000 ° C. in a steam atmosphere or a carbon dioxide gas atmosphere alone or in the presence of a metal salt. And is modified. These modified activated carbons increase the capacity of the electric double layer capacitor compared to unmodified activated carbons. Further, it also has the effect of increasing the conductivity, and since it can be used without adding a conductive agent to the electrode mixture, it is possible to charge to a higher voltage. With these, it is possible to supply an electric double layer capacitor having high capacity and high energy density.
【０００６】本発明で用いられるキャパシタ用活性炭
は、フェノール系、アクリル系、レーヨン系、ピッチ系
などから合成された繊維状活性炭、あるいはヤシ殻系、
石炭系、木質系素灰などから賦活された活性炭、あるい
は合成高分子から誘導されるガラス状、繊維状カーボン
などが使用される。本発明で用いられるキャパシタ活物
質の平均粒子径は、良好な電極性能を得る上で、１〜５
０μｍ、好ましくは、３〜３０μｍである。本発明で用
いられる金属塩類は塩化ニッケル，塩化鉄などである
が、これに限るものではなく、コバルトやマンガン、銅
などの塩化物，酸化物，酢酸塩などを含む。本発明で用
いられる金属塩類の重量比は約０．４〜１％であるが、
これに限るものではなく、０．１％〜５％の範囲でも効
果が得られる。The activated carbon for capacitors used in the present invention is a fibrous activated carbon synthesized from phenol-based, acrylic-based, rayon-based, pitch-based, etc., or coconut shell-based carbon.
Activated carbon activated from coal-based or wood-based ash, or glassy or fibrous carbon derived from a synthetic polymer is used. The average particle size of the capacitor active material used in the present invention is 1 to 5 in order to obtain good electrode performance.
It is 0 μm, preferably 3 to 30 μm. The metal salts used in the present invention are nickel chloride, iron chloride and the like, but are not limited to these, and include chlorides such as cobalt, manganese and copper, oxides and acetates. The weight ratio of the metal salts used in the present invention is about 0.4-1%,
The effect is not limited to this, and the effect can be obtained in the range of 0.1% to 5%.
【０００７】本発明の塗布ペーストは、前記活性炭黒鉛
系あるいはアセチレンブラック、ファーネスブラックな
どのカーボン系導電性物質を併せて８０重量％〜９８．
５重量％とポリフッ化ビニリデン（ＰＶｄＦ）やラテッ
クス（スチレンブタジエン系ゴム（ＳＢＲ）を水系溶剤
に分散したもの），テフロン（登録商標）などの結着剤
を含んでいることを特徴とする電気二重層キャパシタ電
極用塗布ペーストである。また、導電性物質を含まずと
も使用できる電気二重層キャパシタ電極用塗布ペースト
である。本発明の集電体の金属箔としては、アルミニウ
ム、ニッケル、ステンレススチール、銅などの金属箔、
金属網状物、金属多孔体等の１μｍ〜１００μｍの厚み
のものが用いられる。本発明のキャパシタ電極は、前記
塗布ペーストを、前記金属箔に、ドクターブレド法、各
種コーター法、グラビヤ法、インクジェット法等の任意
の方法で塗布し、絶乾し、電極を得る。必要ならば、更
にプレスしてもよい。本発明の塗布ペースト及び非水系
二次電池電極は、キャパシタ活物質と黒鉛系あるいはア
セチレンブラック、ファーネスブラックなどの導電性物
質を併せて８０重量％〜９８．５重量％とポリフッ化ビ
ニリデン（ＰＶｄＦ）やラテックス（スチレンブタジエ
ン系ゴム（ＳＢＲ）を水系溶剤に分散したもの），テフ
ロンなどの結着剤を含んでいることを特徴とする電気二
重層キャパシタ電極用塗布ペーストである。また、導電
性物質を含まずとも使用できる電気二重層キャパシタ電
極用塗布ペーストである。キャパシタ活物質が、９８．
５重量％を越えると集電体への接着が、悪くなり充放電
サイクル寿命に劣る。また８０重量％未満では、キャパ
シタとして、体積当たりの容量が低下し好ましくない。The coating paste of the present invention contains 80% by weight to 98% by weight of the activated carbon graphite-based or carbon-based conductive material such as acetylene black and furnace black.
