JP2016027599A - Carbon porous electrode and method for manufacturing the same - Google Patents
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Abstract
Description
本発明は、電気二重層キャパシタ、リチウムイオンキャパシタ等の蓄電デバイスの電極として用いられる炭素多孔質電極およびその製造方法に関する。 The present invention relates to a carbon porous electrode used as an electrode of an electric storage device such as an electric double layer capacitor and a lithium ion capacitor, and a method for producing the same.
電気二重層キャパシタの電極としては、１ｇあたりに１０００〜２０００ｍ2という非常に広い表面積を有する活性炭の粒子をバインダで固めたものが使用されている。 As an electrode of the electric double layer capacitor, an activated carbon particle having a very large surface area of 1000 to 2000 m 2 per 1 g is used, which is hardened with a binder.
また、下記特許文献１，２には、気孔形成剤を用いて多孔質とした樹脂を窒素雰囲気下で熱処理して炭素化することによりマクロ孔を有する炭素多孔体とし、その後、水蒸気または二酸化炭素の存在下での熱処理による賦活処理を施してミクロ孔を形成することにより得られる、バインダを含まない炭素多孔質電極が提案されている。 Further, in Patent Documents 1 and 2 below, a porous resin using a pore forming agent is heat-treated in a nitrogen atmosphere and carbonized to obtain a carbon porous body having macropores, and then water vapor or carbon dioxide. There has been proposed a carbon porous electrode that does not contain a binder, which is obtained by applying an activation treatment by heat treatment in the presence of a micropore to form micropores.
前述のマクロ孔の形成に関して、特許文献１においては気孔形成剤として液体で蒸発型の発泡剤が使用されているので（［００３８］−［００４０］）、孔径の制御が困難であり、孔径が不均一となる、という課題がある。特許文献２においては、樹脂に予め混入され、樹脂の硬化後に水洗して除去される米澱粉が用いられているので（実施例１）、工程が煩雑になるという課題がある。 Regarding the formation of the above-mentioned macropores, in Patent Document 1, since a liquid and evaporating foaming agent is used as a pore-forming agent ([0038]-[0040]), it is difficult to control the pore diameter, and the pore diameter is There is a problem of non-uniformity. In patent document 2, since the rice starch previously mixed with resin and washed and removed after hardening of resin is used (Example 1), there exists a subject that a process becomes complicated.
また、特許文献１，２においては、電極の厚みを薄くするためには、硬化後の樹脂成形体のブロックを薄く切り出す工程を必要とするが、これもまた工程を煩雑化する。 Further, in Patent Documents 1 and 2, in order to reduce the thickness of the electrode, a process of cutting out the block of the resin molded body after curing is required, but this also complicates the process.
さらに、キャパシタの内部抵抗を低くするためには、電極の材料そのものの固有抵抗値（体積抵抗率）が低いことが望ましい。 Furthermore, in order to reduce the internal resistance of the capacitor, it is desirable that the specific resistance value (volume resistivity) of the electrode material itself be low.
したがって本発明の目的は、比較的簡潔な工程により、バインダを含まない炭素多孔質電極を得ることにある。 Accordingly, an object of the present invention is to obtain a carbon porous electrode containing no binder by a relatively simple process.
本発明のさらなる目的は、固有抵抗値の低い材料が用いられた炭素多孔質電極を提供することにある。 A further object of the present invention is to provide a carbon porous electrode using a material having a low specific resistance value.
本発明によれば、アモルファス炭素を含み、平均孔径０．１μｍ以上のマクロ孔および平均孔径１０nm以下のミクロ孔を有し、固有抵抗値が１Ω・cm以下である炭素多孔質電極が提供される。 According to the present invention, there is provided a carbon porous electrode containing amorphous carbon, having macropores having an average pore diameter of 0.1 μm or more and micropores having an average pore diameter of 10 nm or less and having a specific resistance value of 1 Ω · cm or less. .
本発明の炭素多孔質電極は、密度が略均一であることができる。ここで、本明細書において、略均一であるとは、ばらつきが１０％以内、８％以内、又は７％以内であることを言うものである。 The carbon porous electrode of the present invention can have a substantially uniform density. Here, in this specification, being substantially uniform means that the variation is within 10%, within 8%, or within 7%.
