JP2014029035A - Carbon fiber felt, method for producing the same and electrode - Google Patents
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- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
Description
本発明は、導電性が高く、電解質液など流体の透過性、浸透性の良い炭素繊維フェルトとその製造方法、及び炭素繊維フェルトからなる電極に関する。 TECHNICAL FIELD The present invention relates to a carbon fiber felt having high conductivity and good fluid permeability such as an electrolyte solution and good permeability, a method for producing the same, and an electrode comprising the carbon fiber felt.
近年、クリーンな電気エネルギーの需要が急速に伸び、太陽光発電や風力発電といった新エネルギーの導入が積極的に進められている。しかし、これらの発電方式は、天候に左右される為、発電周波数や出力が安定化せず、制御が難しいという課題がある。その対策として、蓄電池を経由して出力することで、出力変動の平準化、余剰電力の貯蔵、負荷平準化を図ることが検討されている。 In recent years, the demand for clean electric energy has increased rapidly, and the introduction of new energy such as solar power generation and wind power generation has been actively promoted. However, since these power generation methods are influenced by the weather, the power generation frequency and output are not stabilized, and there is a problem that control is difficult. As countermeasures, it has been studied to achieve output leveling, surplus power storage, and load leveling by outputting via a storage battery.
蓄電池の一つであるレドックスフロー型蓄電池は、比較的安全なイオンを用いること、室温で作動する為、熱源が必要なく、高効率で運転できること、サイクル寿命が１万回以上と長寿命であるなどの優れた特徴を備え、また容易に大型化が可能であることから、大型の二次蓄電池として期待されている。 Redox flow storage batteries, one of the storage batteries, use relatively safe ions, operate at room temperature, do not require a heat source, can be operated with high efficiency, and have a long cycle life of 10,000 cycles or more. Therefore, it is expected to be a large-sized secondary storage battery.
図１１は、レドックスフロー型電池の動作原理を示す概念図である。 FIG. 11 is a conceptual diagram showing the operating principle of the redox flow battery.
レドックスフロー型電池４２の主要部は、充電／放電反応を行うセル部４４と、電力を貯蔵する電解液タンク部４６、４８とから構成されている。セル部４４には、２種類の電解液(送液ポンプ５６、５８によるそれぞれの電解液の流れ方向を矢印Ｘ、Ｙで示す)が隔膜５４で隔てられて供給されている。更に、供給されるそれぞれの電解液に接して、正極６０及び負極６２が設けられる。充電時においては、正極６０で溶質の酸化反応が行われ、負極６２で溶質の還元反応が行われる。放電時には、正極６０で溶質の還元反応が行われ、負極６２で溶質の酸化反応が行われる。これらの酸化還元反応を繰り返すことにより、充放電が行われる。
The main part of the
その電極としては、導電性があり、化学的に安定な素材であることから炭素材料が好ましく用いられている。この炭素材料のうちでも、電極反応を効率的に実施する必要から表面積が大きいことが好ましいため、細い繊維の集合体である炭素繊維フェルトが更に好ましく用いられている。電極として使用されるフェルトには、電解液を少ない流通抵抗で循環させるため、液体透過性、浸透性が良いことが求められる。その解決策として、熱プレスや切削加工などにより炭素繊維フェルト表面に電解液流通用の溝を形成することが提案されている(例えば、特許文献１)。 As the electrode, a carbon material is preferably used because it is electrically conductive and is a chemically stable material. Among these carbon materials, since it is preferable that the surface area is large because it is necessary to efficiently perform the electrode reaction, a carbon fiber felt that is an aggregate of thin fibers is more preferably used. Felts used as electrodes are required to have good liquid permeability and permeability in order to circulate the electrolyte solution with a small flow resistance. As a solution to this problem, it has been proposed to form grooves for circulating an electrolytic solution on the surface of the carbon fiber felt by hot pressing or cutting (for example, Patent Document 1).
特許文献１では、炭素繊維前駆体フェルトの片面に熱プレス又は切削加工により溝を形成させた後、フェルトを炭素化することで、片面に溝が形成された炭素繊維フェルトを得ている。 In patent document 1, after forming a groove | channel on the single side | surface of a carbon fiber precursor felt by hot press or cutting, the carbon fiber felt by which the groove | channel was formed in the single side | surface is obtained by carbonizing a felt.
しかし、このようにして得られる炭素繊維フェルトは、熱プレス又は切削加工などが施された部分の繊維が損傷するため、炭素繊維フェルトの強度が低下し、取扱性が低下する。また、熱プレスされていない部分(畝)は密度が低く、電極として使用する時の圧力により、畝が潰れ、溝が閉塞されてしまうため、通液が阻害される場合もある。 However, in the carbon fiber felt obtained in this manner, the fiber in the portion subjected to hot pressing or cutting is damaged, so that the strength of the carbon fiber felt is lowered and the handleability is lowered. In addition, the density of the portion that is not hot-pressed (wrinkle) is low, and the wrinkle is crushed and the groove is blocked by the pressure when used as an electrode.
この問題を避けるため、嵩密度の高いフェルトを用いると、熱プレスされた部分の嵩密度が更に高くなり、この部分の通液性が悪くなる問題がある。 In order to avoid this problem, when a felt having a high bulk density is used, there is a problem that the bulk density of the hot-pressed portion is further increased and the liquid permeability of this portion is deteriorated.
本発明は、電解質液などの流体の透過性、浸透性が良く、厚み方向の導電性が高く、取扱性に優れる炭素繊維フェルト、そのフェルトの製造方法、及びそのフェルトからなる電極を提供することを目的とする。 The present invention provides a carbon fiber felt having good permeability and permeability of an electrolyte solution and the like, high conductivity in the thickness direction, and excellent handleability, a method for producing the felt, and an electrode comprising the felt. With the goal.
本発明者らは、上記課題について鋭意検討しているうち、炭素繊維前駆体フェルトの一面に切込みを形成し、このフェルトの表裏の熱収縮率の制御や、炭素化工程での張力を制御して炭素化することで、その切込みから溝が形成され、溝でない部分は畝になることを見出した。 The inventors of the present invention have been diligently studying the above problems, and forming a cut on one surface of the carbon fiber precursor felt to control the thermal contraction rate of the front and back of the felt and to control the tension in the carbonization process. As a result of the carbonization, it was found that a groove was formed from the cut, and the non-groove portion became a wrinkle.
得られる炭素繊維フェルトは、畝部の嵩密度が、溝部の嵩密度より高く、電解質液など流体の透過性、浸透性が良く、厚み方向への導電性に優れ、取扱性に優れていることを見出し、本発明を完成するに至った。 The resulting carbon fiber felt has a bulk density higher than that of the groove, good permeability and permeability of fluid such as electrolyte solution, excellent conductivity in the thickness direction, and excellent handling properties. As a result, the present invention has been completed.
上記目的を達成する本発明は、以下に記載のものである。 The present invention for achieving the above object is as follows.
[１] 少なくとも片面に帯状に外方に突出する複数の畝部分と、前記複数の畝部分の間に形成される溝部分とからなる凹凸形状を有する炭素繊維フェルトであって、畝部分のフェルトの嵩密度が、溝部分の底壁を構成するフェルトの嵩密度よりも高いことを特徴とする炭素繊維フェルト。 [1] A carbon fiber felt having a concavo-convex shape including a plurality of ridge portions protruding outward in a band shape on at least one surface and a groove portion formed between the plurality of ridge portions, A carbon fiber felt, wherein the bulk density of the felt is higher than the bulk density of the felt constituting the bottom wall of the groove portion.
[２] 溝が、フェルト表面において、直線状、格子状、ダイヤ状、又は、波状に形成されている[１]に記載の炭素繊維フェルト。 [2] The carbon fiber felt according to [1], wherein the groove is formed in a linear shape, a lattice shape, a diamond shape, or a wave shape on the felt surface.
[３] 溝幅が０．５〜１０ｍｍ、溝深さが炭素繊維フェルトの厚みに対して１０〜９０％、溝ピッチが０．５〜１００ｍｍで形成されている[１]又は[２]に記載の炭素繊維フェルト。 [3] In [1] or [2], the groove width is 0.5 to 10 mm, the groove depth is 10 to 90% with respect to the thickness of the carbon fiber felt, and the groove pitch is 0.5 to 100 mm. The described carbon fiber felt.
