JPH08236406A - Electrode for electric double layer capacitor and manufacture thereof - Google Patents
Electrode for electric double layer capacitor and manufacture thereofInfo
- Publication number
- JPH08236406A JPH08236406A JP7074136A JP7413695A JPH08236406A JP H08236406 A JPH08236406 A JP H08236406A JP 7074136 A JP7074136 A JP 7074136A JP 7413695 A JP7413695 A JP 7413695A JP H08236406 A JPH08236406 A JP H08236406A
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- double layer
- electric double
- layer capacitor
- polyvinylidene chloride
- 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.)
- Granted
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
Landscapes
- Carbon And Carbon Compounds (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電気二重層コンデンサ用
電極及びその製法に関し、特に大静電容量を得るのに最
適な電気二重層コンデンサ用電極及びその製法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrode for an electric double layer capacitor and its manufacturing method, and more particularly to an electrode for an electric double layer capacitor most suitable for obtaining a large capacitance and a manufacturing method thereof.
【０００２】[0002]
【従来の技術】近年、電気二重層に基づく電荷の蓄積、
すなわち電気二重層原理を用いた電気二重層コンデンサ
が開発されて製品化されており、該コンデンサは大静電
容量が得られるため、小型のものは電子機器の半導体メ
モリ−用のバックアップ電源から、大型のものは車載の
鉛バッテリの用途の一部にまで使用されている。2. Description of the Related Art In recent years, charge accumulation based on electric double layers,
That is, an electric double layer capacitor using the electric double layer principle has been developed and commercialized.Since the capacitor can obtain a large electrostatic capacity, a small one is used as a backup power source for a semiconductor memory of an electronic device, The large ones are even used in some of the applications of lead batteries in vehicles.
【０００３】この種の電気二重層コンデンサ用の電極材
として、微細な細孔を有する活性炭微粒子が使用されて
おり、この活性炭微粒子については従来より種々の研究
がなされている。As the electrode material for this type of electric double layer capacitor, fine particles of activated carbon having fine pores are used, and various studies have been made on the fine particles of activated carbon.
【０００４】また、特許文献としても、例えば特開昭５
９−１３８３２７号公報、特開昭５９−１７２２３０号
公報、特開昭６０−２１１８２１号公報、特開昭６１−
１０２０２３号公報、特開昭６１−２１４４１７号公
報、特開昭６３−１８７６１４号公報、特開平１−１６
５１０８号公報、特開平１−２２７４１７号公報に開示
されており、これらはすべて活性炭を電極材としてい
る。ただし、電気二重層コンデンサ用の電極としては均
一な細孔径を有する材料を必要としているのに対し、活
性炭の細孔径分布は広い範囲の分布をしており、必ずし
も電気二重層コンデンサ用の電極材料として最適である
とは云い難い。Also, as a patent document, for example, Japanese Patent Laid-Open No.
9-138327, JP-A-59-172230, JP-A-60-212821, and JP-A-61-161.
No. 102023, JP-A-61-214417, JP-A-63-187614, and JP-A-1-16.
5108 and Japanese Patent Application Laid-Open No. 1-227417, all of which use activated carbon as an electrode material. However, while an electrode for an electric double layer capacitor requires a material having a uniform pore size, the pore size distribution of activated carbon has a wide range of distribution, and it is not always the electrode material for an electric double layer capacitor. It is hard to say that it is optimal as.
【０００５】こうした事情に鑑み、本出願人は、電気二
重層コンデンサ用電極に関して鋭意研究開発を行った結
果、ポリ塩化ビニリデン樹脂を非酸化雰囲気中で加熱
し、それによって原子および分子欠陥を生じさせて細孔
を形成した電極材料を開発し、これについて特許出願を
行った（特願平６−６７８２７号）。この材料は、非常
に微細な細孔を有する多孔質炭素材料であって、従来の
活性炭に比べ高容量の電極材料となっている。In view of these circumstances, the present applicant has conducted extensive research and development on electrodes for electric double layer capacitors, and as a result, heats polyvinylidene chloride resin in a non-oxidizing atmosphere, thereby causing atomic and molecular defects. An electrode material having pores formed therein was developed, and a patent application for this was made (Japanese Patent Application No. 6-67827). This material is a porous carbon material having extremely fine pores and has a higher capacity than that of conventional activated carbon.
