JP5777595B2 - Fuel cell, carbon composite structure, and manufacturing method thereof - Google Patents
Fuel cell, carbon composite structure, and manufacturing method thereof Download PDFInfo
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- JP5777595B2 JP5777595B2 JP2012250561A JP2012250561A JP5777595B2 JP 5777595 B2 JP5777595 B2 JP 5777595B2 JP 2012250561 A JP2012250561 A JP 2012250561A JP 2012250561 A JP2012250561 A JP 2012250561A JP 5777595 B2 JP5777595 B2 JP 5777595B2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 49
- 229910052799 carbon Inorganic materials 0.000 title claims description 49
- 239000002131 composite material Substances 0.000 title claims description 23
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000446 fuel Substances 0.000 title description 24
- 229920001410 Microfiber Polymers 0.000 claims description 42
- 239000003658 microfiber Substances 0.000 claims description 42
- 239000002121 nanofiber Substances 0.000 claims description 34
- 229920000642 polymer Polymers 0.000 claims description 25
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 12
- 239000005011 phenolic resin Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 4
- 238000009987 spinning Methods 0.000 claims description 4
- 239000002798 polar solvent Substances 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229920000647 polyepoxide Polymers 0.000 claims description 2
- 238000010030 laminating Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 description 35
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 31
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- 239000002134 carbon nanofiber Substances 0.000 description 29
- 239000004745 nonwoven fabric Substances 0.000 description 16
- 239000011148 porous material Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 5
- 239000000835 fiber Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229920001568 phenolic resin Polymers 0.000 description 5
- 229920002994 synthetic fiber Polymers 0.000 description 5
- 239000012209 synthetic fiber Substances 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010041 electrostatic spinning Methods 0.000 description 3
- 238000007731 hot pressing Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- -1 oxygen ions Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
- Laminated Bodies (AREA)
- Nonwoven Fabrics (AREA)
- Inert Electrodes (AREA)
Description
本発明は燃料電池、炭素複合構造、およびその作製方法に関する。 The present invention relates to a fuel cell, a carbon composite structure, and a manufacturing method thereof.
燃料電池は、２つの触媒層、２つのガス拡散層、２つのバイポーラプレート、２つの電流コレクタ、および２つのエンドプレートの間に挟みこまれたプロトン伝導膜からなる。燃料電池（ＦＣ）のプロトン伝導膜により分けられた２つの側面は、それぞれ、アノード（水素、改質ガスまたはメタノール）およびカソード（酸素または空気）となる。酸化反応がアノードで進行し、化学的還元反応がカソードで進行する。水素（またはメタノール）がアノードの触媒層（例えば白金またはその合金）に接触すると、水素はプロトンと電子とに解離する。電子は、（アノードとカソードとを連結している）電気的ブリッジ（electrical bridge）を通ってアノードからカソードへと流れる。プロトンは、アノードからプロトン伝導膜を通り抜けてカソードに達する。留意すべきは、プロトン伝導膜は湿潤膜（wet film）であり、水分子を伴うプロトンはそれを通り抜けることができるが、その他の空気分子は通り抜けられないという点である。カソードの触媒は酸素と電気的ブリッジからの電子とを結合して酸素イオンを形成することができる。酸素イオンはプロトン伝導膜を通り抜けたプロトンと反応し、水分子が形成される。上述した反応は電気化学的酸化および還元反応である。 The fuel cell consists of a proton conducting membrane sandwiched between two catalyst layers, two gas diffusion layers, two bipolar plates, two current collectors, and two end plates. The two sides separated by the proton conducting membrane of the fuel cell (FC) are the anode (hydrogen, reformed gas or methanol) and the cathode (oxygen or air), respectively. An oxidation reaction proceeds at the anode and a chemical reduction reaction proceeds at the cathode. When hydrogen (or methanol) contacts the anode catalyst layer (eg, platinum or an alloy thereof), the hydrogen dissociates into protons and electrons. The electrons flow from the anode to the cathode through an electrical bridge (connecting the anode and cathode). Protons pass from the anode through the proton conducting membrane to the cathode. It should be noted that the proton conducting membrane is a wet film, and protons with water molecules can pass through it but other air molecules cannot pass through it. The cathode catalyst can combine oxygen and electrons from the electrical bridge to form oxygen ions. Oxygen ions react with protons that have passed through the proton conducting membrane to form water molecules. The reactions described above are electrochemical oxidation and reduction reactions.