[４] 厚みが０．５〜１０ｍｍ、目付が１００〜１０００ｇ／ｍ2、厚み方向の電気抵抗値が５００ｍΩ／ｃｍ2以下である[１]乃至[３]の何れかに記載の炭素繊維フェルト。 [4] The carbon fiber felt according to any one of [1] to [3], wherein the thickness is 0.5 to 10 mm, the basis weight is 100 to 1000 g / m 2 , and the electric resistance value in the thickness direction is 500 mΩ / cm 2 or less. .
[５］ [１]乃至[４]の何れかに記載の炭素繊維フェルトからなる電極。 [5] An electrode comprising the carbon fiber felt according to any one of [1] to [4].
[６] 炭素繊維前駆体フェルトを不活性雰囲気下で炭素化する炭素繊維フェルトの製造方法であって、片面又は両面に切込みを入れた前駆体フェルトを、切込み方向と直交する方向に張力を付与しながら炭素化することを特徴とする炭素繊維フェルトの製造方法。 [6] A carbon fiber felt manufacturing method in which carbon fiber precursor felt is carbonized under an inert atmosphere, and a tension is applied to the precursor felt incised on one or both sides in a direction perpendicular to the incision direction. And carbonizing the carbon fiber felt.
[７] 炭素繊維前駆体フェルトを不活性雰囲気下で炭素化する炭素繊維フェルトの製造方法であって、前駆体フェルトが表裏面で熱収縮率が異なる構造のフェルトであり、且つその高収縮側のフェルトに切込みを入れたフェルトを炭素化することを特徴とする炭素繊維フェルトの製造方法。 [7] A method for producing a carbon fiber felt in which a carbon fiber precursor felt is carbonized under an inert atmosphere, wherein the precursor felt is a felt having a structure having different heat shrinkage rates on the front and back surfaces, and the high shrinkage side thereof. A method for producing a carbon fiber felt, characterized by carbonizing a felt having a notch formed therein.
本発明の炭素繊維フェルトは、畝部分の嵩密度が高いため、炭素繊維フェルト表面に形成された溝が潰れにくく、電解液の流通を阻害しないため電極の材料として、好適に使用できる。 Since the carbon fiber felt of the present invention has a high bulk density at the heel portion, the groove formed on the surface of the carbon fiber felt is not easily crushed and does not hinder the flow of the electrolyte solution, and therefore can be suitably used as an electrode material.
本発明の炭素繊維フェルトの製造方法によれば、表裏での熱収縮率の制御や、炭素化工程での張力を制御しながら不活性雰囲気下で炭素化しているので、得られる炭素繊維フェルトの畝部分の嵩密度を高くでき、炭素繊維フェルト表面に形成される溝は潰れにくい。そのため、レドックスフロー型電池に用いる場合、電解液の流通を阻害しないので、電極の材料として好適に使用できる炭素繊維フェルトを得ることができる。 According to the method for producing a carbon fiber felt of the present invention, since carbonization is performed in an inert atmosphere while controlling the thermal contraction rate on the front and back sides and controlling the tension in the carbonization process, The bulk density of the heel portion can be increased, and the grooves formed on the surface of the carbon fiber felt are not easily crushed. Therefore, when used in a redox flow type battery, the carbon fiber felt that can be suitably used as an electrode material can be obtained because it does not hinder the flow of the electrolyte.
本発明の炭素繊維フェルトの一例を図１に示す。図１中、２は炭素繊維フェルトで、このフェルト２の片面には所定間隔で離れた複数(本図では５本)の畝部４が、フェルト２の片面から外方に帯状に突出して形成されている。６は溝部で、前記互いに隣接する畝部４の間に、フェルト２の内方に向かって形成されている。
An example of the carbon fiber felt of the present invention is shown in FIG. In FIG. 1,
畝部４の嵩密度は、溝部の底壁８の嵩密度より高い。本発明において、畝部４の嵩密度は、溝部の底壁８の嵩密度の１．０１〜２倍であることが好ましい。
The bulk density of the
畝部４の嵩密度が、溝部の底壁８の嵩密度より高く構成することで、セルに組み込まれる時に、圧力で畝が潰され難く、溝が確保できるため、循環する電解液の流通を阻害しない。
Since the bulk density of the
そのため、本発明の炭素繊維フェルトを用いた電極は、循環させる電解液の通液圧力損失が低く、電解液循環に必要なポンプ稼動のエネルギー消費量を低減できる。 Therefore, the electrode using the carbon fiber felt of the present invention has a low flow pressure loss of the electrolyte to be circulated, and can reduce the energy consumption of the pump operation necessary for the electrolyte circulation.
本発明の炭素繊維フェルトにおいては、畝及び溝をフェルト２の片面のみに有する炭素繊維フェルトが、フェルト２の両面に有する炭素繊維フェルトよりも好ましい。後述する集電体との接触面積を広く確保でき、導電抵抗による発熱ロスを低減でき、発電効率を高めることができるためである。
In the carbon fiber felt of the present invention, a carbon fiber felt having ridges and grooves only on one side of the
畝部の嵩密度は、０．０８ｇ／ｃｍ3以上が好ましい。０．０８ｇ／ｃｍ3未満の場合は、セルに組み込まれた時の圧力により、畝が潰れ、溝が閉塞しやすい傾向がある。 The bulk density of the buttocks is preferably 0.08 g / cm 3 or more. In the case of less than 0.08 g / cm 3, the wrinkles tend to be crushed and the grooves tend to close due to the pressure when incorporated in the cell.
溝部の底壁を構成するフェルトの嵩密度は、０．０５ｇ／ｃｍ3以上が好ましい。０．０５ｇ／ｃｍ3未満の場合は、厚み方向の電気抵抗値が高く、セル抵抗が高くなる傾向がある。 The bulk density of the felt constituting the bottom wall of the groove is preferably 0.05 g / cm 3 or more. When it is less than 0.05 g / cm 3 , the electric resistance value in the thickness direction is high, and the cell resistance tends to be high.
嵩密度は、炭素繊維前駆体フェルト作製時のパンチング数、原料繊維となる前駆体繊維、特に耐炎繊維の比重、原料繊維に混合する物質(混綿物質)の種類や量により制御できる。 The bulk density can be controlled by the number of punching at the time of producing the carbon fiber precursor felt, the specific gravity of the precursor fiber as the raw fiber, particularly the flame resistant fiber, and the kind and amount of the substance (mixed cotton substance) mixed with the raw fiber.
本発明の炭素繊維フェルトの畝部の嵩密度は、溝部の嵩密度より高い。畝部の嵩密度が、溝部の嵩密度と同一又は低い場合は、セルに組み込まれた時の圧力により、畝が潰れ、溝が閉塞する。嵩密度の差は、用いる前駆体繊維又は耐炎繊維の比重の差や、混合する物質(混綿物質)の種類や量を調節することで制御できる。 The bulk density of the collar part of the carbon fiber felt of the present invention is higher than the bulk density of the groove part. When the bulk density of the heel portion is the same as or lower than the bulk density of the groove portion, the heel is crushed and the groove is closed by the pressure when incorporated in the cell. The difference in bulk density can be controlled by adjusting the difference in specific gravity of the precursor fiber or flame resistant fiber to be used and the type and amount of the substance to be mixed (mixed cotton substance).
本発明においてフェルト表面における溝の形態は、図２〜５に示すような、直線状、格子状、ダイヤ状、波状であることが好ましい。 In the present invention, the shape of the groove on the felt surface is preferably a linear shape, a lattice shape, a diamond shape, or a wave shape as shown in FIGS.
また、本発明における溝の断面形状の例を、図６〜８に示す。図６は、フェルト２の内部に向かうに従って狭くなる断面Ｖ形状の溝を示す。図７は、断面が矩形の溝を示す。図８は、断面形状が逆台形の溝を示す。
Moreover, the example of the cross-sectional shape of the groove | channel in this invention is shown to FIGS. FIG. 6 shows a groove having a V-shaped cross section that becomes narrower toward the inside of the
図２〜８において、４は畝であり、６は溝であり、１０は電池セル部材である。溝は電解液の流路として働く。また、畝４自体も炭素繊維から構成されている為、電極として機能し、反応可能な有効面積を低下させることがない。
2 to 8, 4 is a ridge, 6 is a groove, and 10 is a battery cell member. The groove serves as a flow path for the electrolyte. Moreover, since the cage |
フェルト２の表面における溝幅は、０．５〜１０ｍｍが好ましく、０．７〜５ｍｍがより好ましい。０．５ｍｍ未満の場合は、圧力損失の低減効果が十分でなく、ポンプの消費エネルギーロスが大きい。１０ｍｍを超える場合は、切込み(スリット)から溝を形成する方法では作製が困難である。 The groove width on the surface of the felt 2 is preferably 0.5 to 10 mm, and more preferably 0.7 to 5 mm. If it is less than 0.5 mm, the effect of reducing the pressure loss is not sufficient, and the energy consumption loss of the pump is large. If it exceeds 10 mm, it is difficult to produce by a method of forming a groove from a slit (slit).