【０００６】[0006]
【発明の解決しようとする課題】この新規な電極材料
は、上述の如く優秀な材料であるが、電極として成形固
形化する時の工程などに、未だ改良の余地を残したもの
であった。例えば多孔質炭化材料の粉末を成形すると
き、その形状の保持が困難なこと、粉末を相互に接合し
固形化するには相当のエネルギ−を要すること等の点で
ある。This novel electrode material is an excellent material as described above, but it still leaves room for improvement in the process of molding and solidifying as an electrode. For example, when molding powder of a porous carbonized material, it is difficult to maintain its shape, and considerable energy is required to bond and solidify the powder to each other.
【０００７】[0007]
【課題を解決するための手段】この発明は、前記の課題
を解決し、また、製造コストの低減を目的として、非酸
化雰囲気中で加熱処理して炭化させたポリ塩化ビニリデ
ン樹脂の炭化粉末粒子と、ポリ塩化ビニリデン樹脂の粉
末粒子とを混合し、この混合粒子を加圧成形した後、さ
らに非酸化雰囲気又は非酸化水蒸気雰囲気中で加熱処理
して固形化させた点を特徴とする。ポリ塩化ビニリデン
樹脂の炭化粉末粒子とポリ塩化ビニリデン樹脂の粉末粒
子との混合割合は５：５〜７：３の割合であることが好
ましい。また、始めにポリ塩化ビニリデン樹脂を加熱す
る時の温度は７００℃〜９００℃であることが好まし
く、また、加圧成形後の固形化する時の加熱温度及び加
熱時間は、始めの加熱の時と同程度であることが望まし
い。The present invention solves the above-mentioned problems and, for the purpose of reducing the manufacturing cost, carbonized powder particles of a polyvinylidene chloride resin which are carbonized by heat treatment in a non-oxidizing atmosphere. And powder particles of polyvinylidene chloride resin are mixed, the mixed particles are pressure-molded, and then heat-treated in a non-oxidizing atmosphere or a non-oxidizing steam atmosphere to be solidified. The mixing ratio of the carbonized powder particles of the polyvinylidene chloride resin and the powder particles of the polyvinylidene chloride resin is preferably 5: 5 to 7: 3. The temperature at the time of initially heating the polyvinylidene chloride resin is preferably 700 ° C to 900 ° C, and the heating temperature and the heating time at the time of solidification after pressure molding are the same as those at the time of the first heating. It is desirable to be about the same.
【０００８】[0008]
【作用】炭化されたポリ塩化ビニリデン樹脂の粉末粒子
に対し、炭化されていない粉末粒子（ポリ塩化ビニリデ
ン樹脂そのものの粉末）はバインダ−として作用する。
つまり、炭化粉末粒子に「濡れ性」を付与することによ
り炭化粉末粒子相互間の粘着力を高め、加圧成形時にお
ける形状の保持性を大幅に向上させる。さらに、加熱処
理によって固形化することが可能であるので、固形化の
ために大量の電力を消費するものと比べると、はるかに
少ないエネルギ−で固形化することができ、装置として
も通常のものを使用することができる。The non-carbonized powder particles (powder of the polyvinylidene chloride resin itself) act as a binder with respect to the powder particles of the carbonized polyvinylidene chloride resin.
That is, by imparting "wetting" to the carbonized powder particles, the adhesive force between the carbonized powder particles is increased, and the shape retention during pressure molding is significantly improved. Furthermore, since it can be solidified by heat treatment, it can be solidified with far less energy than that which consumes a large amount of electric power for solidification, and it is a normal device. Can be used.
【０００９】製造された多孔質炭素材料は、もともとポ
リ塩化ビニリデン樹脂を原料とするものであるから、電
気二重層コンデンサの電極としての性能は、始めから炭
化粒子となっているもののみを固形化したものと比べ、
勝ってはいても劣ることはない。Since the manufactured porous carbon material is originally made of polyvinylidene chloride resin as a raw material, the performance as an electrode of the electric double layer capacitor is solidified only from carbonized particles from the beginning. Compared to what you did,
Winning is not inferior.