電気化学反応を利用するプロトン交換膜燃料電池（ＰＥＭＦＣ）またはメタノール直接型燃料電池（ＤＭＦＣ）は、高効率、無公害、高速応答などの特性を有する。かかる燃料電池は、電気的ブリッジの電圧を高めるために直列接続することができ、また、電流を増大させるためには、燃料電池の電極反応面積が増大され得る。酸素（通常は空気）が無尽蔵に供給されることより、電力がデバイスに継続的に供給され得る。よって、燃料電池は小型システム電源として用いることができ、また大型発電所、分散電源もしくは移動可能な電源として設計することも可能である。 A proton exchange membrane fuel cell (PEMFC) or a methanol direct fuel cell (DMFC) using an electrochemical reaction has characteristics such as high efficiency, no pollution, and high-speed response. Such fuel cells can be connected in series to increase the voltage of the electrical bridge, and to increase the current, the electrode reaction area of the fuel cell can be increased. By supplying inexhaustible oxygen (usually air), power can be continuously supplied to the device. Thus, the fuel cell can be used as a small system power source, and can also be designed as a large power plant, a distributed power source or a movable power source.
ガス拡散層を形成する主な方法は抄紙プロセスであり、炭素繊維紙を熱可塑性樹脂中に浸漬し、ホットプレスし、熱炭化（thermal carbonized）させてから、適した大きさにカットして、ガス拡散層を形成するというものである。従来の方法において、燃料電池のガス拡散層は炭化樹脂（carbonized resin）を炭素繊維に接着することにより形成される。しかし、この従来の方法は複雑であるため、製造コストを高め、かつ電池の性能を低下させてしまう。 The main method of forming the gas diffusion layer is a papermaking process, where carbon fiber paper is immersed in a thermoplastic resin, hot pressed, thermally carbonized, then cut to a suitable size, A gas diffusion layer is formed. In the conventional method, the gas diffusion layer of the fuel cell is formed by adhering carbonized resin to carbon fiber. However, since this conventional method is complicated, the manufacturing cost is increased and the performance of the battery is lowered.
本発明の一実施形態は、炭素ナノ繊維網層（carbon nano fiber net layer）、および炭素ナノ繊維網層上の炭素マイクロ繊維網層を含む炭素複合構造を提供する。 One embodiment of the present invention provides a carbon composite structure including a carbon nanofiber net layer and a carbon microfiber network layer on the carbon nanofiber network layer.
本発明の一実施形態は、炭素複合構造を作製する方法であって、酸化ポリマーナノ繊維網および酸化マイクロ繊維網を提供する工程、酸化ナノ繊維網および酸化マイクロ繊維網を積層して積層構造を形成する工程、積層構造を樹脂中に含浸する工程、樹脂を酸化する工程、ならびに、酸化ナノ繊維網、酸化マイクロ繊維網、および酸化した樹脂を炭化して炭素複合構造を形成する工程、を含む方法を提供する。 One embodiment of the present invention is a method for producing a carbon composite structure, the method comprising providing an oxidized polymer nanofiber network and an oxidized microfiber network, and stacking an oxidized nanofiber network and an oxidized microfiber network to form a stacked structure. A step of forming, a step of impregnating a laminated structure in a resin, a step of oxidizing a resin, and a step of carbonizing an oxidized nanofiber network, an oxidized microfiber network, and an oxidized resin to form a carbon composite structure. Provide a method.