図６〜８に示すように、溝の深さ(ｔ)は、フェルト厚み(Ｔ)に対し、１０〜９０％が好ましく、２０〜８０％がより好ましい。１０％未満の場合は、圧力損失の低減効果が十分でなく、ポンプの消費エネルギーロスが大きい。９０％を超える場合は、強力が低減し、炭素化時の張力や、積層時の張力により破断する可能性がある為、好ましくない。溝の深さ(ｔ)は、後述するスリットの深さにより制御できる。 As shown in FIGS. 6 to 8, the depth (t) of the groove is preferably 10 to 90% and more preferably 20 to 80% with respect to the felt thickness (T). If it is less than 10%, the effect of reducing the pressure loss is not sufficient, and the energy consumption loss of the pump is large. If it exceeds 90%, the strength is reduced, and there is a possibility of breakage due to the tension during carbonization or the tension during lamination, such being undesirable. The depth (t) of the groove can be controlled by the depth of the slit described later.
溝ピッチ(並行する溝の中心間の距離)は、０．５〜１００ｍｍが好ましく、０．８〜５０ｍｍがより好ましい。０．５ｍｍ未満の場合は、間隔が狭く、スリット加工できない。１００ｍｍを超えると圧力損失の低減効果が十分でなく、ポンプの消費エネルギーロスが大きい。溝ピッチは、スリット刃の間隔等で制御できる。 The groove pitch (distance between the centers of the parallel grooves) is preferably 0.5 to 100 mm, and more preferably 0.8 to 50 mm. When it is less than 0.5 mm, the interval is narrow and slit processing cannot be performed. If it exceeds 100 mm, the effect of reducing the pressure loss is not sufficient, and the energy consumption loss of the pump is large. The groove pitch can be controlled by the interval of the slit blades.
溝の断面形状は、スリット刃の形状や工程張力で制御できる。 The cross-sectional shape of the groove can be controlled by the shape of the slit blade and the process tension.
炭素繊維フェルトの厚み(Ｔ)は、０．５〜１０ｍｍが好ましく、０．８〜７ｍｍがより好ましい。０．５ｍｍ未満の場合は、溝付きの炭素繊維フェルトであっても圧力損失低減効果が小さく、ポンプの消費エネルギーロスが大きくなる為、好ましくない。１０ｍｍを超えると、システムが大きくなりすぎ、設計の自由度が下がる為、好ましくない。厚みは、混綿物質の仕込み量(目付)やパンチング数により制御できる。 The thickness (T) of the carbon fiber felt is preferably 0.5 to 10 mm, and more preferably 0.8 to 7 mm. If it is less than 0.5 mm, even if it is a grooved carbon fiber felt, the effect of reducing the pressure loss is small, and the energy consumption loss of the pump becomes large, which is not preferable. If it exceeds 10 mm, the system becomes too large, and the degree of freedom in design decreases, which is not preferable. The thickness can be controlled by the amount (weight per unit) of the mixed cotton material and the number of punching.
畝を形成した本炭素繊維フェルト２の目付は、１００〜１０００ｇ／ｍ2が好ましく、２００〜８００ｇ／ｍ2がより好ましい。１００ｇ／ｍ2未満の場合は、圧力損失低減効果が小さく、ポンプの消費エネルギーロスが大きくなる、反応に寄与する表面積が小さくなる為、好ましくない。１０００ｇ／ｍ2を超える場合は、システムが大きくなりすぎ、設計の自由度が下がる為、好ましくない。目付は、混綿物質の仕込み量やウェブの積層数により制御できる。 Basis weight of the carbon fiber felt 2 formed with ridges, preferably 100 to 1000 g / m 2, 200 to 800 g / m 2 is more preferable. If it is less than 100 g / m 2, the effect of reducing pressure loss is small, the energy loss of the pump is large, and the surface area contributing to the reaction is small, which is not preferable. If it exceeds 1000 g / m 2 , the system becomes too large, and the degree of freedom in design decreases, which is not preferable. The basis weight can be controlled by the amount of blended cotton material and the number of laminated webs.
厚み方向の電気抵抗値は５００ｍΩ／ｃｍ2以下が好ましく、４００ｍΩ／ｃｍ2がより好ましい。５００ｍΩ／ｃｍ2を超えると電極として使用した場合に、導電抵抗が高く、充放電のロスが大きくなる為、好ましくない。厚み方向の電気抵抗値は、パンチング数や炭素化温度により制御できる。 The electric resistance value in the thickness direction is preferably 500 mΩ / cm 2 or less, and more preferably 400 mΩ / cm 2 . If it exceeds 500 mΩ / cm 2 , when used as an electrode, the conductive resistance is high and the charge / discharge loss increases, which is not preferable. The electric resistance value in the thickness direction can be controlled by the punching number and the carbonization temperature.
溝の断面積は０．５〜１００ｍｍ2が好ましく、１〜３０ｍｍ2がより好ましい。０．５ｍｍ2未満の場合は、十分な流路が形成されておらず、圧力損失の低減効果が十分でなく、ポンプの消費エネルギーロスが大きい。１００ｍｍ2を超える場合は、本製造方法で作製することが困難である。上記断面積となれば、その形状は特に指定されない。断面積は、溝幅、溝深さ、張力、フェルトの表裏熱収縮差、混綿物質の種類により制御できる。 Sectional area is preferably 0.5 to 100 mm 2 of the groove, 1 to 30 mm 2 is more preferable. If it is less than 0.5 mm 2 , a sufficient flow path is not formed, the effect of reducing pressure loss is not sufficient, and the energy consumption loss of the pump is large. If it exceeds 100 mm 2 , it is difficult to produce by this production method. If it becomes the said cross-sectional area, the shape in particular will not be designated. The cross-sectional area can be controlled by the groove width, groove depth, tension, felt front / back heat shrinkage difference, and type of blended material.
フェルト断面積に対する溝断面積の割合は、１〜７５％であり、好ましくは１．５〜６０％であり、より好ましくは５〜５０％である。１％未満の場合は、十分な流路が形成されておらず、圧力損失の低減効果が十分でなく、ポンプの消費エネルギーロスが大きい。７５％を超える場合は、電気抵抗値が大きくなる、必要な強度が確保できない等、不具合が生ずる。上記、割合となれば、その形状は特に指定されない。断面積は、溝幅、溝深さ、張力、ピッチ、フェルトの表裏熱収縮差、混綿物質の種類により制御できる。 The ratio of the groove cross-sectional area to the felt cross-sectional area is 1 to 75%, preferably 1.5 to 60%, and more preferably 5 to 50%. If it is less than 1%, a sufficient flow path is not formed, the pressure loss reduction effect is not sufficient, and the energy consumption loss of the pump is large. If it exceeds 75%, problems such as an increase in the electric resistance value and the inability to secure the required strength occur. If it becomes the said ratio, the shape will not be specified in particular. The cross-sectional area can be controlled by the groove width, groove depth, tension, pitch, felt front and back heat shrinkage difference, and the type of the mixed cotton material.
［炭素繊維織物の製造方法］
本発明の炭素繊維フェルトの製造方法は特に限定されるものではなく、何れの方法で製造しても良いが、以下の方法が好ましい。
[Method for producing carbon fiber fabric]
The method for producing the carbon fiber felt of the present invention is not particularly limited and may be produced by any method, but the following method is preferred.
(製造方法Ａ)
この方法においては、先ず炭素繊維前駆体フェルトの片面又は両面に溝形成用の切込みが形成された炭素繊維前駆体フェルトを用意する。次いで、切込み幅が拡がる方向に張力を付与しながら不活性雰囲気下で炭素化する。これにより本発明の炭素繊維フェルトが得られる。
(Production method A)
In this method, first, a carbon fiber precursor felt in which notches for forming grooves are formed on one side or both sides of the carbon fiber precursor felt is prepared. Next, carbonization is performed in an inert atmosphere while applying tension in a direction in which the cut width increases. Thereby, the carbon fiber felt of the present invention is obtained.