【００１０】[0010]
【実施例】この発明の電気二重層コンデンサ電極用多孔
質炭素材料の製造工程を図１に示す。まず、実施例１に
ついて説明する。粉末状のポリ塩化ビニリデン樹脂（Ｐ
ＶＤＣ）を加熱処理し、これを炭化してポリ塩化ビニリ
デン樹脂の炭化粉末粒子を製造する。この工程では、窒
素ガス雰囲気等非酸化雰囲気中の加熱炉において、７０
０℃〜９００℃の温度で約１時間第一の加熱処理を行
う。その結果、ポリ塩化ビニリデン樹脂からは、水素、
一酸化炭素、メタノ−ル、塩化水素ガスが放出され、ポ
リ塩化ビニリデン樹脂には原子又は分子欠陥による微細
な細孔が形成される。これらの細孔は極めて均一な状態
で形成され、また、イオンの吸着性に優れており、電気
二重層コンデンサに使用したときに、大容量の電荷の蓄
積が可能となる。EXAMPLE FIG. 1 shows a manufacturing process of a porous carbon material for an electric double layer capacitor electrode of the present invention. First, the first embodiment will be described. Powdered polyvinylidene chloride resin (P
VDC) is heat-treated and carbonized to produce carbonized powder particles of polyvinylidene chloride resin. In this step, in a heating furnace in a non-oxidizing atmosphere such as a nitrogen gas atmosphere, 70
The first heat treatment is performed at a temperature of 0 ° C. to 900 ° C. for about 1 hour. As a result, from the polyvinylidene chloride resin, hydrogen,
Carbon monoxide, methanol and hydrogen chloride gas are released, and fine pores are formed in the polyvinylidene chloride resin due to atomic or molecular defects. These pores are formed in an extremely uniform state and have excellent ion adsorption, and when used in an electric double layer capacitor, a large amount of charge can be stored.
【００１１】このようにして形成したポリ塩化ビニリデ
ン樹脂の炭化粉末粒子と、そのままのポリ塩化ビニリデ
ン樹脂粉末粒子とを混合する。炭化粉末粒子とそのまま
の粉末粒子との割合は、炭化粉末粒子：そのままの粉末
粒子、の比率が５：５〜７：３（重量比）の範囲であ
る。さらに、このように混合した粉末粒子を金型に入
れ、約5,000kg ／cm2 〜5,500kg ／cm2 の圧力でバルク
状に成形する。The carbonized powder particles of the polyvinylidene chloride resin thus formed are mixed with the polyvinylidene chloride resin powder particles as they are. The ratio of the carbonized powder particles to the powder particles as they are is such that the ratio of carbonized powder particles to the powder particles as they are is in the range of 5: 5 to 7: 3 (weight ratio). Further, the powder particles thus mixed are put into a mold and molded into a bulk at a pressure of about 5,000 kg / cm @ 2 to 5,500 kg / cm @ 2.
【００１２】このときに、ポリ塩化ビニリデン樹脂の粉
末粒子は、炭化されたものに対してバインダ−の役目を
果たす。すなわち、炭化粒子表面に「濡れ」を生じさ
せ、相互の粘着力を大きくして形状の保持性を高め、ま
た、成分蒸発に伴う凝集力で炭化粒子間の距離を短くし
て炭化粒子間の相互接合性を高める。At this time, the polyvinylidene chloride resin powder particles serve as a binder for the carbonized particles. That is, "wetting" is caused on the surface of the carbonized particles, the mutual adhesive force is increased to improve the shape retention, and the cohesive force accompanying the component evaporation shortens the distance between the carbonized particles to reduce the distance between the carbonized particles. Increase mutual connectivity.
【００１３】次いで、バルク状に形成した材料を、再
度、第二の加熱処理を行って固形化する。このときの加
熱温度及び加熱時間は、始めにポリ塩化ビニリデン樹脂
の粉末を炭化する時と同程度とすることが好ましい。さ
らに、雰囲気としては、始めの加熱処理の時と同様窒素
ガス雰囲気等非酸化雰囲気とした。再度の加熱処理によ
って、バインダ−として作用したポリ塩化ビニリデン樹
脂の粉末粒子も炭化し、そこには、予め炭化した粒子と
同様な細孔が形成されることになる。Next, the material formed in bulk is subjected to the second heat treatment again to be solidified. It is preferable that the heating temperature and the heating time at this time are the same as those at the time of first carbonizing the powder of polyvinylidene chloride resin. Further, the atmosphere was a non-oxidizing atmosphere such as a nitrogen gas atmosphere as in the first heat treatment. By the heat treatment again, the powder particles of the polyvinylidene chloride resin acting as the binder are also carbonized, and the same pores as the carbonized particles are formed therein.