前述の固有抵抗値は０．１Ω・cm以下であることが望ましい。 The above-mentioned specific resistance value is desirably 0.1 Ω · cm or less.
この炭素多孔質電極は、例えば、前記アモルファス炭素中に均一に分散した炭素粉末をさらに含んでいる。 The carbon porous electrode further includes, for example, carbon powder uniformly dispersed in the amorphous carbon.
前記アモルファス炭素は、例えば、炭素含有樹脂の炭素化により得られたものであり、前記マクロ孔は前記炭素含有樹脂中に均一に分散し前記炭素化の過程で消失して気孔を形成する穴開け材粒子により形成されたものである。 The amorphous carbon is obtained, for example, by carbonization of a carbon-containing resin, and the macropores are uniformly dispersed in the carbon-containing resin and disappear in the carbonization process to form pores. It is formed by material particles.
前述の炭素多孔質電極は、炭素含有樹脂に穴開け材粒子を均一に分散させ、前記穴開け材粒子を分散させた前記炭素含有樹脂を非酸化雰囲気中で熱処理することにより前記炭素含有樹脂を炭素化するとともに前記穴開け材粒子を消失させて平均孔径０．１μｍ以上のマクロ孔を形成し、前記マクロ孔が形成された炭素化物に賦活処理を施すことにより平均孔径１０nm以下のミクロ孔を形成することを含む方法により製造される。 The carbon porous electrode described above is obtained by uniformly dispersing the hole-forming material particles in the carbon-containing resin and heat-treating the carbon-containing resin in which the hole-forming material particles are dispersed in a non-oxidizing atmosphere. Carbonization and disappearance of the perforating material particles to form macropores having an average pore diameter of 0.1 μm or more, and by applying an activation treatment to the carbonized material in which the macropores are formed, micropores having an average pore diameter of 10 nm or less Manufactured by a method comprising forming.
炭素含有樹脂としては、残炭率７％以上、１０％以上、又は１５％以上の樹脂を使用することができる。炭素含有樹脂としては、例えばポリ塩化ビニル樹脂、フェノール樹脂、エポキシ樹脂、ポリアクリロニトリル樹脂等が挙げられる。 As the carbon-containing resin, a resin having a residual carbon ratio of 7% or more, 10% or more, or 15% or more can be used. Examples of the carbon-containing resin include polyvinyl chloride resin, phenol resin, epoxy resin, and polyacrylonitrile resin.
ここで、本明細書において、残炭率とは、炭素化前の樹脂中の炭素に対する、炭素化後に得られるアモルファス炭素の割合を言うものである。 Here, in this specification, the residual carbon ratio refers to the ratio of amorphous carbon obtained after carbonization to carbon in the resin before carbonization.
穴開け材粒子としては、残炭率５％以下、３％以下、又は１％以下の樹脂から成る粒子が挙げられる。この樹脂としては、例えばポリエチレン、ポリスチレン、及びポリテトラフルオロエチレン等のポリオレフィン、ポリアセタール等のポリアルデヒド、並びにポリメチルメタクリレート（ＰＭＭＡ）等のアクリル樹脂等が挙げられる。 Examples of the drilling material particles include particles made of a resin having a residual carbon ratio of 5% or less, 3% or less, or 1% or less. Examples of this resin include polyolefins such as polyethylene, polystyrene, and polytetrafluoroethylene, polyaldehydes such as polyacetal, and acrylic resins such as polymethyl methacrylate (PMMA).
この方法は、前記炭素化の前において、前記穴開け材粒子が分散した炭素含有樹脂を押出成形によりシート状に成形することをさらに含むことが好ましい。 Preferably, this method further includes forming the carbon-containing resin in which the perforating material particles are dispersed into a sheet by extrusion molding before the carbonization.
この方法は、前記炭素含有樹脂にさらに炭素粉末を均一に分散させることをさらに含むことがさらに好ましい。 More preferably, the method further includes uniformly dispersing carbon powder in the carbon-containing resin.
前述の炭素粉末は、例えば、黒鉛粉末、カーボンナノチューブ、活性炭粉末、非晶性炭素粉末および炭素繊維からなる群から選択される。 The aforementioned carbon powder is selected from the group consisting of, for example, graphite powder, carbon nanotube, activated carbon powder, amorphous carbon powder, and carbon fiber.