炭素繊維フェルトの製造原料としては、ポリアクリロニトリル(ＰＡＮ)系耐炎繊維、又は、ピッチ系繊維、レーヨン繊維、セルロース等の従来公知の何れの炭素繊維前駆体繊維が挙げられる。なお、各種製造原料の中でも、繊維の柔軟性や加工性の面から、ＰＡＮ系耐炎繊維が好ましい。ＰＡＮ系耐炎繊維とは、ＰＡＮ系原料繊維を空気中で２００〜４００℃で酸化処理することによって得られる繊維である。 Examples of the raw material for producing the carbon fiber felt include polyacrylonitrile (PAN) flame resistant fibers, or any conventionally known carbon fiber precursor fibers such as pitch fibers, rayon fibers, and cellulose. Among various production raw materials, PAN-based flame resistant fibers are preferable from the viewpoints of fiber flexibility and processability. The PAN-based flame resistant fiber is a fiber obtained by oxidizing a PAN-based raw fiber at 200 to 400 ° C. in the air.
先ず、炭素繊維前駆体繊維又は耐炎繊維を公知の方法でフェルト化する。フェルト化の方法はカードによって開繊し、多層化し、多層化されたウェブをニードルパンチによりフェルト化する方法があるが、フェルトにする方法であればこの方法に限定されない。 First, the carbon fiber precursor fiber or the flame resistant fiber is felted by a known method. As a felting method, there is a method in which a card is opened and multilayered, and the multilayered web is felted by a needle punch. However, the felting method is not limited to this method.
また、フェルトの表裏において熱収縮の差を付ける為に、異なった種類、量の原料繊維等からなるウェブを多層積層してフェルト化したり、異なった種類、量の原料繊維等を混合してウェブを作製し、フェルト化しても良い。 Also, in order to make a difference in heat shrinkage between the front and back of the felt, webs made of different types and amounts of raw fibers are laminated in layers to make a felt, or different types and amounts of raw fibers are mixed to create a web. May be made and felted.
フェルト化後の切込み形成前のフェルトには、スリット刃などにより切込み(スリット)を入れる。 A slit (slit) is made by a slit blade or the like in the felt before forming the cut after felting.
図９は、本発明の炭素繊維フェルトの製造方法に原料として用いるフェルトを示す。このフェルトは均一に形成されている。フェルト２２には切込み２４が形成されている。
FIG. 9 shows a felt used as a raw material in the method for producing a carbon fiber felt of the present invention. This felt is formed uniformly. A
得られる切込み２４が形成されていないプレーン層２６と切込み２４を形成しているスリット層とからなる炭素繊維前駆体フェルト２２は、切込み幅が拡がる方向に張力Ｓ、Ｒを付与しながら不活性雰囲気下で炭素化される。この場合は、切込み方向に直角方向である。
The carbon fiber precursor felt 22 composed of the
張力は、２〜１００Ｎ／ｍが好ましく、３〜５０Ｎ／ｍがより好ましい。２Ｎ／ｍ未満の場合は、目標とする溝幅が得られない。１００Ｎ／ｍを超える場合は、張力により変形(ウネリや折れ目)が発生し、得られる本発明の炭素繊維フェルトは電極として使用できない。 The tension is preferably 2 to 100 N / m, more preferably 3 to 50 N / m. If it is less than 2 N / m, the target groove width cannot be obtained. When it exceeds 100 N / m, deformation (undel or crease) occurs due to tension, and the obtained carbon fiber felt of the present invention cannot be used as an electrode.
(製造方法Ｂ)
図１０は、本発明の炭素繊維フェルトの他の製造方法を示す説明図である。
(Production method B)
FIG. 10 is an explanatory view showing another method for producing the carbon fiber felt of the present invention.
この方法においては、先ず炭素化する際に熱収縮する低収縮層３２を用意する。次いで、低収縮層３２よりも炭素化する際の熱収縮率が高い高収縮層３４を積層する。積層はパンチング等による。
In this method, first, a
その後、切込み２４を形成する。この切込みを形成した部分はスリット層２６となり、切込みを形成していない部分はプレーン層２８になる。この切込みを形成したフェルトを炭素化すると、低収縮層３２と高収縮層３４との炭素化時の収縮率の違いに基いて、切込み２４が広がり、溝を自然に形成する。
Thereafter, a
また、本発明の２つの炭素繊維フェルトの製造方法(製造方法Ａ及びＢ)を組み合わせてもよい。 Moreover, you may combine the manufacturing method (manufacturing method A and B) of the two carbon fiber felts of this invention.
この場合、高収縮層と低収縮層とからなる炭素繊維前駆体フェルトにおいて溝を形成する為の張力は、０．０５〜１００Ｎ／ｍが好ましく、１〜５０Ｎ／ｍがより好ましい。張力が０．０５Ｎ未満の場合においては、張力のみで溝を形成させるには十分でない。１００Ｎ／ｍを超える場合には、焼成時に延伸によりウネリが生じ、外観不良となる為、好ましくない。 In this case, the tension for forming the groove in the carbon fiber precursor felt composed of the high shrinkage layer and the low shrinkage layer is preferably 0.05 to 100 N / m, and more preferably 1 to 50 N / m. When the tension is less than 0.05N, it is not sufficient to form the groove only with the tension. When it exceeds 100 N / m, undulation is generated by stretching during firing, resulting in poor appearance.
炭素繊維前駆体フェルトにおいて、低収縮層と高収縮層との熱収縮差は、４００℃において、２％以上が好ましく、５〜５０％がより好ましい。熱収縮差が２％未満の場合は、無張力下で炭素化した場合、溝形成が不十分である。 In the carbon fiber precursor felt, the thermal shrinkage difference between the low shrinkage layer and the high shrinkage layer is preferably 2% or more, more preferably 5 to 50% at 400 ° C. When the heat shrinkage difference is less than 2%, groove formation is insufficient when carbonized under no tension.
高収縮層の作製方法としては、主原料の耐炎繊維として低比重の耐炎繊維を用いる方法、主原料の耐炎繊維にそれより低比重の耐炎繊維を混綿する方法、又は、ポリビニルアルコール(ＰＶＡ)、ポリエステル(ＰＥＴ)、ポリプロピレン(ＰＰ)、アクリル、セルロース等の有機繊維や天然繊維などの高収縮繊維(混綿物質)を主原料の耐炎繊維に混綿する方法などで、高収縮層を形成することができる。 As a method for producing the high shrinkage layer, a method using a flame resistant fiber having a low specific gravity as the flame resistant fiber of the main material, a method of blending a flame resistant fiber having a lower specific gravity into the flame resistant fiber of the main material, or polyvinyl alcohol (PVA), A high shrinkage layer can be formed by a method of blending high shrinkage fibers (blend material) such as organic fibers such as polyester (PET), polypropylene (PP), acrylic, and cellulose, and natural fibers into a flame resistant fiber as a main raw material. it can.
なかでも、繊維が柔らかく交絡処理が容易であることから、有機繊維や天然繊維を用いることが好ましく、特に炭素化時の残渣の少ないポリビニルアルコール(ＰＶＡ)がより好ましい。耐炎繊維の比重は、製造時の処理温度や処理時間により制御できる。収縮量は、低比重の耐炎繊維量や高収縮繊維の含有量により制御できる。 Among these, organic fibers and natural fibers are preferably used because the fibers are soft and easy to be entangled, and polyvinyl alcohol (PVA) is particularly preferable because it has little residue during carbonization. The specific gravity of the flame resistant fiber can be controlled by the treatment temperature and treatment time during production. The amount of shrinkage can be controlled by the amount of low specific gravity flame resistant fiber and the content of high shrinkage fiber.
低収縮層は、主として比重が１．３８を超える耐炎繊維を使用する方法により形成できる。熱収縮率の差が２％以上確保できれば、いかなる方法で作製しても良い。 The low shrinkage layer can be formed mainly by a method using flame resistant fibers having a specific gravity exceeding 1.38. Any method may be used as long as the difference in heat shrinkage rate can be 2% or more.
形成される溝のフェルト表面における形態は、直線状、格子状、ダイヤ状、波状があり、スリット刃の形状等で制御できる。 Forms on the felt surface of the groove to be formed include a straight line shape, a lattice shape, a diamond shape, and a wave shape, and can be controlled by the shape of the slit blade.