5% by weight of polyvinylidene fluoride (PVdF), latex (styrene-butadiene rubber (SBR) dispersed in an aqueous solvent), Teflon (registered trademark), etc. It is a coating paste for a multilayer capacitor electrode. Further, it is an electric double layer capacitor electrode coating paste which can be used without containing a conductive substance. As the metal foil of the current collector of the present invention, aluminum, nickel, stainless steel, metal foil such as copper,
A metal net, a metal porous body or the like having a thickness of 1 μm to 100 μm is used. The capacitor electrode of the present invention is obtained by applying the coating paste to the metal foil by an arbitrary method such as a doctor blade method, various coater methods, a gravure method, an inkjet method, etc. and drying to obtain an electrode. Further pressing may be performed if necessary. The coating paste and the non-aqueous secondary battery electrode of the present invention include a capacitor active material and a conductive material such as graphite-based or acetylene black or furnace black in an amount of 80 wt% to 98.5 wt% and polyvinylidene fluoride (PVdF). A coating paste for an electric double layer capacitor electrode, characterized in that it contains a binder such as latex, latex (styrene-butadiene rubber (SBR) dispersed in an aqueous solvent), and Teflon. Further, it is an electric double layer capacitor electrode coating paste which can be used without containing a conductive substance. The capacitor active material is 98.
If it exceeds 5% by weight, the adhesion to the current collector will be poor and the charge / discharge cycle life will be poor. On the other hand, if it is less than 80% by weight, the capacity per volume of the capacitor decreases, which is not preferable.
【０００８】本発明の電極に使用する電解液は、非プロ
トン性有機溶媒、例えばプロピレンカーボネート、エチ
レンカーボネート、ジメチルカーボネート、エチルメチ
ルカニボネート、ジエチルカーボネニト、γ−ブチロラ
クトン、スルホラン等であって、とくに限定されるわけ
でない。電解塩としてはＥｔ４ＮＢＦ４，Ｅｔ４ＮＰＦ
６，Ｅｔ４ＰＢＦ４，Ｅｔ３ＭｅＮＢＦ４ などがあ
る。但し Ｅｔ はＣ２Ｈ５ のＭｅはＣＨ３を略した
ものである。またこれらの 塩に ＬｉＣ１０４、Ｌｉ
ＢＦ４，ＬｉＰＦ６、ＬｉＡＳＦ６、ＣＦ３ＳＯ３Ｌ
ｉ、（ＣＦ３ＳＯ２）２ＮＬｉ等のリチウム塩を添加し
ても良い。本発明の電極に使用する電解液は、水溶液系
でも可能であり、この場合は電解質塩としては硫酸、苛
性カリなどが使用される。本発明の電極は円筒形、シー
ト形、角形等の任意の形状にして電極に用いられる。The electrolytic solution used in the electrode of the present invention is an aprotic organic solvent such as propylene carbonate, ethylene carbonate, dimethyl carbonate, ethylmethyl cannibonate, diethylcarbonenite, γ-butyrolactone, sulfolane and the like. It is not limited. As the electrolytic salt, Et 4 NBF 4 , Et 4 NPF is used.
6 , Et 4 PBF 4 , Et 3 MeNBF 4, and the like. However, Et is an abbreviation for C 3 H 5 and CH 3 . Further, these salts may be added to LiC10 4 , Li
BF 4 , LiPF 6 , LiA S F 6 , CF 3 SO 3 L
A lithium salt such as i, (CF 3 SO 2 ) 2 NLi may be added. The electrolytic solution used for the electrode of the present invention may be an aqueous solution, and in this case, sulfuric acid, caustic potash, etc. are used as the electrolyte salt. The electrode of the present invention is formed into any shape such as a cylindrical shape, a sheet shape, and a rectangular shape, and is used as the electrode.
【０００９】［実施の形態］以下に本発明の実施例を説
明する。但し、以下に示す実施例は、本発明の例示であ
って本発明の電極は、これらに限定されるものではな
い。[Embodiment] An embodiment of the present invention will be described below. However, the examples described below are examples of the present invention, and the electrodes of the present invention are not limited thereto.