前述の炭素多孔質電極には、随意の金属層を積層させてもよい。金属層を構成する金属としては、アルミニウム、金、白金、銀、クロム、ニッケル、チタン、鉄、錫、パラジウム等、及びこれらの合金が挙げられる。 An optional metal layer may be laminated on the aforementioned carbon porous electrode. Examples of the metal constituting the metal layer include aluminum, gold, platinum, silver, chromium, nickel, titanium, iron, tin, palladium, and alloys thereof.
例えば、本発明の炭素多孔質電極を電気二重層キャパシタの分極性電極として使用する場合、金属層を積層することによりこの金属を集電極として機能させることができるため、電気二重層キャパシタを構成する部品の数を減らすことができる等の利点を有する。 For example, when the carbon porous electrode of the present invention is used as a polarizable electrode of an electric double layer capacitor, the metal can be made to function as a collecting electrode by stacking metal layers, so that an electric double layer capacitor is configured. The advantage is that the number of parts can be reduced.
炭素含有樹脂に、炭素含有樹脂の炭素化の過程で消失して気孔を形成する穴開け材の粒子を予め均一に分散させて炭素化することにより、簡潔な工程で、マクロ孔を有する炭素多孔体を得ることができる。この場合に、穴開け材粒子の形状と大きさに応じた形状と大きさの気孔が形成されるので、穴開け材粒子の平均粒径および粒径分布を適切に選択することでマクロ孔の平均孔径および孔径分布を任意に制御することができる。また、炭素化の前において押出成形によりシート状に成形することで、樹脂ブロックを薄く切り出す工程が不要となり、要求される厚みの電極を容易に得ることができる。 A carbon porous resin having macropores in a simple process by carbonizing the carbon containing resin by uniformly dispersing in advance the particles of the drilling material that disappears in the process of carbonization of the carbon containing resin to form pores. You can get a body. In this case, since pores having a shape and size corresponding to the shape and size of the drilling material particles are formed, the macropores can be formed by appropriately selecting the average particle size and the particle size distribution of the drilling material particles. The average pore size and the pore size distribution can be arbitrarily controlled. Further, by forming into a sheet form by extrusion before carbonization, a step of cutting out the resin block is unnecessary, and an electrode having a required thickness can be easily obtained.
電極材料の固有抵抗値を１Ω・cm以下、望ましくは０．１Ω・cm以下とすることで、キャパシタの内部抵抗を低くすることができる。電極に含まれるアモルファス炭素中に炭素粉末、例えば、黒鉛粉末、カーボンナノチューブ、活性炭素粉末、非晶性炭素粉末および炭素繊維からなる群から選択される炭素粉末を分散させることで、電極材料の固有抵抗値を低くすることができる。この炭素粉末は炭素化前の樹脂の成形を容易にするフィラーとしての役割も果たす。 By setting the specific resistance value of the electrode material to 1 Ω · cm or less, preferably 0.1 Ω · cm or less, the internal resistance of the capacitor can be lowered. By dispersing carbon powder selected from the group consisting of, for example, graphite powder, carbon nanotubes, activated carbon powder, amorphous carbon powder, and carbon fiber in amorphous carbon contained in the electrode, the electrode material is unique. The resistance value can be lowered. This carbon powder also serves as a filler that facilitates molding of the resin before carbonization.
図１に、本発明の炭素多孔質電極の製造方法の一実施形態に係る製造工程の概略を示す。 In FIG. 1, the outline of the manufacturing process which concerns on one Embodiment of the manufacturing method of the carbon porous electrode of this invention is shown.