【００１４】こうして製造した多孔質炭素材料は、図２
に示す電気二重層コンデンサの固形電極として利用され
る。この多孔質炭素材料を用いた電気二重層コンデンサ
の固形電極の電気容量等についての実験結果を図３及び
図４に示す。これによると、第一及び第二の加熱処理温
度８００℃でＰＶＤＣ炭化粒子／ＰＶＤＣ含有率が６：
４の場合が一番体積比容量が大きくなった。また各温度
ともＰＶＤＣ炭化粒子／ＰＶＤＣ含有率が６：４の場合
が一番容量が大きくなっている。この原因は、炭化前の
ＰＶＤＣが炭化される際、不純物が排出される時に出来
る細孔が電解液の侵入を促進し、含有率６：４の場合が
電極密度とこの細孔の兼ね合いが最も良好のためと考え
られる。加熱処理温度での容量の違いは、加熱処理温度
が高い８５０℃では容量が小さくなっている。これは、
ＰＶＤＣ炭化粒子の細孔が炭化処理中に炭素原子の移動
によって潰されるためと考えられる。The porous carbon material produced in this manner is shown in FIG.
It is used as a solid electrode of the electric double layer capacitor shown in. Experimental results on the electric capacity of the solid electrode of the electric double layer capacitor using this porous carbon material are shown in FIGS. 3 and 4. According to this, at the first and second heat treatment temperatures of 800 ° C., the PVDC carbon particle / PVDC content ratio is 6:
In the case of 4, the volume specific capacity was the largest. Further, at each temperature, the capacity is largest when the PVDC carbonized particles / PVDC content is 6: 4. The reason for this is that when PVDC before carbonization is carbonized, the pores formed when impurities are discharged promote the invasion of the electrolytic solution, and in the case where the content is 6: 4, the balance between the electrode density and the pores is the most. Probably because of good condition. The difference in the capacity at the heat treatment temperature is that the capacity is small at 850 ° C., where the heat treatment temperature is high. this is,
It is considered that the pores of the PVDC carbonized particles are crushed by the movement of carbon atoms during the carbonization treatment.
【００１５】次に、実施例２として、図１の第一の加熱
処理温度を８００℃とし、第二の加熱処理の際の雰囲気
を、窒素ガス等を温水にバブリングして生成した窒素ガ
ス等と水蒸気との混合気体雰囲気とし、加熱温度を７０
０℃とし、加熱時間を１時間又は４時間とした以外は第
一の実施例と同様にして多孔質炭素材料を製造した。Next, as Example 2, the first heat treatment temperature in FIG. 1 was set to 800 ° C., and the atmosphere during the second heat treatment was nitrogen gas produced by bubbling nitrogen gas or the like into hot water. A mixed gas atmosphere of water and water vapor is used, and the heating temperature is 70
A porous carbon material was produced in the same manner as in Example 1 except that the temperature was 0 ° C. and the heating time was 1 hour or 4 hours.
【００１６】こうして製造した多孔質炭素材料は、実施
例１と同様に、図２に示す電気二重層コンデンサの固形
電極として利用される。この多孔質炭素材料を用いた電
気二重層コンデンサの固形電極の電気容量等についての
実験結果を図５に示す。これによると、第二の加熱処理
時間を１時間とした場合の方が４時間とした場合よりも
容量が大きく、またＰＶＤＣ炭化粒子：ＰＶＤＣ含有率
が７：３の場合が一番容量が大きくなっている。ここ
で、ＰＶＤＣ炭化粒子：ＰＶＤＣ含有率が７：３以上で
は成形できないため、ＰＶＤＣ炭化粒子：ＰＶＤＣ含有
率が７：３の場合の容量が最も大きいことが分かった。
さらに、ベストのものの比較では実施例２の方が実施例
１に比較して約５０％容量が大きいことが分かった。The porous carbon material thus produced is used as a solid electrode of the electric double layer capacitor shown in FIG. FIG. 5 shows the experimental results on the electric capacity of the solid electrode of the electric double layer capacitor using this porous carbon material. According to this, when the second heat treatment time is 1 hour, the capacity is larger than when it is 4 hours, and the capacity is the largest when the PVDC carbon particle: PVDC content ratio is 7: 3. Has become. Here, it was found that when the PVDC carbonized particle: PVDC content ratio is 7: 3 or more, molding cannot be performed, and therefore the capacity is largest when the PVDC carbonized particle: PVDC content ratio is 7: 3.