本発明の一実施形態は、２つのエンドプレートの間に配置されるプロトン伝導膜を含む燃料電池を提供する。触媒層、ガス拡散層、バイポーラプレート、および電流コレクタが、プロトン伝導膜とエンドプレートとの間に順次配置され、前記ガス拡散層は、炭素複合構造を形成する、炭素ナノ繊維網層およびその上に積層される炭素マイクロ繊維網層を含む。 One embodiment of the present invention provides a fuel cell that includes a proton conducting membrane disposed between two end plates. A catalyst layer, a gas diffusion layer, a bipolar plate, and a current collector are sequentially disposed between the proton conducting membrane and the end plate, and the gas diffusion layer includes a carbon nanofiber network layer and a carbon nanofiber network layer formed thereon Including a carbon microfiber network layer laminated to the substrate.
２層からなる炭素複合構造は、単層の炭素ナノ繊維網または単層の炭素マイクロ繊維網と比較してより高い導電率を有する。また、２層からなる炭素複合構造は単層の炭素ナノ繊維網に比べて細孔径分布（pore size distribution）がより低かった。 A two-layer carbon composite structure has a higher electrical conductivity than a single-layer carbon nanofiber network or a single-layer carbon microfiber network. In addition, the two-layer carbon composite structure had a lower pore size distribution than the single-layer carbon nanofiber network.
以下の詳細な説明および実施例により、そして、添付の図面を参照することにより、本発明はより十分に理解される。 The invention will be more fully understood by the following detailed description and examples, and by reference to the accompanying drawings.
以下の発明の詳細な説明においては、本発明を説明する目的で、開示される実施形態が十分に理解されるよう、多数の具体的詳細が示されている。しかしながら、これら具体的詳細が無くとも１つまたは複数の実施形態が実施され得ることは明らかである。他の例においては、図面を簡単にするべく、周知の構造およびデバイスは概略的に示してある。 In the following detailed description, for the purposes of illustrating the present invention, numerous specific details are set forth in order to provide a thorough understanding of the disclosed embodiments. It may be evident, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are schematically shown in order to simplify the drawing.
本発明は炭素複合構造を形成する方法を提供する。先ず、酸化マイクロ繊維網が提供される。一実施形態において、Ｔｏｒａｙ−０９０およびＳＧＬ−３５ＥＣなどの市販の炭素マイクロ繊維網が熱酸化され、酸化マイクロ繊維網が形成される。別の実施形態では、マイクロスケールの直径を有する酸化炭素マイクロ繊維を、ニードルパンチ、抄紙、または製織することにより、不織布、紙、または織布を形成して酸化マイクロ繊維網とする。一実施形態では、酸化マイクロ繊維網は熱プレスにさらにより薄型にされる。 The present invention provides a method of forming a carbon composite structure. First, an oxidized microfiber network is provided. In one embodiment, commercially available carbon microfiber networks such as Toray-090 and SGL-35EC are thermally oxidized to form an oxidized microfiber network. In another embodiment, carbon oxide microfibers having a microscale diameter are needle punched, paper-made, or woven to form a nonwoven fabric, paper, or woven fabric into an oxidized microfiber network. In one embodiment, the oxidized microfiber network is made even thinner for hot pressing.