【０００１０】［実施例１］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）を８０℃の塩化ニッケル水溶液中で４時
間撹拌した後、１１０℃で乾燥する。このときの塩化ニ
ッケルの量は活性炭に対し０．４３重量部とする。乾燥
後活性炭を電気炉に入れ、不活性ガス気流下で８５０℃
まで昇温し、２時間保持する。導入するガスを二酸化炭
素に切り替え、さらに３時間熱処理したのち、再度不活
性ガスを導入しつつ冷却する。この活性炭８０重量部に
導電剤１０重量部、結着剤としてＰＶｄＦ１０重量部と
なるようにＰＶｄＦのＮＭＰ溶液を加えて撹拌し、活性
炭を分散させ、塗工液とする。これを表面を粗くした２
０μｍのアルミ箔に膜厚２００μｍになるように塗布す
る。１３０°Ｃで真空乾燥を行う。これを１６ｍｍφに
打抜き、電極とする。Example 1 Steam-activated activated carbon for electric double layer capacitor electrodes (manufactured by Kureha Chemical Industry Co., Ltd.) having an average particle size of 20 μm was stirred in an aqueous nickel chloride solution at 80 ° C. for 4 hours and then at 110 ° C. dry. The amount of nickel chloride at this time is 0.43 parts by weight with respect to the activated carbon. After drying, put the activated carbon in an electric furnace and in an inert gas stream at 850 ° C.
The temperature is raised to and held for 2 hours. The gas to be introduced is switched to carbon dioxide, heat treatment is further performed for 3 hours, and then cooling is performed while introducing an inert gas again. A conductive agent (10 parts by weight) and a PVdF NMP solution as a binder (10 parts by weight) were added to 80 parts by weight of this activated carbon and stirred to disperse the activated carbon to obtain a coating liquid. Roughened the surface of this 2
It is applied to a 0 μm aluminum foil so as to have a film thickness of 200 μm. Vacuum dry at 130 ° C. This is punched out into 16 mmφ and used as an electrode.
【０００１１】［実施例２］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）を８０℃の塩化ニッケル水溶液中で４時
間撹拌した後、１１０℃で乾燥する。このときの塩化ニ
ッケルの量は活性炭に対し０．４３重量部とする。乾燥
後活性炭を電気炉に入れ、不活性ガス気流下で８５０℃
まで昇温し、２時間保持する。導入するガスを水蒸気に
切り替え、さらに３時間熱処理したのち、再度不活性ガ
スを導入しつつ冷却する。この活性炭８０重量部に導電
剤１０重量部、結着剤としてＰＶｄＦ１０重量部となる
ようにＰＶｄＦのＮＭＰ溶液を加えて撹拌し、活性炭を
分散させ、塗工液とする。これを表面を粗くした２０μ
ｍのアルミ箔に膜厚２００μｍになるように塗布する。
１３０°Ｃで真空乾燥を行う。これを１６ｍｍφに打抜
き、電極とする。Example 2 Steam-activated activated carbon for electric double layer capacitor electrodes (manufactured by Kureha Chemical Industry Co., Ltd.) having an average particle size of 20 μm was stirred in an aqueous solution of nickel chloride at 80 ° C. for 4 hours and then at 110 ° C. dry. The amount of nickel chloride at this time is 0.43 parts by weight with respect to the activated carbon. After drying, put the activated carbon in an electric furnace and in an inert gas stream at 850 ° C.
The temperature is raised to and held for 2 hours. The gas to be introduced is changed to water vapor, heat treatment is further performed for 3 hours, and then the inert gas is again introduced and cooled. A conductive agent (10 parts by weight) and a PVdF NMP solution as a binder (10 parts by weight) were added to 80 parts by weight of this activated carbon and stirred to disperse the activated carbon to obtain a coating liquid. 20μ with roughened surface
m aluminum foil to a film thickness of 200 μm.
Vacuum dry at 130 ° C. This is punched out into 16 mmφ and used as an electrode.