Further, in comparison of the best one, it was found that the capacity of Example 2 was about 50% larger than that of Example 1.
【００１７】また、比較のため、図６には、ＰＶＤＣの
代わりにフェノ−ル樹脂をバインダ−として用いた場合
のＰＶＤＣ炭化試料含有率に対するキャパシタ容量の関
係を示す。この結果より、バインダにＰＶＤＣを用いた
実施例１又は実施例２と比較すると、フェノ−ル樹脂を
バインダ−として用いた場合はＰＶＤＣ炭化試料含有率
に関係なく重量比容量、体積比容量ともに小さな値とな
った。これは、バインダ−として用いたＰＶＤＣは炭化
されると容量に関与できるが、フェノ−ル樹脂は炭化さ
れても、容量に関与しないためと考えられる。また、フ
ェノ−ル樹脂がＰＶＤＣ表面の細孔に入り込み細孔を潰
してしまっている可能性も考えられる。For comparison, FIG. 6 shows the relationship between the capacitance of the PVDC carbonized sample and the capacitance of the capacitor when a phenol resin is used as the binder instead of PVDC. From this result, as compared with Example 1 or Example 2 in which PVDC was used as the binder, both the weight specific capacity and the volume specific capacity were small when the phenol resin was used as the binder regardless of the PVDC carbonized sample content. It became a value. It is considered that this is because the PVDC used as the binder can contribute to the capacity when carbonized, but the phenol resin does not contribute to the capacity even when carbonized. It is also possible that the phenol resin has entered the pores on the PVDC surface and crushed the pores.
【００１８】実施例１と実施例２とのベストの容量を発
揮したサンプルについてその細孔分布を画像分析法で調
査した。炭素の細孔分析について詳しくは信州大学工学
部教授遠藤守信氏らの論文「活性炭繊維におけるポア構
造のフラクタル解析」（電子情報通信学会論文誌Ｃ−
（ギリシャの２）Ｎｏ．３ Ｐ１３９〜１４７ １９９
４年３月）に記載してありそれを参照願いたい。今回の
画像分析法はサンプルを撮影する電子顕微鏡として加速
電圧４００ＫＶの透過型電子顕微鏡を用い、これにより
倍率２０万倍の画像を得、この画像を更に３０倍に拡大
して印画紙に焼き付けたものを原画像とした。実施例１
及び実施例２の原画像をそれぞれ図７、図８に示す。つ
いでこれらの原画像を高分析能のＣＣＤカメラによりコ
ンピュ−タに読み込んで細孔を分析した。すなわち、原
画像から読み込んだ濃淡デ−タを二次元フ−リエ変換
し、その変換デ−タから細孔径を求め、これらのデ−タ
を統計的に解析して細孔径の分布を求めた。実施例１及
び実施例２についてこの画像分析法によって得られた細
孔径分布をそれぞれ図９、図１０に示す。これらの図の
横軸は細孔径を表し、縦軸は細孔の相対的な頻度を表し
ており絶対数ではない。The pore distributions of the samples exhibiting the best capacity in Examples 1 and 2 were examined by image analysis. For details on the pore analysis of carbon, see the paper “Fractal Analysis of Pore Structure in Activated Carbon Fiber” by Morinobu Endo, a professor of Faculty of Engineering, Shinshu University.
(Greek 2) No. 3 P139 ~ 147 199
(March 4), please refer to it. In this image analysis method, a transmission electron microscope with an accelerating voltage of 400 KV was used as an electron microscope for photographing a sample, and an image with a magnification of 200,000 was obtained by this. The original image was used. Example 1
7 and 8 show the original images of Example 2 and Example 2, respectively. Then, these original images were read into a computer with a CCD camera having a high analysis capability to analyze the pores. That is, the grayscale data read from the original image was subjected to a two-dimensional Fourier transform, the pore size was obtained from the transformed data, and the pore size distribution was obtained by statistically analyzing these data. . The pore size distributions obtained by this image analysis method for Example 1 and Example 2 are shown in FIGS. 9 and 10, respectively. The horizontal axis of these figures represents the pore diameter, and the vertical axis represents the relative frequency of the pores, not the absolute number.