次いで、ポリアクリロニトリル（ＰＡＮ）などのポリマー、ピッチ、またはフェノール化合物を極性溶媒中に溶解してポリマー溶液を形成する。ポリマーを溶解するために適切な極性溶媒としてはＮ，Ｎ−ジメチルホルムアミド、Ｎ，Ｎ−ジメチルエチルアミン、ジメチルスルホキシドが挙げられる。ポリマー溶液の濃度は約５ｗｔ％から３０ｗｔ％である。その後、ポリマー溶液は紡糸され、網のように積み重ねられた複数のポリマーナノ繊維が形成される。このポリマーナノ繊維の直径は約１００ｎｍから８００ｎｍである。紡糸方法としては静電紡糸（electrostatic spinning）または溶液紡糸であってもよい。静電紡糸は約２０ｋＶから５０ｋＶの電圧で行なわれ、溶液紡糸はノズルの空気圧を約１ｋｇ／ｃｍ2から５ｋｇ／ｃｍ2に設定して行なわれる。電圧をより高める、ノズルの空気圧をより高める、またはポリマー溶液の濃度をより低めることによって、より小さな直径を有するナノ繊維が得られる。 A polymer such as polyacrylonitrile (PAN), pitch, or phenolic compound is then dissolved in a polar solvent to form a polymer solution. Suitable polar solvents for dissolving the polymer include N, N-dimethylformamide, N, N-dimethylethylamine, dimethyl sulfoxide. The concentration of the polymer solution is about 5 wt% to 30 wt%. The polymer solution is then spun to form a plurality of polymer nanofibers stacked like a net. The diameter of the polymer nanofiber is about 100 nm to 800 nm. The spinning method may be electrostatic spinning or solution spinning. Electrospinning is performed at a voltage of about 20 kV to 50 kV, and solution spinning is performed with the nozzle air pressure set to about 1 kg / cm 2 to 5 kg / cm 2 . By increasing the voltage, increasing the air pressure of the nozzle, or decreasing the concentration of the polymer solution, nanofibers with smaller diameters are obtained.
ポリマーナノ繊維網は、酸化ナノ繊維網を形成するために熱酸化される。酸化ナノ繊維網および酸化マイクロ繊維網は積層され、そしてその後、接着のために樹脂中に含浸される。樹脂としては、フェノール樹脂、エポキシ樹脂、またはこれらの組み合わせであってもよい。含浸の工程が省かれた場合、酸化ナノ繊維網および酸化マイクロ繊維網の積層体（stack）は薄い層に裂け易くなり、電池の性能が低下する。一実施形態では、酸化ナノ繊維網および酸化マイクロ繊維網は積層され、そしてその後、フェノール樹脂中に含浸される。その後、フェノール樹脂は酸化され、そして、積層体は窒素下、高温で熱炭化される。これにより、酸化ナノ繊維網、酸化マイクロ繊維網および酸化フェノール樹脂が炭化して、炭素複合構造が形成される。炭化工程の熱源としては、マイクロ波または高温炉が挙げられる。 The polymer nanofiber network is thermally oxidized to form an oxidized nanofiber network. The oxidized nanofiber network and oxidized microfiber network are laminated and then impregnated into the resin for adhesion. The resin may be a phenol resin, an epoxy resin, or a combination thereof. If the impregnation step is omitted, the stack of oxidized nanofiber network and oxidized microfiber network is easily broken into thin layers, and the performance of the battery is degraded. In one embodiment, the oxidized nanofiber network and oxidized microfiber network are laminated and then impregnated in a phenolic resin. Thereafter, the phenolic resin is oxidized and the laminate is thermally carbonized at a high temperature under nitrogen. As a result, the oxidized nanofiber network, the oxidized microfiber network, and the oxidized phenol resin are carbonized to form a carbon composite structure. As a heat source for the carbonization step, a microwave or a high temperature furnace can be used.
別の実施形態では、酸化ナノ繊維網を市販の炭素マイクロ繊維網上に直接積層してから、フェノール樹脂中に含浸してもよい。その後、フェノール樹脂を酸化し、そして、酸化積層体を窒素下、高温で炭化させて、２層からなる炭素複合構造が形成される。 In another embodiment, the oxidized nanofiber network may be laminated directly onto a commercially available carbon microfiber network and then impregnated into the phenolic resin. Thereafter, the phenol resin is oxidized, and the oxidized laminate is carbonized at a high temperature under nitrogen to form a two-layer carbon composite structure.