【０００１２】［実施例３］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）をを電気炉に入れ、不活性ガス気流下で
８５０℃まで昇温し、２時間保持する。導入するガスを
二酸化炭素に切り替え、さらに３時間熱処理したのち、
再度不活性ガスを導入しつつ冷却する。この活性炭８０
重量部に導電剤１０重量部、結着剤としてＰＶｄＦ１０
重量部となるようにＰＶｄＦのＮＭＰ溶液を加えて撹拌
し、活性炭を分散させ、塗工液とする。これを表面を粗
くした２０μｍのアルミ箔に膜厚２００μｍになるよう
に塗布する。１３０°Ｃで真空乾燥を行う。これを１６
ｍｍφに打抜き、電極とする。[Example 3] Activated carbon for steam-activated electric double layer capacitor electrodes (manufactured by Kureha Chemical Industry Co., Ltd.) having an average particle size of 20 µm was placed in an electric furnace and heated to 850 ° C under an inert gas stream. And hold for 2 hours. After changing the gas to be introduced to carbon dioxide and performing heat treatment for 3 hours,
Cool while introducing the inert gas again. This activated carbon 80
10 parts by weight of conductive agent, PVdF10 as a binder
An NMP solution of PVdF is added so as to be a weight part and stirred, and activated carbon is dispersed to obtain a coating liquid. This is applied to a 20 μm-thick aluminum foil having a roughened surface so as to have a film thickness of 200 μm. Vacuum dry at 130 ° C. This 16
It is punched into mmφ and used as an electrode.
【０００１３】［実施例４］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）をを電気炉に入れ、不活性ガス気流下で
８５０℃まで昇温し、２時間保持する。導入するガスを
水蒸気に切り替え、さらに３時間熱処理したのち、再度
不活性ガスを導入しつつ冷却する。この活性炭８０重量
部に導電剤１０重量部、結着剤としてＰＶｄＦ１０重量
部となるようにＰＶｄＦのＮＭＰ溶液を加えて撹拌し、
活性炭を分散させ、塗工液とする。これを表面を粗くし
た２０μｍのアルミ箔に膜厚２００μｍになるように塗
布する。１３０°Ｃで真空乾燥を行う。これを１６ｍｍ
φに打抜き、電極とする。[Example 4] Activated carbon for steam activated electric double layer capacitor electrodes (manufactured by Kureha Chemical Industry Co., Ltd.) having an average particle diameter of 20 µm was placed in an electric furnace and heated to 850 ° C under an inert gas stream. And hold for 2 hours. The gas to be introduced is changed to water vapor, heat treatment is further performed for 3 hours, and then the inert gas is again introduced and cooled. To 80 parts by weight of this activated carbon, 10 parts by weight of a conductive agent and 10 parts by weight of PVdF as a binder were added and stirred with an NMP solution of PVdF,
Activated carbon is dispersed to obtain a coating liquid. This is applied to a 20 μm-thick aluminum foil having a roughened surface so as to have a film thickness of 200 μm. Vacuum dry at 130 ° C. This is 16mm
Punch into φ and use as electrode.
【０００１４】［実施例５］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）を８０℃の塩化第二鉄水溶液中で４時間
撹拌した後、１１０℃で乾燥する。このときの塩化第二
鉄の量は活性炭に対し０．４３重量部とする。乾燥後活
性炭を電気炉に入れ、不活性ガス気流下で８５０℃まで
昇温し、２時間保持する。導入するガスを二酸化炭素に
切り替え、さらに３時間熱処理したのち、再度不活性ガ
スを導入しつつ冷却する。この活性炭８０重量部に導電
剤１０重量部、結着剤としてＰＶｄＦ１０重量部となる
ようにＰＶｄＦのＮＭＰ溶液を加えて撹拌し、活性炭を
分散させ、塗工液とする。これを表面を粗くした２０μ
ｍのアルミ箔に膜厚２００μｍになるように塗布する。
１３０°Ｃで真空乾燥を行う。これを１６ｍｍφに打抜
き、電極とする。Example 5 Steam-activated activated carbon for electric double layer capacitor electrodes (Kureha Chemical Industry Co., Ltd.) having an average particle size of 20 μm was stirred in an aqueous ferric chloride solution at 80 ° C. for 4 hours, and then 110 Dry at ℃. The amount of ferric chloride at this time is 0.43 parts by weight with respect to the activated carbon. After drying, the activated carbon is put into an electric furnace, heated to 850 ° C. under an inert gas stream, and kept for 2 hours. The gas to be introduced is switched to carbon dioxide, heat treatment is further performed for 3 hours, and then cooling is performed while introducing an inert gas again. A conductive agent (10 parts by weight) and a PVdF NMP solution as a binder (10 parts by weight) were added to 80 parts by weight of this activated carbon and stirred to disperse the activated carbon to obtain a coating liquid. 20μ with roughened surface
m aluminum foil to a film thickness of 200 μm.