【００１９】これら図９、図１０から実施例１のサンプ
ルは直径が１０オングストロ−ム以下の細孔が約３５％
有るが、実施例２のサンプルでは約１０％と非常に減少
していることが分かった。また、直径が１０〜２０オン
グストロ−ムの範囲の細孔が、実施例１のサンプルでは
約４０％であるが、実施例２のサンプルでは約５０％と
増加していることが分かった。これらの結果から、１０
オングストロ−ム以下の細孔は容量にあまり寄与せず、
１０〜２０オングストロ−ムの範囲の細孔が、容量に大
きく寄与しているものと考えられ、第二の加熱処理を非
酸化・水蒸気雰囲気下で行うことは、１０オングストロ
−ム以下の細孔を１０〜２０オングストロ−ムの範囲の
細孔に成長させる効果が有るものと考えられる。9 and 10, the sample of Example 1 has about 35% of pores having a diameter of 10 angstroms or less.
However, it was found that the sample of Example 2 was extremely reduced to about 10%. Further, it was found that the number of pores having a diameter in the range of 10 to 20 angstrom was about 40% in the sample of Example 1 and about 50% in the sample of Example 2. From these results, 10
Pores smaller than angstrom do not contribute much to the capacity,
It is considered that pores in the range of 10 to 20 angstroms contribute significantly to the capacity, and performing the second heat treatment in a non-oxidizing / water vapor atmosphere means that pores of 10 angstroms or less. Is considered to have the effect of growing into the pores in the range of 10 to 20 angstrom.
【００２０】[0020]
【発明の効果】上述のように、この発明によれば、ポリ
塩化ビニリデンの粉末粒子を炭化させて固化した電気二
重層コンデンサ用電極を、通常の装置を使用して、簡易
にしかも低コストで製造できる。また、電極としての性
能は、全て予め炭化した粉末粒子を固形化するものと比
べ、同等の性能を確保することができる。さらに、フェ
ノ−ル樹脂等をバインダ−として使用して炭化させるも
のと比べると、原料がポリ塩化ビニリデンのみであるの
で、電極性能の面で優れている。なお、バインダ−を炭
化させない炭素材料電極もあるが、このような材料では
バインダ−が劣化する問題点があるのに対し、この発明
の多孔質炭素材料にはその欠点がない。さらに、成形後
の第二の加熱処理の際に、非酸化・水蒸気雰囲気中で熱
処理を行うことにより第一の加熱処理（炭化）で生成さ
れた静電容量に寄与しない範囲の細孔、すなわち細孔径
が１０オングストロ−ム以下（過去の実験結果から５〜
６オングストロ−ム以下の細孔であると考えられるが、
そのようなサンプルが製造できていないので明確ではな
い。）の細孔が静電容量に寄与する直径１０オングスト
ロ−ム近辺の細孔となり静電容量のさらなる向上ができ
る。As described above, according to the present invention, an electrode for an electric double layer capacitor obtained by carbonizing and solidifying powdery particles of polyvinylidene chloride can be easily and inexpensively manufactured by using an ordinary apparatus. Can be manufactured. Further, the performance as an electrode can ensure the same performance as that of solidifying all the powder particles which have been carbonized in advance. Further, as compared with the case where a phenol resin or the like is used as a binder for carbonization, the raw material is only polyvinylidene chloride, which is excellent in electrode performance. Although there is a carbon material electrode that does not carbonize the binder, such a material has a problem of degrading the binder, whereas the porous carbon material of the present invention does not have the drawback. Furthermore, during the second heat treatment after molding, by performing heat treatment in a non-oxidizing / steam atmosphere, pores in a range not contributing to the capacitance generated in the first heat treatment (carbonization), that is, Pore size less than 10 angstrom (from past experimental results
It is considered that the pores are 6 angstroms or less,
It is not clear as such samples have not been produced. The pores of 4) become pores in the vicinity of the diameter of 10 angstroms that contribute to the electrostatic capacity, and the electrostatic capacity can be further improved.
【図１】この発明の多孔質炭素材料の製造過程を示す工
程図である。FIG. 1 is a process drawing showing a process for producing a porous carbon material of the present invention.