ポリマーナノ繊維網を約２００℃から３５０℃の温度で約１時間から４時間、熱的に酸化する。フェノール樹脂を約１５０℃から２５０℃の温度で約１時間から４時間、酸化する。炭素複合構造は、炭素ナノ繊維網および炭素マイクロ繊維網の２層積層構造である。一実施形態において、炭素ナノ繊維網層の炭素ナノ繊維の直径は１００ｎｍから８００ｎｍであり、そして、炭素ナノ繊維網層の細孔の細孔径（pore size）は約１００ｎｍから２．５μｍである。炭素ナノ繊維網の厚さは約１０μｍから１００μｍまたは約３０μｍから８０μｍである。直径が過度に小さい炭素ナノ繊維は、熱収縮係数が過度に大きいために、接着に困難がある。直径が過度に大きい炭素ナノ繊維は、炭素ナノ繊維網に過度の大きな細孔を有させる。炭素ナノ繊維網の過度に小さな細孔は、メタノールを移動させることができない。一方、過度に大きい細孔は、メタノールを遮断することができない。過度に薄い炭素ナノ繊維網は破損し易く、そして、過度に厚い炭素ナノ繊維網は過度に小さな細孔を有する。 The polymer nanofiber network is thermally oxidized at a temperature of about 200 ° C. to 350 ° C. for about 1 to 4 hours. The phenolic resin is oxidized at a temperature of about 150 ° C. to 250 ° C. for about 1 to 4 hours. The carbon composite structure is a two-layer laminated structure of a carbon nanofiber network and a carbon microfiber network. In one embodiment, the carbon nanofiber diameter of the carbon nanofiber network layer is from 100 nm to 800 nm, and the pore size of the pores of the carbon nanofiber network layer is from about 100 nm to 2.5 μm. The thickness of the carbon nanofiber network is about 10 μm to 100 μm or about 30 μm to 80 μm. Carbon nanofibers having an excessively small diameter are difficult to bond due to an excessively large thermal shrinkage coefficient. Carbon nanofibers with an excessively large diameter cause the carbon nanofiber network to have excessively large pores. The excessively small pores in the carbon nanofiber network cannot move methanol. On the other hand, excessively large pores cannot block methanol. An excessively thin carbon nanofiber network is prone to breakage, and an excessively thick carbon nanofiber network has excessively small pores.
一実施形態において、炭素マイクロ繊維網層の炭素マイクロ繊維の直径は約２μｍから１０μｍまたは約２μｍから８μｍであり、そして、炭素マイクロ繊維網層の細孔の細孔径は約３μｍから１２μｍである。炭素マイクロ繊維網の厚さは約１００μｍから６００μｍである。炭素マイクロ繊維網層は炭素繊維が交絡している３次元構造を有し、かかる炭素繊維間の導電網（electrically conductive net）は、炭素マイクロ繊維網層の導電性を大幅に高めることができる。 In one embodiment, the carbon microfiber diameter of the carbon microfiber network layer is about 2 μm to 10 μm or about 2 μm to 8 μm, and the pore diameter of the pores of the carbon microfiber network layer is about 3 μm to 12 μm. The thickness of the carbon microfiber network is about 100 μm to 600 μm. The carbon microfiber network layer has a three-dimensional structure in which carbon fibers are entangled, and the electrically conductive net between the carbon fibers can greatly increase the conductivity of the carbon microfiber network layer.
一実施形態において、２層積層構造中の炭素ナノ繊維網および炭素マイクロ繊維網の厚さ比は約１〜１０：１０〜６０または２〜６：２５〜３５である。 In one embodiment, the thickness ratio of the carbon nanofiber network and the carbon microfiber network in the two-layer laminate structure is about 1-10: 10-60 or 2-6: 25-35.