耐炎繊維の密度は特に限定されるものではないが、１．３３〜１．４５ｇ／ｃｍ3であることが好ましい。耐炎繊維の密度が１．３３ｇ／ｃｍ3未満の場合は、炭素化時の収縮が大きく、工程が不安定になり易い傾向がある。耐炎繊維の密度が１．４５ｇ／ｃｍ3を超える場合は、繊維が脆く、フェルト加工等の交絡処理時に脱落が多く、加工性が低下する傾向にある。 The density of the flame resistant fiber is not particularly limited, but is preferably 1.33-1.45 g / cm 3 . When the density of the flame resistant fiber is less than 1.33 g / cm 3 , the shrinkage during carbonization is large and the process tends to become unstable. When the density of the flame resistant fiber exceeds 1.45 g / cm 3 , the fiber is fragile, and often falls during confounding treatment such as felt processing, so that the workability tends to be lowered.
原料繊維の繊度は、原料繊維が炭素繊維前駆体繊維の場合、０．１〜５．０ｄｔｅｘであることが好ましく、０．５〜３．５ｄｔｅｘであることがより好ましく、１．０〜３．３ｄｔｅｘが特に好ましい。炭素繊維前駆体の繊度が０．１ｄｔｅｘ未満の場合は、開繊性が悪く、均質な混合が難しい。炭素繊維前駆体の繊度が５．０ｄｔｅｘを超える場合は、強度の高いフェルトが得られない。また、繊維間の接点が低減し、炭素化後の電気抵抗値が高くなる。 When the raw fiber is a carbon fiber precursor fiber, the fineness of the raw fiber is preferably 0.1 to 5.0 dtex, more preferably 0.5 to 3.5 dtex, and 1.0 to 3. 3 dtex is particularly preferred. When the fineness of the carbon fiber precursor is less than 0.1 dtex, the spreadability is poor and uniform mixing is difficult. When the fineness of the carbon fiber precursor exceeds 5.0 dtex, a high strength felt cannot be obtained. Moreover, the contact between fibers decreases and the electrical resistance value after carbonization becomes high.
原料繊維の中でも特にＰＡＮ系耐炎繊維の場合、その繊度は０．５〜３．５ｄｔｅｘであることが好ましく、１．０〜３．３ｄｔｅｘがより好ましい。 Among the raw material fibers, in particular, in the case of a PAN-based flame resistant fiber, the fineness is preferably 0.5 to 3.5 dtex, and more preferably 1.0 to 3.3 dtex.
本発明の炭素繊維前駆体フェルトに用いる炭素繊維前駆体ステープルとしては、炭素繊維前駆体ステープルの繊維長が３０〜７５ｍｍ、繊度が０．５〜３．５ｄｔｅｘ、クリンプ数４〜２０ヶ／２．５４ｃｍ、クリンプ率４〜２０％に加工したものが好ましい。 As the carbon fiber precursor staple used for the carbon fiber precursor felt of the present invention, the fiber length of the carbon fiber precursor staple is 30 to 75 mm, the fineness is 0.5 to 3.5 dtex, and the number of crimps is 4 to 20/2. What processed 54 cm and the crimp rate of 4-20% is preferable.
フェルト加工等の交絡処理は、ニードルパンチ方法が好ましい。交絡処理回数が５０回／ｃｍ2未満の場合は、交絡処理回数が少なく、強度が低くなる。また厚み方向の電気抵抗値が高くなる。交絡処理回数が１０００回／ｃｍ2を超える場合は、交絡処理による繊維への損傷が大きく、脱落毛羽などが大量に発生する虞がある為、好ましくない。 The entanglement process such as felting is preferably a needle punch method. When the number of entanglement processes is less than 50 times / cm 2 , the number of entanglement processes is small and the strength is low. Moreover, the electrical resistance value in the thickness direction increases. When the number of entanglement treatments exceeds 1000 times / cm 2 , damage to the fiber due to the entanglement treatment is large, and a large amount of falling fluff may occur, which is not preferable.
以上のように炭素繊維前駆体フェルトを作製した後、これを炭素化処理することで、溝を有する炭素繊維フェルトが得られる。 After producing the carbon fiber precursor felt as described above, a carbon fiber felt having a groove is obtained by carbonizing this.
炭素化処理は、製造方法Ａ、Ｂ共に、炭素繊維前駆体フェルトを不活性雰囲気下、最高温度を１３００〜２３００℃にして、０．５〜１０分間焼成することにより行う。好ましくは、第１炭素化処理と第２炭素化処理との２段階で行う。その場合、第１炭素化処理は、交絡処理後の炭素繊維前駆体フェルトを、不活性雰囲気下３００〜１０００℃で焼成して分解ガスを処理する。第２炭素化処理は、第１炭素化処理された炭素繊維前駆体フェルトを、不活性雰囲気下、最高温度１３００〜２３００℃にして０．５〜１０分間焼成して行うことが好ましい。この炭素化処理時の最高温度は、１４００℃〜２３００℃の範囲であることがより好ましい。 The carbonization treatment is performed in both production methods A and B by firing the carbon fiber precursor felt under an inert atmosphere at a maximum temperature of 1300 to 2300 ° C. for 0.5 to 10 minutes. Preferably, the first carbonization treatment and the second carbonization treatment are performed in two stages. In that case, a 1st carbonization process bakes the carbon fiber precursor felt after a confounding process at 300-1000 degreeC by inert atmosphere, and processes a decomposition gas. The second carbonization treatment is preferably performed by firing the carbon fiber precursor felt subjected to the first carbonization treatment at a maximum temperature of 1300 to 2300 ° C. in an inert atmosphere for 0.5 to 10 minutes. As for the maximum temperature at the time of this carbonization process, it is more preferable that it is the range of 1400 degreeC-2300 degreeC.
炭素化処理時の最高温度が１３００℃未満の場合は、得られる炭素繊維フェルトの炭素含有率が９３質量％以上にならない。かかる炭素繊維フェルトは、電気伝導性が低く、良好な燃料電池性能を提供できないため好ましくない。炭素化処理時の最高温度が２３００℃を超える場合は、炭素繊維フェルトが剛直となって、強度が低下し、更には、炭素微粉末が発生する等の不具合が生ずる為、好ましくない。 When the maximum temperature at the time of carbonization is less than 1300 ° C., the carbon content of the obtained carbon fiber felt is not 93% by mass or more. Such carbon fiber felt is not preferred because it has low electrical conductivity and cannot provide good fuel cell performance. When the maximum temperature during the carbonization treatment exceeds 2300 ° C., the carbon fiber felt becomes stiff, the strength is lowered, and furthermore, problems such as the generation of fine carbon powder occur.
炭素繊維フェルトの炭素含有率は９３質量％以上が好ましく、９５質量％以上がより好ましい。炭素含有率が９３質量％未満の場合は、電気抵抗が高く、抵抗熱が多量に発生して反応ロスとなる為、電池効率が低下する傾向がある。 The carbon content of the carbon fiber felt is preferably 93% by mass or more, and more preferably 95% by mass or more. When the carbon content is less than 93% by mass, the electric resistance is high, and a large amount of resistance heat is generated, resulting in a reaction loss, so that the battery efficiency tends to decrease.
炭素繊維フェルトに用いられる炭素繊維の単繊維直径は５〜２０μｍであることが好ましく、６〜１５μｍがより好ましい。炭素繊維の単繊維直径が５μｍ未満の場合は、単繊維直径が細すぎて、カード工程などの加工性が悪く、また繊維の強力が低いため、炭素繊維フェルトから炭素繊維が脱落しやすくなる虞がある。炭素繊維の単繊維直径が２０μｍを超える場合は、繊維間の接触点が減少することで電気抵抗値が上昇して、反応効率が低下しやすくなる。また、炭素化後の繊維が剛直であり、脆くなる為、炭素繊維微粉末が多量に発生しやすくなる虞がある。 It is preferable that the single fiber diameter of the carbon fiber used for carbon fiber felt is 5-20 micrometers, and 6-15 micrometers is more preferable. When the single fiber diameter of the carbon fiber is less than 5 μm, the single fiber diameter is too thin, the processability such as the carding process is poor, and the strength of the fiber is low, so that the carbon fiber may be easily dropped from the carbon fiber felt. There is. When the single fiber diameter of the carbon fiber exceeds 20 μm, the contact point between the fibers decreases, the electrical resistance value increases, and the reaction efficiency tends to decrease. Moreover, since the carbonized fiber is rigid and brittle, there is a possibility that a large amount of carbon fiber fine powder is likely to be generated.