【図２】電気二重層コンデンサの構造を示す断面図であ
る。FIG. 2 is a sectional view showing a structure of an electric double layer capacitor.
【図３】この発明の実施例１の多孔質炭素材料の電気的
性能を実験した一デ−タを示すグラフである。FIG. 3 is a graph showing data obtained by conducting an experiment on electrical performance of the porous carbon material of Example 1 of the present invention.
【図４】この発明の実施例１の多孔質炭素材料の電気的
性能を実験した別のデ−タを示すグラフである。FIG. 4 is a graph showing another data in which the electrical performance of the porous carbon material of Example 1 of the present invention was tested.
【図５】この発明の実施例２の多孔質炭素材料の電気的
性能を実験した一デ−タを示すグラフである。FIG. 5 is a graph showing data obtained by conducting an experiment on electrical performance of the porous carbon material of Example 2 of the present invention.
【図６】バインダ−としてフェノ−ル樹脂を使用し製造
した炭素材料と比較したデ−タを示すグラフである。FIG. 6 is a graph showing data compared with a carbon material produced by using a phenol resin as a binder.
【図７】実施例１の多孔質炭素材料の透過型電子顕微鏡
で撮影した原画像を示す写真である。FIG. 7 is a photograph showing an original image of the porous carbon material of Example 1 taken with a transmission electron microscope.
【図８】実施例２の多孔質炭素材料の透過型電子顕微鏡
で撮影した原画像を示す写真である。FIG. 8 is a photograph showing an original image of the porous carbon material of Example 2 taken with a transmission electron microscope.
【図９】実施例１の多孔質炭素材料の細孔径の分布を表
す図である。9 is a diagram showing a distribution of pore diameters of the porous carbon material of Example 1. FIG.
【図１０】実施例２の多孔質炭素材料の細孔径の分布を
表す図である。FIG. 10 is a diagram showing a distribution of pore diameters of the porous carbon material of Example 2.
Claims (7)
リ塩化ビニリデン樹脂の炭化粉末粒子と、ポリ塩化ビニ
リデン樹脂の粉末粒子とを混合し、この混合粒子を加圧
成形した後、さらに非酸化雰囲気中で第二の加熱処理を
行うことを特徴とする電気二重層コンデンサの電極用炭
素材料の製造方法。1. A carbonized powder particle of a polyvinylidene chloride resin, which has been first heat-treated in a non-oxidizing atmosphere, and a powder particle of a polyvinylidene chloride resin are mixed, and the mixed particle is pressure-molded, and then further mixed. A method for producing a carbon material for an electrode of an electric double layer capacitor, which comprises performing a second heat treatment in a non-oxidizing atmosphere.
中で行うことを特徴とする請求項１に記載の電気二重層
コンデンサの電極用炭素材料の製造方法。2. The method for producing a carbon material for an electrode of an electric double layer capacitor according to claim 1, wherein the second heat treatment is performed in a non-oxidizing water vapor atmosphere.
ポリ塩化ビニリデン樹脂の粉末粒子との重量比が５：５
〜７：３の範囲にあることを特徴とする請求項１又は２
に記載の電気二重層コンデンサの電極用炭素材料の製造
方法。3. A weight ratio of carbonized powder particles of polyvinylidene chloride resin to powder particles of polyvinylidene chloride resin is 5: 5.
It is in the range of to 7: 3.
A method for producing a carbon material for an electrode of an electric double layer capacitor according to.
００℃の範囲にあることを特徴とする請求項１ないし３
のいずれかに記載の電気二重層コンデンサの電極用炭素
材料の製造方法。4. The temperature of the first heat treatment is 700 ° C. to 9 ° C.
4. The composition according to claim 1, which is in the range of 00.degree.
5. A method for producing a carbon material for an electrode of an electric double layer capacitor according to any one of 1.
時間と、第二の加熱処理における加熱温度及び時間とが
同程度であることを特徴とする請求項１ないし４のいず
れかに記載の電気二重層コンデンサの電極用炭素材料の
製造方法。5. The heating temperature and the heating time in the first heat treatment and the heating temperature and the time in the second heat treatment are approximately the same. A method for manufacturing a carbon material for an electrode of an electric double layer capacitor.