以下に、当業者に容易に理解されるよう、添付の図面を参照にして例示的な実施形態を詳細に説明する。本発明の発明概念は、本明細書に記載されるこれら例示的な実施形態に限定されることなく、様々な形式で具体化され得る。記載を明確にするため、周知の部分についての説明は省かれており、また全体を通して、類似する参照番号は類似する要素を示すものとする。 Hereinafter, exemplary embodiments will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily understand them. The inventive concept of the invention is not limited to these exemplary embodiments described herein, but may be embodied in various forms. For clarity of description, descriptions of well-known portions have been omitted, and like reference numerals refer to like elements throughout.
実施例１（炭素マイクロ繊維網の製造）
６μｍから７μｍの直径を有するＰＡＮの酸化繊維（SHINKONG SYNTHETIC FIBER社により市販されている）にニードルパンチを施して不織布とした。不織布の厚さは３ｍｍ、坪量は３００ｇ／ｍ2であった。この不織布を窒素下、加熱速度１０℃／分で１５００℃まで加熱し、これにより不織布の酸化繊維を炭化させて炭素マイクロ繊維網を形成した。炭素マイクロ繊維網の表面抵抗は２９９ｍΩ／□、体積抵抗は７ｍΩ・ｃｍ、導電率は１３３Ｓ／ｃｍ、耐圧性（pressure durability）は１００ｋｇ／ｃｍ2、細孔径分布は３μｍから１２μｍであった。
Example 1 (Production of carbon microfiber network)
A PAN oxide fiber (commercially available from SHINKONG SYNTHETIC FIBER) having a diameter of 6 μm to 7 μm was needle punched into a nonwoven fabric. The nonwoven fabric had a thickness of 3 mm and a basis weight of 300 g / m 2 . The nonwoven fabric was heated to 1500 ° C. at a heating rate of 10 ° C./min under nitrogen, thereby carbonizing the oxidized fibers of the nonwoven fabric to form a carbon microfiber network. The surface resistance of the carbon microfiber network was 299 mΩ / □, the volume resistance was 7 mΩ · cm, the conductivity was 133 S / cm, the pressure durability was 100 kg / cm 2 , and the pore size distribution was 3 μm to 12 μm.
実施例２（炭素マイクロ繊維網の製造）
６μｍから７μｍの直径を有するＰＡＮの酸化繊維（SHINKONG SYNTHETIC FIBER社により市販されている）にニードルパンチを施して不織布とした。不織布の厚さは３ｍｍ、坪量は３００ｇ／ｍ2であった。この不織布を熱プレスにより薄くして、厚さ１．５ｍｍのより緻密な不織布とした。薄くされた不織布を窒素下、加熱速度１０℃／分で１５００℃まで加熱し、これにより薄くされた不織布の酸化繊維を炭化させて炭素マイクロ繊維網を形成した。炭素マイクロ繊維網の表面抵抗は２４６ｍΩ／□、体積抵抗は６ｍΩ・ｃｍ、導電率は１６２Ｓ／ｃｍ、耐圧性は１００ｋｇ／ｃｍ2、細孔径分布は３μｍから１０μｍであった。炭素マイクロ繊維網の厚さは約３００±１０μｍであった。
Example 2 (Production of carbon microfiber network)
A PAN oxide fiber (commercially available from SHINKONG SYNTHETIC FIBER) having a diameter of 6 μm to 7 μm was needle punched into a nonwoven fabric. The nonwoven fabric had a thickness of 3 mm and a basis weight of 300 g / m 2 . This nonwoven fabric was thinned by hot pressing to obtain a denser nonwoven fabric having a thickness of 1.5 mm. The thinned nonwoven fabric was heated to 1500 ° C. at a heating rate of 10 ° C./min under nitrogen, whereby the oxidized fibers of the thinned nonwoven fabric were carbonized to form a carbon microfiber network. The surface resistance of the carbon microfiber network was 246 mΩ / □, the volume resistance was 6 mΩ · cm, the conductivity was 162 S / cm, the pressure resistance was 100 kg / cm 2 , and the pore size distribution was 3 μm to 10 μm. The thickness of the carbon microfiber network was about 300 ± 10 μm.