Vacuum dry at 130 ° C. This is punched out into 16 mmφ and used as an electrode.
【０００１５】［比較例１］平均粒子径２０μｍの水蒸
気賦活の電気二重層キャパシタ電極用活性炭（呉羽化学
工業（株）製）８０重量部に導電剤１０重量部、結着剤
としてＰＶｄＦ１０重量部となるようにＰＶｄＦのＮＭ
Ｐ溶液を加えて撹拌し、活性炭を分散させ、塗工液とす
る。これを表面を粗くした２０μｍのアルミ箔に膜厚２
００μｍになるように塗布する。１３０°Ｃで真空乾燥
を行う。これを１６ｍｍφに打抜き、電極とする。[Comparative Example 1] 80 parts by weight of activated carbon (produced by Kureha Chemical Industry Co., Ltd.) for an electric double layer capacitor electrode of water vapor activation having an average particle size of 20 μm, 10 parts by weight of a conductive agent, and 10 parts by weight of PVdF as a binder. To be PVdF NM
The P solution is added and stirred to disperse the activated carbon to obtain a coating liquid. This is applied to a 20 μm aluminum foil with a roughened surface to a film thickness of 2
Apply so as to have a thickness of 00 μm. Vacuum dry at 130 ° C. This is punched out into 16 mmφ and used as an electrode.
【０００１６】［キャパシタの作製とその評価］実施例
１〜５」及び比較例１に記述した電極材を正負両極とし
て、あらかじめ１５０℃で真空乾燥したガラス繊維濾紙
（ＡＤＶＡＮＴＥＣ：ＧＡ１００）をセパレーターとし
て介在させ、１モル／リットルの（Ｃ２Ｈ５）４・ＮＢ
Ｆ４のプロピレンカーボネート溶液を電解液として電気
二重層キャパシタを作製した。[Production of capacitor and its evaluation] The electrode materials described in Examples 1 to 5 "and Comparative Example 1 were used as positive and negative electrodes, and glass fiber filter paper (ADVANTEC: GA100) preliminarily vacuum dried at 150 ° C was used as a separator. 1 mol / liter of (C 2 H 5 ) 4 · NB
An electric double layer capacitor was produced using a propylene carbonate solution of F 4 as an electrolytic solution.
【０００１７】充放電の測定は、東洋システム製電池用
充放電測定装置ＴＯＳＣＡＴ３１００Ｕ型を使用し、充
電０．８ｍＡの定電流充電を行い、３Ｖまで充電を行っ
た。放電は０．８ｍＡの定電流放電を行い、終止電圧を
０Ｖとした。The charge / discharge was measured by using a battery charge / discharge measuring device TOSCAT3100U manufactured by Toyo System Co., Ltd., and constant current charging of 0.8 mA was performed to charge up to 3V. The discharge was a constant current discharge of 0.8 mA, and the final voltage was 0V.
【０００１８】静電容量は次のようにして求めた。The capacitance was determined as follows.
【０００１９】放電曲線（放電電圧−放電時間）から放
電エネルギー（放電電圧ｘ電流（０．８ｍＡ）の時間積
分として合計放電エネルギー（Ｗ・ｓ）を求め、静電容
量（Ｆ）＝２ｘ合計放電エネルギー（Ｗ・ｓ）／（放電
開始電圧（Ｖ））２の式を用いて評価セルの静電容量を
求め、この静電容量を用いた活性炭の単位重量当たり静
電容量（Ｆ／ｇ）とした。From the discharge curve (discharge voltage-discharge time), the total discharge energy (Ws) was obtained as the time integration of the discharge energy (discharge voltage x current (0.8 mA), and electrostatic capacity (F) = 2 x total discharge The capacitance of the evaluation cell is calculated using the formula of energy (Ws) / (discharge starting voltage (V)) 2 , and the capacitance per unit weight of activated carbon (F / g) is calculated using this capacitance. And
【０００２０】実施例、比較例に記した電極を用いて作
製した電気二重層キャパシタの静電容量を表１に示す。Table 1 shows the electrostatic capacities of the electric double layer capacitors produced by using the electrodes described in Examples and Comparative Examples.