図１において、アモルファス炭素源である炭素含有樹脂、例えば塩化ビニル樹脂に、フィラーとしての炭素粉末、例えば黒鉛粉末、カーボンナノチューブ活性炭粉末、非晶性炭素粉末または炭素繊維を混合し、さらに穴開け材としての例えばＰＭＭＡ粒子を混合する（ステップ１００）。この混合物をミキサーにかけて炭素粉末と穴開け材粒子を炭素含有樹脂中に分散させ、混練機で充分に混練する（ステップ１０２）。これを、スリット状の断面を有するダイが装着された押出成形機でシート状に成形し（ステップ１０４）、１８０℃程度に加熱して不融化処理を行った後に、非酸化雰囲気中、例えば窒素雰囲気中で熱処理をして炭素含有樹脂を炭素化すると同時に穴開け材粒子を消失させて気孔を形成させる（ステップ１０６）。このようにしてマクロ孔が形成された炭素シートに対して、二酸化炭素または水蒸気の存在下で炭素化の温度よりも高い温度で熱処理をしてミクロ孔を形成させる賦活処理を行って、所望の厚みの炭素多孔質電極を得る（ステップ１０８）。 In FIG. 1, a carbon-containing resin as an amorphous carbon source, such as a vinyl chloride resin, is mixed with a carbon powder as a filler, such as graphite powder, carbon nanotube activated carbon powder, amorphous carbon powder or carbon fiber, and further a perforating material. For example, PMMA particles are mixed (step 100). This mixture is put into a mixer to disperse the carbon powder and the hole-opening material particles in the carbon-containing resin and sufficiently kneaded with a kneader (step 102). This is formed into a sheet by an extruder equipped with a die having a slit-like cross section (step 104), heated to about 180 ° C. and infusibilized, and then in a non-oxidizing atmosphere such as nitrogen. Heat treatment is performed in an atmosphere to carbonize the carbon-containing resin, and at the same time, the perforating material particles are lost to form pores (step 106). The carbon sheet with the macropores formed in this manner is subjected to an activation process in which micropores are formed by heat treatment at a temperature higher than the carbonization temperature in the presence of carbon dioxide or water vapor. A carbon porous electrode having a thickness is obtained (step 108).
（実施例１）アモルファス炭素源としての塩化ビニル樹脂４５部と平均粒径５μｍの黒鉛３部に、気孔形成のための穴開け材としての平均粒径５μｍのＰＭＭＡを５３部配合した組成物に対して可塑剤としてジアリルフタレートモノマーを添加して、ヘンシェルミキサーを用いて分散させた後、加圧ニーダーを用いて十分に混練を繰り返して組成物を得、ペレタイザーによってペレット化し成形用組成物を得た。この成型用組成物のパレットを押出成形で厚さ４００μｍのシート状の成型物とした。このシート状成形物を１８０℃のエアオーブン中で２時間処理しプリカーサー（炭素前駆体）とした。その後、窒素ガス中で２０℃／ｈの昇温速度で昇温し、８００℃で３時間保持し自然冷却して焼成・炭素化を完了した。その後、二酸化炭素雰囲気中で９００℃で４．５時間保持した後、自然冷却して賦活処理を完了した。 Example 1 A composition comprising 45 parts of vinyl chloride resin as an amorphous carbon source and 3 parts of graphite having an average particle diameter of 5 μm and 53 parts of PMMA having an average particle diameter of 5 μm as a hole forming material for pore formation. In contrast, after adding a diallyl phthalate monomer as a plasticizer and dispersing it using a Henschel mixer, the composition is obtained by repeatedly kneading sufficiently using a pressure kneader, and pelletized by a pelletizer to obtain a molding composition. It was. The pallet of this molding composition was formed into a sheet-like molded product having a thickness of 400 μm by extrusion molding. This sheet-like molded product was treated in an air oven at 180 ° C. for 2 hours to obtain a precursor (carbon precursor). Thereafter, the temperature was raised in nitrogen gas at a rate of 20 ° C./h, held at 800 ° C. for 3 hours, and naturally cooled to complete firing and carbonization. Then, after hold | maintaining at 900 degreeC in a carbon dioxide atmosphere for 4.5 hours, it naturally cooled and completed the activation process.
このようにして得られた電極の気孔率（気孔を含む全体の体積、質量および炭素の密度１．５ｇ／cm3から計算される気孔率）は７６％、ＰＭＭＡ粒子の消失により形成された気孔の平均気孔径は３μｍであった。電極の厚みは約２００μｍ、曲げ強度７．４MPa、ヤング率１．３GPa、密度０．３６ｇ／cm3、窒素吸着法で測定した１点ＢＥＴ比表面積は８６７ｍ2／ｇ、窒素吸着法で測定した細孔分布のピークは２nm（２０オングストローム）、４端子法で測定した固有抵抗値は０．０６Ω・cm、と優れた物性を有するものであった。 The porosity of the electrode thus obtained (the porosity calculated from the total volume including pores, mass and carbon density of 1.5 g / cm 3 ) is 76%, and the porosity formed by the disappearance of the PMMA particles The average pore diameter of was 3 μm. The electrode thickness was about 200 μm, the bending strength was 7.4 MPa, the Young's modulus was 1.3 GPa, the density was 0.36 g / cm 3 , the one-point BET specific surface area measured by the nitrogen adsorption method was 867 m 2 / g, and the nitrogen adsorption method was used. The peak of the pore distribution was 2 nm (20 angstroms), and the specific resistance value measured by the 4-terminal method was 0.06 Ω · cm.