レドックスフロー型電池における電解液として水溶液を用いる場合には、その濡れ性向上の為、炭素繊維フェルトを酸化処理した後、電極として用いても良い。酸化処理には、液相酸化方法と気相酸化方法があり、特に限定される物ではない。 When an aqueous solution is used as the electrolytic solution in the redox flow battery, the carbon fiber felt may be oxidized and then used as an electrode in order to improve its wettability. The oxidation treatment includes a liquid phase oxidation method and a gas phase oxidation method, and is not particularly limited.
液相酸化方法としては、過酸化水素水や次亜塩素酸ソーダでの高温酸化処理や、電解液を用いた電解層中における電解質(硫酸、苛性ソーダ、硫酸アンモニウム、食塩等)での電解酸化処理方法が用いられる。 Liquid phase oxidation methods include high-temperature oxidation with hydrogen peroxide and sodium hypochlorite, and electrolytic oxidation with electrolytes (sulfuric acid, caustic soda, ammonium sulfate, sodium chloride, etc.) in the electrolyte layer using the electrolyte. Is used.
気相酸化では、空気酸化(３００〜８００℃)、オゾン酸化(２５〜４００℃)や水蒸気や二酸化炭素による酸化(５００〜９５０℃)方法等が用いられる。 In the gas phase oxidation, air oxidation (300 to 800 ° C.), ozone oxidation (25 to 400 ° C.), oxidation with water vapor or carbon dioxide (500 to 950 ° C.), or the like is used.
このようにして得られた本発明の炭素繊維フェルトは、例えば導電性と通液性などが必要とされる電極や、燃料電池用のガス拡散層や、コンポジットや、摺動材などの強化繊維としても、適用できる。中でも、レドックスフロー二次電池の電極、ナトリウム-硫黄二次電池の電極として好ましく用いることができる。 The carbon fiber felt of the present invention thus obtained includes reinforcing fibers such as electrodes that require conductivity and liquid permeability, gas diffusion layers for fuel cells, composites, and sliding materials. It can also be applied. Especially, it can use preferably as an electrode of a redox flow secondary battery and an electrode of a sodium-sulfur secondary battery.
本発明の炭素繊維フェルトからなる電極は、例えば、レドックスフロー二次電池の電極、ナトリウム-硫黄二次電池の電極、その他導電性と通液性、通水性などが必要とされる電極として、好適に使用できる。 The electrode made of the carbon fiber felt of the present invention is suitable, for example, as an electrode of a redox flow secondary battery, an electrode of a sodium-sulfur secondary battery, and other electrodes that require conductivity, liquid permeability, water permeability, etc. Can be used for
本発明の炭素繊維フェルトからなる電極を、上記レドックスフロー型電池用電極等の通液性などが必要とされる電極として用いる場合、電解槽内における電解液の流れ方向と溝の形成方向が一致するように配置することで通液圧力損失を軽減することが出来る。 When the electrode comprising the carbon fiber felt of the present invention is used as an electrode that requires liquid permeability, such as the above-mentioned redox flow battery electrode, the flow direction of the electrolyte in the electrolytic cell and the groove forming direction are the same. By arranging in such a way, it is possible to reduce the loss of liquid passing pressure.
以下、実施例により本発明を更に具体的に説明するが、本発明はこれら実施例に限定されるものではない。なお、操作条件の評価、各物性の測定は次の方法によった。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, evaluation of operation conditions and measurement of each physical property were based on the following methods.
[溝深さ(ｔ)]
溝形成面において、形成された溝の最深部を深さとした。
[Groove depth (t)]
On the groove forming surface, the deepest portion of the formed groove was defined as the depth.
[溝幅]
フェルト表面での溝の広さを幅とした。
[Groove width]
The width of the groove on the felt surface was taken as the width.
[溝ピッチ]
並行する隣り合った溝について、溝幅方向に沿って溝中心部間の距離を測定し、これを溝ピッチとした。
[Groove pitch]
About the adjacent groove | channel adjacent in parallel, the distance between groove | channel center parts was measured along the groove width direction, and this was made into groove pitch.
[溝断面積]
溝の長手方向に直交する裁断面で、１０ｃｍ長さにフェルトのサンプルを切り出し、ｎ＝５の溝断面を、その断面形状に応じて三角形、台形、長方形近似し、ｎ＝５で個々の溝の断面積を算出した。それら断面積の平均値を求め、これを溝断面積とした。
[Groove cross section]
Cut a felt sample to a length of 10 cm with a cross section orthogonal to the longitudinal direction of the groove, and approximate the groove cross section of n = 5 to a triangle, trapezoid, or rectangle according to the cross sectional shape, and each groove with n = 5 The cross-sectional area of was calculated. The average value of the cross-sectional areas was determined and this was used as the groove cross-sectional area.
[嵩密度]
畝の部分、溝の部分を、それぞれフェルト厚み方向に沿ってサンプルを切り出して測定したｎ＝２０の厚みと目付から算出し、それぞれ嵩密度(畝部)、嵩密度(溝部)とした。
[The bulk density]
The wrinkle part and the groove part were calculated from the thickness and basis weight of n = 20, which were measured by cutting out samples along the felt thickness direction, respectively, and were taken as the bulk density (gutter part) and bulk density (groove part), respectively.
[溝断面積比]
溝の長手方向に直交する裁断面で、１０ｃｍ長さにフェルトのサンプルを切り出し、ｎ＝５の溝断面を、その断面形状に応じて三角形、台形、長方形近似し、ｎ＝５で算出した個々の溝の断面積について総和を求め、この総和を、上記溝の長手方向に直交する裁断面の面積[１０ｃｍ長さ×厚み(Ｔ)]で除したものを溝断面積比とした。
[Groove cross-sectional area ratio]
A felt sample was cut out to a length of 10 cm with a cut surface orthogonal to the longitudinal direction of the groove, and an n = 5 groove cross section was approximated to a triangle, trapezoid, or rectangle according to the cross sectional shape, and each calculated with n = 5 The total sum of the cross-sectional areas of the grooves was determined, and the total sum was divided by the area [10 cm length × thickness (T)] of the cut surface perpendicular to the longitudinal direction of the grooves.
[目付]
サンプルとして２０ｃｍ角(０．２ｍ角)のフェルトを３枚切り出し、これを１０５℃、１時間乾燥した後の重量を、サンプル面積(０．２ｍ×０．２ｍ＝０．０４ｍ2)で除したものの３枚の平均値を目付とした。
[Body weight]
Three 20 cm square (0.2 m square) felts were cut out as samples, and the weight after drying this at 105 ° C. for 1 hour was divided by the sample area (0.2 m × 0.2 m = 0.04 m 2 ). The average value of three items was taken as the basis weight.
[熱収縮率]
縦２０ｃｍ×横２０ｃｍの耐炎繊維フェルトを切り出し、窒素雰囲気下で４００℃で３０分間熱処理した時の、縦横の寸法変化量を元長さで除したものの平均値を熱収縮率(４００℃)とした。
[Heat shrinkage]
When the heat-resistant fiber felt 20 cm long × 20 cm wide was cut out and heat-treated at 400 ° C. for 30 minutes in a nitrogen atmosphere, the average value obtained by dividing the vertical and horizontal dimensional change by the original length was the heat shrinkage rate (400 ° C.). did.
[フェルト厚み(Ｔ)]
シックネスゲージ(６．９ｋＰａ)を用い、溝が形成されていない部分で、且つ幅方向に５点測定した基材厚みの平均値をフェルト厚み(Ｔ)とした。
[Felt thickness (T)]
A thickness gauge (6.9 kPa) was used, and the average thickness of the base material measured at five points in the width direction in a portion where no groove was formed was defined as the felt thickness (T).
[厚み方向の電気抵抗値]
５０ｍｍ角のサンプルを切り出し、そのサンプルを２枚の５０ｍｍ角(厚み１０ｍｍ)の金メッキした電極で、全面接触するように挟み、サンプルの厚み方向に１０ｋＰａの荷重をかけたときの、厚み方向の電気抵抗値を測定し、電極面積で除して単位面積あたりの電気抵抗値を求めた。
[Electrical resistance value in the thickness direction]
A 50 mm square sample was cut out, and the sample was sandwiched between two 50 mm square (10 mm thick) gold-plated electrodes so that they were in full contact with each other, and a 10 kPa load was applied in the thickness direction of the sample. The resistance value was measured and divided by the electrode area to obtain the electric resistance value per unit area.