【０００２１】[00021]
【表１】 [Table 1]
【０００２２】［発明の効果］表１の如く、本発明によ
る電極は、比較例１に示す再賦活を行わない市販の活性
炭に対して最大で約２５％大きな静電容量を示した。ま
た図１に示すがごとく、長いサイクルにわたり、市販の
活性炭より大きな容量を示しており、高エネルギー密度
でかつ長寿命の電気二重層キャパシタを供与することが
可能である。さらに図２に示すがごとく、高い電流密度
で充放電を行った場合でも容量の低下が少なく優れた電
気二重層キャパシタを作成することを可能とした。[Effects of the Invention] As shown in Table 1, the electrode according to the present invention showed a maximum capacitance of about 25% larger than that of the commercially available activated carbon shown in Comparative Example 1 which was not reactivated. Further, as shown in FIG. 1, it exhibits a larger capacity than a commercially available activated carbon over a long cycle, and it is possible to provide an electric double layer capacitor having a high energy density and a long life. Further, as shown in FIG. 2, it is possible to produce an excellent electric double layer capacitor with a small decrease in capacity even when charged and discharged at a high current density.
【００２３】[0023]
【図１】（ａ）塩化ニッケルと炭酸ガスにより再賦活し
た活性炭及び（ｂ）市販の活性炭を用いた電気二重層キ
ャパシタのサイクル特性FIG. 1 is a cycle characteristic of an electric double layer capacitor using (a) activated carbon reactivated by nickel chloride and carbon dioxide and (b) commercially available activated carbon.
【図２】（ａ）塩化ニッケルと炭酸ガスにより再賦活し
た活性炭及び（ｂ）市販の活性炭を用いた電気二重層キ
ャパシタの放電レート特性FIG. 2 is a discharge rate characteristic of an electric double layer capacitor using (a) activated carbon reactivated by nickel chloride and carbon dioxide and (b) commercially available activated carbon.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 磯野 健一 福岡県三池郡高田町原1018 ─────────────────────────────────────────────────── ─── Continued front page (72) Inventor Kenichi Isono 1018 Takadachobara, Miike District, Fukuoka Prefecture
Claims (4)
気賦活あるいはＫＯＨ賦活法等による）を金属塩共存下
で、炭酸ガス雰囲気中７００〜１０００℃で加熱して改
質することを特徴とする電気二重層キャパシタ用活性炭
の改質方法。1. A method of modifying a known activated carbon for electric double layer (by a conventional steam activation or KOH activation method) in the presence of a metal salt at 700 to 1000 ° C. in a carbon dioxide gas atmosphere for modification. Method for reforming activated carbon for electric double layer capacitor.
賦活あるいはＫＯＨ賦活法等による）をさらに金属塩共
存下で、水蒸気雰囲気中７００〜１０００℃で加熱して
改質することを特徴とする電気二重層キャパシタ用活性
炭の改質方法。あるいは既知の電気二重層用活性炭を炭
酸ガス雰囲気中７００〜１０００℃で加熱して改質する
ことを特徴とする電気二重層キャパシタ用活性炭の改質
方法。2. A known electric double layer activated carbon (usually steam activated or KOH activated) is further heated in a steam atmosphere at 700 to 1000 ° C. for reforming in the presence of a metal salt. A method for reforming activated carbon for electric double layer capacitors. Alternatively, a known method for reforming activated carbon for an electric double layer capacitor is characterized by heating the activated carbon for an electric double layer at 700 to 1000 ° C. in a carbon dioxide gas atmosphere for reforming.
電気二重層キャパシタ電極3. An electric double layer capacitor electrode produced according to claim 1 or 2.