（実施例２〜５）
塩化ビニル樹脂に対する黒鉛およびＰＭＭＡの配合比と賦活処理の時間を変え、それ以外の条件は実施例１と同じにして電極を作成し、特性を測定した。
(Examples 2 to 5)
An electrode was prepared under the same conditions as in Example 1 except that the mixing ratio of graphite and PMMA to the vinyl chloride resin and the activation treatment time were changed, and the characteristics were measured.
図２に、一例として、実施例５において得られた電極の断面写真を示す。図２中、１０はアモルファス炭素、１２は黒鉛、１４はＰＭＭＡの消失により形成されたマクロ孔である。図３に、一例として、実施例２において得られた電極の細孔（ミクロ孔）分布の測定結果を示す。 FIG. 2 shows a cross-sectional photograph of the electrode obtained in Example 5 as an example. In FIG. 2, 10 is amorphous carbon, 12 is graphite, and 14 is macropores formed by disappearance of PMMA. FIG. 3 shows, as an example, the measurement results of the pore (micropore) distribution of the electrode obtained in Example 2.
表１に実施例１〜５の条件を示し、表２に特性の測定結果を示す。なお、平均気孔径はいずれも３μｍであり、電極の厚みはいずれも２００μｍであり、細孔分布のピークはいずれも２nm（２０オングストローム）であった。 Table 1 shows the conditions of Examples 1 to 5, and Table 2 shows the measurement results of the characteristics. The average pore diameter was 3 μm, the electrode thickness was 200 μm, and the pore distribution peak was 2 nm (20 Å).
図４には実施例１〜５で得られた電極の賦活重量収率と比表面積との関係を示す。横軸の賦活重量収率が減少することは賦活処理により重量が減少することを意味し、それとともに、たて軸の比表面積が増加している。 FIG. 4 shows the relationship between the activation weight yield of the electrodes obtained in Examples 1 to 5 and the specific surface area. Decreasing the activated weight yield on the horizontal axis means that the weight is reduced by the activation treatment, and at the same time, the specific surface area of the vertical axis is increased.
（実施例６〜８）
配合する黒鉛の量を増やして電極に含まれる黒鉛の量と固有抵抗値との関係を調べた。表３に各実施例の条件を示す。実施例６〜８では、炭素含有樹脂として塩素化ビニル樹脂が使われている。これら以外の条件は実施例１と同じである。表４には、炭素化後の炭素複合体中に含まれる黒鉛の割合と、賦活後の密度と固有抵抗値を示す。なお、炭素化後の黒鉛の割合は、炭素化の条件により定まる既知の塩素化ビニル樹脂の残炭率（炭素化前の樹脂に対する炭素化後に得られるアモルファス炭素の割合）と、使用された塩素化ビニル樹脂および黒鉛の量から計算した。表４より、炭素化後にアモルファス炭素と黒鉛が等量になる程度まで黒鉛を配合すれば、電極の固有抵抗値を０．００８７Ω・cmまで下げることが可能であることがわかる。
(Examples 6 to 8)
The relationship between the amount of graphite contained in the electrode and the specific resistance value was investigated by increasing the amount of graphite to be blended. Table 3 shows the conditions for each example. In Examples 6 to 8, a chlorinated vinyl resin is used as the carbon-containing resin. Conditions other than these are the same as in Example 1. Table 4 shows the ratio of graphite contained in the carbon composite after carbonization, the density after activation, and the specific resistance value. In addition, the ratio of graphite after carbonization is the residual carbon ratio of the known chlorinated vinyl resin (the ratio of amorphous carbon obtained after carbonization to the resin before carbonization) determined by the carbonization conditions and the chlorine used. It was calculated from the amount of vinyl chloride resin and graphite. From Table 4, it can be seen that the specific resistance of the electrode can be lowered to 0.0087 Ω · cm if graphite is blended to an extent that amorphous carbon and graphite are equivalent after carbonization.