[通液圧力損失]
通液方向に３０ｃｍ、幅方向(流路幅)に５０ｃｍ、電極基材の厚みの６０％であるスペーサーで形成されたセルスタックを用意した。作製された電極基材を通液方向２０ｃｍ、幅方向５０ｃｍに切って設置し、５０リットル／時のイオン交換水を流通させ、セルスタックの出入口の通液圧力損失を測定した。ブランクとして電極基材を設置しない系で同様に測定し、測定値とブランク測定値との差を電極基材の通液圧力損失とした。
[Liquid pressure loss]
A cell stack formed of a spacer that is 30 cm in the liquid passing direction, 50 cm in the width direction (flow channel width), and 60% of the thickness of the electrode substrate was prepared. The produced electrode base material was cut into a liquid passing direction of 20 cm and a width direction of 50 cm, and 50 liters / hour of ion exchange water was circulated to measure the liquid passing pressure loss at the inlet / outlet of the cell stack. It measured similarly by the system which does not install an electrode base material as a blank, and made the difference between a measured value and a blank measured value the liquid passing pressure loss of an electrode base material.
本評価において、通液圧力損失は、１１ｋＰａ(８０ｍｍＨｇ)以下が好ましく、８．６５ｋＰａ(６５ｍｍＨｇ)以下がより好ましく、５．５ｋＰａ(５０ｍｍＨｇ)以下が更に好ましい。通液圧力損失が１１ｋＰａ(８０ｍｍＨｇ)を超えると、電解液を循環させる為のポンプ容量が大きくなり、ポンプに使用される電力の為に、電力ロスが大きくなる。 In this evaluation, the flow pressure loss is preferably 11 kPa (80 mmHg) or less, more preferably 8.65 kPa (65 mmHg) or less, and even more preferably 5.5 kPa (50 mmHg) or less. When the flow pressure loss exceeds 11 kPa (80 mmHg), the pump capacity for circulating the electrolyte increases, and the power loss increases due to the power used for the pump.
[実施例１]
高収縮層として、ポリビニルアルコール(ＰＶＡ)ステープル２０質量％を、炭素繊維前駆体ステープルとしてＰＡＮ系耐炎繊維ステープル(繊維長５１ｍｍ、クリンプ率１０％、クリンプ数４ヶ／ｃｍ)に混合し、目付９０ｇ／ｍ2のＰＶＡ混綿ＰＡＮ系耐炎繊維ウェッブを作製した。これを４枚積層させ、スリット層用のウェッブ積層体を得た。
[Example 1]
As a high shrinkage layer, 20% by mass of polyvinyl alcohol (PVA) staple is mixed with a PAN-based flame resistant fiber staple (fiber length 51 mm,
低収縮層として、目付１００ｇ／ｍ2のＰＡＮ系耐炎繊維ウェッブを作製した。これを３枚積層させ、プレーン層用のウェッブ積層体を得た。 As a low shrinkage layer, a PAN-based flame resistant fiber web having a basis weight of 100 g / m 2 was prepared. Three of these were laminated to obtain a web laminated body for a plain layer.
スリット層用のウェッブ積層体と、プレーン層用のウェッブ積層体とを積層し、４００回／ｃｍ2でニードルパンチを行い、表裏の収縮差を有する炭素繊維前駆体フェルトを作製した。 A web laminate for the slit layer and a web laminate for the plain layer were laminated and needle punched at 400 times / cm 2 to produce a carbon fiber precursor felt having a shrinkage difference between the front and back sides.
この炭素繊維前駆体フェルトの高収縮層側において、幅方向に５ｍｍピッチ、３ｍｍ深さとなるようにスリット処理を実施した。その後、７００℃で、スリットによる切込面に直交する方向に１０Ｎ／ｍの張力を付与しながら、１０分間で前炭素化処理した後、１８００℃、３分間で炭素化し、高収縮層側の表面に溝が形成された炭素繊維フェルトを得た。その炭素繊維フェルトを、空気雰囲気中で５００℃、３０分間の酸化処理を行い、電気抵抗値、通液圧力損失を評価した。 On the high shrinkage layer side of this carbon fiber precursor felt, slitting was performed so that the width was 5 mm pitch and 3 mm depth. Thereafter, pre-carbonization treatment was performed for 10 minutes at 700 ° C. while applying a tension of 10 N / m in a direction orthogonal to the slit cutting surface, and then carbonization was performed at 1800 ° C. for 3 minutes. A carbon fiber felt having grooves formed on the surface was obtained. The carbon fiber felt was subjected to an oxidation treatment at 500 ° C. for 30 minutes in an air atmosphere, and the electrical resistance value and the liquid passing pressure loss were evaluated.
[実施例２〜４]
ＰＶＡを、表１に記載の混綿物質に変更した以外は、実施例１と同様の方法で電極を作製した。
[Examples 2 to 4]
An electrode was produced in the same manner as in Example 1 except that PVA was changed to the mixed cotton material shown in Table 1.
[実施例５]
混綿物質を使用せずに耐炎繊維フェルト単味で、表裏の収縮差を有さない炭素繊維前駆体フェルトを作製し、焼成時の張力を２０Ｎ／ｍとした以外は、実施例１と同様の方法で電極を作製した。
[Example 5]
The same as in Example 1 except that a carbon fiber precursor felt that does not have a shrinkage difference between the front and back sides is prepared without using a mixed cotton substance, and the tension during firing is 20 N / m. The electrode was produced by the method.
[実施例６]
焼成時の張力を０Ｎ／ｍとした以外は、実施例１と同様の方法で電極を作製した。
[Example 6]
An electrode was produced in the same manner as in Example 1 except that the tension during firing was set to 0 N / m.
[実施例７]
高収縮層において、目付９０ｇ／ｍ2のＰＶＡ混綿ＰＡＮ系耐炎繊維ウェッブ６枚積層させた上に、目付５０ｇ／ｍ2のＰＡＮ系耐炎繊維ウェッブ３枚積層させた以外は、実施例１と同様の方法で電極を作製した。
[Example 7]
In the high shrinkage layer, the same as Example 1 except that 6 PVA blended cotton PAN flame resistant fiber webs having a basis weight of 90 g / m 2 were laminated and then 3 PAN flame resistant fiber webs having a basis weight of 50 g / m 2 were laminated. The electrode was produced by the method.
[実施例８]
高収縮層において、収縮の大きい低比重ＯＰＦのみを用いること以外は、実施例１と同様の方法で電極を作製した。
[Example 8]
An electrode was produced in the same manner as in Example 1 except that only the low specific gravity OPF having large shrinkage was used in the high shrinkage layer.
[比較例１]
表裏の収縮差を有さない炭素繊維前駆体単体フェルトとし、溝幅１ｍｍ、溝深さ３ｍｍ、溝ピッチ６ｍｍとなるように作製したプレス板にて、２００℃、５０ｋｇ／ｃｍ2でヒートプレスを行い、溝付き炭素繊維前駆体フェルトを得た。それ以外は、実施例１と同様の方法で電極を作製した。
[Comparative Example 1]
Heat press at 200 ° C. and 50 kg / cm 2 on a press plate produced with a carbon fiber precursor simple felt that does not have a shrinkage difference between the front and back surfaces and a groove width of 1 mm, a groove depth of 3 mm, and a groove pitch of 6 mm. The grooved carbon fiber precursor felt was obtained. Otherwise, electrodes were produced in the same manner as in Example 1.
[比較例２]
表裏の収縮差を有さない炭素繊維前駆体単体フェルトとし、炭素化時に張力を付与しない以外は、実施例１と同様の方法で電極を作製した。
[Comparative Example 2]
An electrode was produced in the same manner as in Example 1 except that the carbon fiber precursor simple felt without front and back shrinkage was used and no tension was applied during carbonization.
表１、２に示すように、実施例１〜８は、電気抵抗値、通液圧力損失が共に低く、良好な結果を示す炭素繊維フェルトが得られた。 As shown in Tables 1 and 2, Examples 1 to 8 had low electric resistance values and low fluid pressure loss, and carbon fiber felts showing good results were obtained.
比較例１は、プレスにより溝を形成させた結果、畝部分の嵩密度が小さく、セルに組んだ際に畝が潰れ、通液圧力損失が高い結果となった。 In Comparative Example 1, as a result of forming the grooves by pressing, the bulk density of the heel portion was small, the heel was crushed when assembled in the cell, and the liquid passing pressure loss was high.