実施例３（炭素ナノ繊維網の製造）
ポリアクリロニトリル（Tong-Hwa Synthetic Fiber社により市販されている）１３ｇをジメチルアセトアミド（ＤＭＡｃ）８７ｇ中に溶解してポリアクリロニトリル溶液を作製した。このポリアクリロニトリル溶液を、印加電圧３９．５ｋＶで静電紡糸により紡糸し、ポリマーナノ繊維網を形成させた。このポリマーナノ繊維の直径は２００ｎｍから７００ｎｍであった。ポリマーナノ繊維網を酸素下、２８０℃の温度で１８０分間酸化し、酸化ナノ繊維網を得た。この酸化ナノ繊維網を窒素下、加熱速度１０℃／分で１５００℃まで加熱して炭化させた。これにより酸化ナノ繊維は炭化され、炭素ナノ繊維網が形成された。炭素ナノ繊維網の厚さは３８μｍから４４μｍ、表面抵抗は９Ω／ｃｍ2、体積抵抗は０．０５Ω・ｃｍ、導電率は１３Ｓ／ｃｍ、耐圧性は１０ｋｇ／ｃｍ2、細孔系分布は１μｍから２μｍであった。実施例２の薄くされた炭素マイクロ繊維網に比べ、実施例３の炭素ナノ繊維網は、体積抵抗が著しく低く、機械的強度および耐圧性がより低かった。
Example 3 (Production of carbon nanofiber network)
A polyacrylonitrile solution was prepared by dissolving 13 g of polyacrylonitrile (commercially available from Tong-Hwa Synthetic Fiber) in 87 g of dimethylacetamide (DMAc). This polyacrylonitrile solution was spun by electrostatic spinning at an applied voltage of 39.5 kV to form a polymer nanofiber network. The diameter of this polymer nanofiber was 200 nm to 700 nm. The polymer nanofiber network was oxidized under oxygen at a temperature of 280 ° C. for 180 minutes to obtain an oxidized nanofiber network. The oxidized nanofiber network was carbonized by heating to 1500 ° C. at a heating rate of 10 ° C./min under nitrogen. As a result, the oxidized nanofibers were carbonized to form a carbon nanofiber network. The carbon nanofiber network has a thickness of 38 μm to 44 μm, a surface resistance of 9 Ω / cm 2 , a volume resistance of 0.05 Ω · cm, a conductivity of 13 S / cm, a pressure resistance of 10 kg / cm 2 , and a pore distribution of 1 μm. To 2 μm. Compared to the thinned carbon microfiber network of Example 2, the carbon nanofiber network of Example 3 had significantly lower volume resistance and lower mechanical strength and pressure resistance.
実施例４（炭素ナノ繊維網および炭素マイクロ繊維網の複合構造の製造）
６μｍから７μｍの直径を有するＰＡＮの酸化繊維（SHINKONG SYNTHETIC FIBER社により市販されている）にニードルパンチを施して不織布とした。不織布の厚さは３ｍｍ、坪量は３００ｇ／ｍ2であった。この不織布を熱プレスにより薄くして、厚さ１．５ｍｍのより緻密な不織布とした。
Example 4 (Production of composite structure of carbon nanofiber network and carbon microfiber network)
A PAN oxide fiber (commercially available from SHINKONG SYNTHETIC FIBER) having a diameter of 6 μm to 7 μm was needle punched into a nonwoven fabric. The nonwoven fabric had a thickness of 3 mm and a basis weight of 300 g / m 2 . This nonwoven fabric was thinned by hot pressing to obtain a denser nonwoven fabric having a thickness of 1.5 mm.