（実施例９）
電極の厚み加工の前後の密度を測定して電極の密度の均一性を評価した。実施例９では、厚みが４４４μｍであり、これら以外の条件は実施例１と同じである。まず、実施例９で得られた電極の密度を測定した。次いで、この電極を表５に示す厚みまで削り取る厚み加工を施し、厚み加工後の電極の密度を測定した。表５には、厚み加工の前後における厚みと密度との関係を示す。表５より、本発明の電極は、部位による密度のばらつきが少ないことが理解される。
Example 9
The density before and after the electrode thickness processing was measured to evaluate the uniformity of the electrode density. In Example 9, the thickness is 444 μm, and conditions other than these are the same as in Example 1. First, the density of the electrode obtained in Example 9 was measured. Next, the electrode was subjected to thickness processing for scraping the electrode to the thickness shown in Table 5, and the density of the electrode after thickness processing was measured. Table 5 shows the relationship between the thickness and the density before and after the thickness processing. From Table 5, it is understood that the electrode of the present invention has little variation in density depending on the part.
（実施例１０）
アルミニウムを蒸着させる前後の表面抵抗を測定した。実施例１０では、実施例１で得られた電極にアルミニウムを蒸着させた。テスターを用い、間隔１２ｍｍにて実施例１及び実施例１０で得られた電極の表面抵抗を測定した。実施例１及び１０で得られた電極の表面抵抗はそれぞれ３５Ω及び１１Ωであった。実施例１及び１０で得られた電極の表面写真をそれぞれ図５及び図６に示す。
(Example 10)
The surface resistance before and after depositing aluminum was measured. In Example 10, aluminum was vapor-deposited on the electrode obtained in Example 1. Using a tester, the surface resistance of the electrodes obtained in Example 1 and Example 10 was measured at an interval of 12 mm. The surface resistances of the electrodes obtained in Examples 1 and 10 were 35Ω and 11Ω, respectively. The surface photographs of the electrodes obtained in Examples 1 and 10 are shown in FIGS. 5 and 6, respectively.
（実施例１１）
実施例１１では、実施例１で得られた電極に白金及びパラジウムの合金を蒸着させた。実施例１１で得られた電極の断面写真を図７に示す。
(Example 11)
In Example 11, an alloy of platinum and palladium was deposited on the electrode obtained in Example 1. A cross-sectional photograph of the electrode obtained in Example 11 is shown in FIG.
Claims (14)
前記穴開け材粒子を分散させた前記炭素含有樹脂を非酸化雰囲気中で熱処理することにより前記炭素含有樹脂を炭素化するとともに前記穴開け材粒子を消失させて平均孔径０．１μｍ以上のマクロ孔を形成し、
前記マクロ孔が形成された炭素化物に賦活処理を施すことにより平均孔径１０nm以下のミクロ孔を形成することを含む炭素多孔質電極の製造方法。 Disperse the drilling material particles uniformly in the carbon-containing resin,
The carbon-containing resin in which the perforating material particles are dispersed is heat-treated in a non-oxidizing atmosphere to carbonize the carbon-containing resin and disappear the perforating material particles to obtain macropores having an average pore diameter of 0.1 μm or more. Form the
A method for producing a carbon porous electrode, comprising forming micropores having an average pore diameter of 10 nm or less by subjecting a carbonized material having macropores to activation treatment.
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| JP2017164667A (en) * | 2016-03-14 | 2017-09-21 | 三菱鉛筆株式会社 | Carbon carrier for catalysts |
| CN107256806A (en) * | 2017-06-23 | 2017-10-17 | 中国科学院宁波材料技术与工程研究所 | A kind of electrode material and ultracapacitor |
| KR20190087679A (en) * | 2017-11-13 | 2019-07-25 | (주) 비비비 | Porous carbon electrode manufacturing method |
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| CN107256806A (en) * | 2017-06-23 | 2017-10-17 | 中国科学院宁波材料技术与工程研究所 | A kind of electrode material and ultracapacitor |
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| KR102055654B1 (en) | 2017-11-13 | 2020-01-22 | (주) 비비비 | Method of manufacturing porous carbon electrode |
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