比較例２は、十分な溝が形成されず、通液圧力損失が高い結果となった。 In Comparative Example 2, sufficient grooves were not formed, and the liquid passing pressure loss was high.
[実施例９]
高収縮層のＰＶＡの混率を５％とした以外は、実施例１と同様の方法で電極を作製した。
[Example 9]
An electrode was produced in the same manner as in Example 1 except that the mixing ratio of PVA in the high shrinkage layer was 5%.
[実施例１０]
炭素化時の張力を２Ｎ／ｍとした以外は、実施例１と同様の方法で電極を作製した。
[Example 10]
An electrode was produced in the same manner as in Example 1 except that the tension during carbonization was 2 N / m.
[実施例１１]
高収縮層のＰＶＡの混率を５０％とした以外は、実施例１と同様の方法で電極を作製した。
[Example 11]
An electrode was produced in the same manner as in Example 1 except that the mixing ratio of PVA in the highly shrinkable layer was 50%.
[実施例１２]
炭素化時の張力を５０Ｎ／ｍとした以外は、実施例１と同様の方法で電極を作製した。
[Example 12]
An electrode was produced in the same manner as in Example 1 except that the tension during carbonization was 50 N / m.
[実施例１３〜１６]
表３、４のスリットの深さ、ピッチとした以外は、実施例１と同様の方法で電極を作製した。
[Examples 13 to 16]
An electrode was produced in the same manner as in Example 1 except that the slit depth and pitch in Tables 3 and 4 were used.
表３、４に示すように、実施例９〜１６は、電気抵抗値、通液圧力損失が共に低く、良好な結果を示す炭素繊維フェルトが得られた。 As shown in Tables 3 and 4, in Examples 9 to 16, both the electric resistance value and the liquid passing pressure loss were low, and carbon fiber felts showing good results were obtained.
[実施例１７〜１８]
表４のスリット形状、ピッチとした以外は、実施例１と同様の方法で電極を作製した。
[Examples 17 to 18]
An electrode was produced in the same manner as in Example 1 except that the slit shape and pitch in Table 4 were used.
[実施例１９]
表５のスリット形状、ピッチとした以外は、実施例１と同様の方法で電極を作製した。
[Example 19]
An electrode was produced in the same manner as in Example 1 except that the slit shape and pitch in Table 5 were used.
[実施例２０]
高収縮層において、目付８０ｇ／ｍ2のＰＶＡ混綿ＰＡＮ系耐炎繊維ウェッブに、目付６０ｇ／ｍ2のＰＡＮ系耐炎繊維ウェッブを積層させた以外は、実施例１と同様の方法で電極を作製した。
[Example 20]
An electrode was prepared in the same manner as in Example 1 except that a PAN-based flame resistant fiber web having a basis weight of 60 g / m 2 was laminated on a PVA blended cotton PAN flame resistant fiber web having a basis weight of 80 g / m 2 . .
[実施例２１]
高収縮層において、目付８５ｇ／ｍ2のＰＶＡ混綿ＰＡＮ系耐炎繊維ウェッブ１０枚に、目付７０ｇ／ｍ2のＰＡＮ系耐炎繊維ウェッブを１０枚積層させた以外は、実施例１と同様の方法で電極を作製した。
[Example 21]
In the high shrinkage layer, the same method as in Example 1 except that 10 PAN-based flame resistant fiber webs having a basis weight of 70 g / m 2 were laminated on 10 PVA blended cotton PAN flame resistant fiber webs having a basis weight of 85 g / m 2. An electrode was produced.
表３に示すように実施例１７〜２１は、電気抵抗値、通液圧力損失が共に低く、良好な結果を示す炭素繊維フェルトが得られた。 As shown in Table 3, in Examples 17 to 21, carbon fiber felts exhibiting good results were obtained with both low electrical resistance values and low fluid pressure loss.
[比較例３]
高収縮層において、ＰＶＡの混率２％とし、炭素化時の張力を２Ｎ／ｍとした以外は、実施例１と同様の方法で電極を作製した。その結果、十分な溝幅を形成できず、通液圧力損失は高い結果となった。
[Comparative Example 3]
An electrode was produced in the same manner as in Example 1 except that the high shrinkage layer was mixed with PVA at 2% and the tension during carbonization was 2 N / m. As a result, a sufficient groove width could not be formed, and the liquid passing pressure loss was high.
[比較例４]
高収縮層の耐炎繊維の比重を１．３３とし、炭素化時の張力を１１０N／ｍとした以外は、実施例１と同様の方法で電極を作製した。溝幅が大きく、接触抵抗が低く、電気抵抗値が高い結果となった。また、炭素化後の変形が大きく、通液圧力損失の評価は不可能であった。
[Comparative Example 4]
An electrode was produced in the same manner as in Example 1, except that the specific gravity of the flame resistant fiber of the high shrinkage layer was 1.33 and the tension during carbonization was 110 N / m. The groove width was large, the contact resistance was low, and the electrical resistance value was high. In addition, deformation after carbonization was large, and evaluation of liquid passing pressure loss was impossible.
[比較例５]
スリットの深さを５．２ｍｍ(厚みに対し９５％)とした以外は、実施例１と同様の方法で電極を作製した。その結果、炭素化時に破断し、評価できなかった。
[Comparative Example 5]
An electrode was produced in the same manner as in Example 1 except that the slit depth was 5.2 mm (95% of the thickness). As a result, it broke during carbonization and could not be evaluated.
[比較例６]
スリットの深さを０．５ｍｍ(厚みに対し９％)とした以外は、実施例１と同様の方法で電極を作製した。その結果、溝が十分に確保できず、目標の通液圧力損失を得られなかった。
[Comparative Example 6]
An electrode was produced in the same manner as in Example 1 except that the slit depth was 0.5 mm (9% with respect to the thickness). As a result, the grooves could not be secured sufficiently, and the target liquid passing pressure loss could not be obtained.
[比較例７]
ピッチ間隔を大きくした以外は、実施例１と同様の方法で電極を作製した。その結果、フェルト断面に対する溝断面(溝断面積比)が小さく、目標の通液圧力損失が得られなかった。
[Comparative Example 7]
An electrode was produced in the same manner as in Example 1 except that the pitch interval was increased. As a result, the groove cross section (groove cross-sectional area ratio) with respect to the felt cross section was small, and the target liquid passing pressure loss could not be obtained.
[比較例８]
高収縮層において、目付９０ｇ／ｍ2のＰＶＡ混綿ＰＡＮ系耐炎繊維ウェッブに、目付４５ｇ／ｍ2のＰＡＮ系耐炎繊維ウェッブを積層させた以外は、実施例１と同様の方法で電極を作製した。その結果、厚みが小さく、目標の通液圧力損失が得られなかった。
[Comparative Example 8]
In the high shrinkage layer, an electrode was produced in the same manner as in Example 1 except that a PAN-based flame resistant fiber web having a basis weight of 45 g / m 2 was laminated on a PVA mixed cotton PAN flame resistant fiber web having a basis weight of 90 g / m 2 . . As a result, the thickness was small and the target liquid passing pressure loss could not be obtained.
[比較例９]
炭素化温度を１２００℃とした以外は、実施例１と同様の方法で電極を作製した。その結果、電気抵抗が高い結果となった。
[Comparative Example 9]
An electrode was produced in the same manner as in Example 1 except that the carbonization temperature was 1200 ° C. As a result, the electrical resistance was high.
２ 炭素繊維フェルト
４ 畝部
６ 溝部
８ 溝部の底壁
１０ 電池セル部材
ｔ 炭素繊維フェルトの厚み
Ｔ 溝の深さ
２２ 炭素繊維前駆体フェルト
２４ 切込み
２６ フェルトにおける切込みを形成していない部分(プレーン層)
２８ フェルトにおける切込みを形成している部分(スリット層)
Ｓ、Ｒ 張力の方向を示す矢印
３２ 低収縮層
３４ 高収縮層
Ｘ、Ｙ 電解液の流れ方向を示す矢印
４２ レドックスフロー型電池
４４ セル部
４６、４８ 電解液タンク部
５０、５２ 集電板
５４ 隔膜
５６、５８ 送液ポンプ
６０、６２ 電極
2 Carbon fiber felt 4
28 The part that forms the cut in the felt (slit layer)
S, R Arrows indicating
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