パシタ4. An electric double layer capacitor manufactured according to claim 3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002153134A JP2003309046A (en) | 2002-04-17 | 2002-04-17 | High energy density electric double layer capacitor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002153134A JP2003309046A (en) | 2002-04-17 | 2002-04-17 | High energy density electric double layer capacitor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2003309046A true JP2003309046A (en) | 2003-10-31 |
Family
ID=29398000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002153134A Pending JP2003309046A (en) | 2002-04-17 | 2002-04-17 | High energy density electric double layer capacitor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2003309046A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311573C (en) * | 2004-03-24 | 2007-04-18 | Tdk株式会社 | Electrode and manufacturing method for the same, electrochemical device manufacturing method and electrochemical device |
| JP2007281427A (en) * | 2007-02-02 | 2007-10-25 | Nfk Holdings Co Ltd | Method for manufacturing activated carbon for electric double layer capacitor or coal as its raw material, and installation for manufacturing activated carbon for electric double layer capacitor |
| JP2008270427A (en) * | 2007-04-18 | 2008-11-06 | Cataler Corp | Carbon material for power storage device electrode, and manufacturing method thereof |
| JP2012049389A (en) * | 2010-08-27 | 2012-03-08 | Nippon Carbon Co Ltd | Method of producing active carbon for capacitor and active carbon |
-
2002
- 2002-04-17 JP JP2002153134A patent/JP2003309046A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1311573C (en) * | 2004-03-24 | 2007-04-18 | Tdk株式会社 | Electrode and manufacturing method for the same, electrochemical device manufacturing method and electrochemical device |
| JP2007281427A (en) * | 2007-02-02 | 2007-10-25 | Nfk Holdings Co Ltd | Method for manufacturing activated carbon for electric double layer capacitor or coal as its raw material, and installation for manufacturing activated carbon for electric double layer capacitor |
| JP2008270427A (en) * | 2007-04-18 | 2008-11-06 | Cataler Corp | Carbon material for power storage device electrode, and manufacturing method thereof |
| JP2012049389A (en) * | 2010-08-27 | 2012-03-08 | Nippon Carbon Co Ltd | Method of producing active carbon for capacitor and active carbon |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5322435B2 (en) | Negative electrode active material for electricity storage devices | |
| CN104810504B (en) | A kind of Flexible graphene collector and active material integrated electrode pole piece and preparation method thereof | |
| US7691782B2 (en) | Active carbon, production method thereof and polarizable electrode | |
| WO2012146046A1 (en) | Polyimide capacitance battery and manufacturing method thereof | |
| WO2011103708A1 (en) | Capacitor cell with high-specific-energy organic system | |
| JP2007115721A (en) | Lithium ion capacitor | |
| JP2013157603A (en) | Activated carbon for lithium ion capacitor, electrode including the same as active material, and lithium ion capacitor using electrode | |
| US20120099246A1 (en) | Lithium ion capacitor | |
| JP2009205918A (en) | Power storage device | |
| CN110993358A (en) | Flexible zinc ion capacitor | |
| JP2007180431A (en) | Lithium ion capacitor | |
| WO2018059180A1 (en) | High-power, high-energy chemical power supply and preparation method therefor | |
| JP7462066B2 (en) | Nonaqueous alkali metal storage element and positive electrode coating fluid | |
| JP4731974B2 (en) | Lithium ion capacitor | |
| JP2001210318A (en) | Manufacturing method of negative electrode for nonaqueous electrolytic solution secondary battery | |
| JP2003309046A (en) | High energy density electric double layer capacitor | |
| JP2007294539A (en) | Lithium ion hybrid capacitor | |
| JP2000306609A (en) | Secondary power supply | |
| WO2018197903A1 (en) | Battery comprising an electrode having carbon additives | |
| JP2008166309A (en) | Lithium ion capacitor | |
| JP4732074B2 (en) | Lithium ion capacitor | |
| CN114188504A (en) | Electrochemical device and electronic device | |
| JP2006310412A (en) | Lithium-ion capacitor | |
| JP2003017370A (en) | Coating paste for capacitor and electric double layer capacitor electrode | |
| JPH1027733A (en) | Electric double-layer capacitor and manufacture thereof |