リ塩化ビニリデン樹脂の炭化粉末粒子と、ポリ塩化ビニ
リデン樹脂の粉末粒子とを混合してこの混合粒子を加圧
成形し、さらに非酸化雰囲気中で第二の加熱処理を行っ
て固形化したことを特徴とする電気二重層コンデンサの
電極用炭素材料。6. A mixture of carbonized powder particles of polyvinylidene chloride resin, which has undergone the first heat treatment in a non-oxidizing atmosphere, and powder particles of polyvinylidene chloride resin, and the mixed particles are pressure-molded. A carbon material for an electrode of an electric double layer capacitor, characterized by being solidified by performing a second heat treatment in an oxidizing atmosphere.
リ塩化ビニリデン樹脂の炭化粉末粒子と、ポリ塩化ビニ
リデン樹脂の粉末粒子とを混合してこの混合粒子を加圧
成形し、さらに非酸化水蒸気雰囲気中で第二の加熱処理
を行って固形化したことを特徴とする電気二重層コンデ
ンサの電極用炭素材料。7. A mixture of carbonized powder particles of polyvinylidene chloride resin subjected to the first heat treatment in a non-oxidizing atmosphere and powder particles of polyvinylidene chloride resin, and the mixed particles are pressure-molded. A carbon material for an electrode of an electric double layer capacitor, characterized by being solidified by performing a second heat treatment in an oxidizing steam atmosphere.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP07413695A JP3527789B2 (en) | 1994-12-29 | 1995-03-30 | Electrode for electric double layer capacitor and its manufacturing method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33911594 | 1994-12-29 | ||
| JP6-339115 | 1994-12-29 | ||
| JP07413695A JP3527789B2 (en) | 1994-12-29 | 1995-03-30 | Electrode for electric double layer capacitor and its manufacturing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH08236406A true JPH08236406A (en) | 1996-09-13 |
| JP3527789B2 JP3527789B2 (en) | 2004-05-17 |
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|---|---|---|---|
| JP07413695A Expired - Fee Related JP3527789B2 (en) | 1994-12-29 | 1995-03-30 | Electrode for electric double layer capacitor and its manufacturing method |
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| Country | Link |
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| JP (1) | JP3527789B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028547A1 (en) * | 1996-02-02 | 1997-08-07 | Takeda Chemical Industries, Ltd. | Activated carbon electrode and process for producing the same |
| CN103482601A (en) * | 2013-09-06 | 2014-01-01 | 浙江大学 | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer |
| JP2015151324A (en) * | 2014-02-18 | 2015-08-24 | 住友電気工業株式会社 | Activated carbon and method for producing the same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5275690A (en) * | 1975-12-19 | 1977-06-24 | Agency Of Ind Science & Technol | Production of carbon materials |
| JPH01111708A (en) * | 1987-10-26 | 1989-04-28 | Pentel Kk | Production of activated carbon molded body |
| JPH05304047A (en) * | 1992-04-28 | 1993-11-16 | Matsushita Electric Ind Co Ltd | Polarized electrode and manufacture thereof |
| JPH06267794A (en) * | 1993-03-12 | 1994-09-22 | Morinobu Endo | Manufacture of polarizable electrode material |
-
1995
- 1995-03-30 JP JP07413695A patent/JP3527789B2/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5275690A (en) * | 1975-12-19 | 1977-06-24 | Agency Of Ind Science & Technol | Production of carbon materials |
| JPH01111708A (en) * | 1987-10-26 | 1989-04-28 | Pentel Kk | Production of activated carbon molded body |
| JPH05304047A (en) * | 1992-04-28 | 1993-11-16 | Matsushita Electric Ind Co Ltd | Polarized electrode and manufacture thereof |
| JPH06267794A (en) * | 1993-03-12 | 1994-09-22 | Morinobu Endo | Manufacture of polarizable electrode material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028547A1 (en) * | 1996-02-02 | 1997-08-07 | Takeda Chemical Industries, Ltd. | Activated carbon electrode and process for producing the same |
| CN103482601A (en) * | 2013-09-06 | 2014-01-01 | 浙江大学 | Preparation method for three-dimensional multistage porous carbon based on polyvinylidene chloride-polystyrene segmented copolymer |
| JP2015151324A (en) * | 2014-02-18 | 2015-08-24 | 住友電気工業株式会社 | Activated carbon and method for producing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3527789B2 (en) | 2004-05-17 |
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