ポリアクリロニトリル（Tong-Hwa Synthetic Fiber社により市販されている）１３ｇをジメチルアセトアミド（ＤＭＡｃ）８７ｇ中に溶解してポリアクリロニトリル溶液を作製した。このポリアクリロニトリル溶液を、印加電圧３９．５ｋＶで静電紡糸により紡糸し、ポリマーナノ繊維網を形成させた。このポリマーナノ繊維の直径は２００ｎｍから７００ｎｍであった。ポリマーナノ繊維網を酸素下、２７０℃の温度で１８０分間酸化させ、酸化ナノ繊維網を得た。この酸化ナノ繊維網の厚さは５９μｍから６４μｍであった。 A polyacrylonitrile solution was prepared by dissolving 13 g of polyacrylonitrile (commercially available from Tong-Hwa Synthetic Fiber) in 87 g of dimethylacetamide (DMAc). This polyacrylonitrile solution was spun by electrostatic spinning at an applied voltage of 39.5 kV to form a polymer nanofiber network. The diameter of this polymer nanofiber was 200 nm to 700 nm. The polymer nanofiber network was oxidized under oxygen at a temperature of 270 ° C. for 180 minutes to obtain an oxidized nanofiber network. The thickness of the oxidized nanofiber network was 59 μm to 64 μm.
酸化ナノ繊維網および薄くされた不織布を積層し、そしてその後、フェノール樹脂中に含浸した。この積層構造を酸素下、２００℃の温度で加熱して、フェノール樹脂を酸化させた。この酸化積層構造を窒素下、加熱速度１０℃／分で１５００℃まで加熱し、これによって酸化ナノ繊維網、不織布および酸化フェノール樹脂を炭化させ、炭素複合構造を形成させた。炭素ナノ繊維網の厚さは３８μｍから４４μｍ、炭素マイクロ繊維網の厚さは約３００±１０μｍであった。炭素複合構造の表面抵抗は２１３ｍΩ／ｃｍ2、体積抵抗は５ｍΩ・ｃｍ、導電率は１９０Ｓ／ｃｍ、耐圧性は１００ｋｇ／ｃｍ2、細孔径分布は１μｍから１．５μｍであった。図２の断面ＳＥＭ写真に示されるように、炭素ナノ繊維網２１および炭素マイクロ繊維網２３は積層され炭素複合構造２０が形成された。 The oxidized nanofiber network and thinned nonwoven were laminated and then impregnated in phenolic resin. This laminated structure was heated at a temperature of 200 ° C. under oxygen to oxidize the phenol resin. This oxidized laminated structure was heated to 1500 ° C. at a heating rate of 10 ° C./min under nitrogen, thereby carbonizing the oxidized nanofiber network, the nonwoven fabric and the oxidized phenol resin to form a carbon composite structure. The thickness of the carbon nanofiber network was 38 μm to 44 μm, and the thickness of the carbon microfiber network was about 300 ± 10 μm. The carbon composite structure had a surface resistance of 213 mΩ / cm 2 , a volume resistance of 5 mΩ · cm, a conductivity of 190 S / cm, a pressure resistance of 100 kg / cm 2 , and a pore size distribution of 1 μm to 1.5 μm. As shown in the cross-sectional SEM photograph of FIG. 2, the carbon nanofiber network 21 and the carbon microfiber network 23 were laminated to form the carbon composite structure 20.
実施例４の２層からなる炭素複合構造は、実施例３の単層炭素ナノ繊維網または実施例２の単層炭素マイクロ繊維網と比較してより高い導電率を有していた。実施例４の２層からなる炭素複合構造の細孔径分布は、実施例３の単層炭素ナノ繊維網に比べてより低いものであった。 The two-layer carbon composite structure of Example 4 had a higher electrical conductivity than the single-layer carbon nanofiber network of Example 3 or the single-layer carbon microfiber network of Example 2. The pore size distribution of the two-layer carbon composite structure of Example 4 was lower than that of the single-layer carbon nanofiber network of Example 3.
実施例５（燃料電池試験）
実施例１から４の試料を５ｃｍ×５ｃｍのサイズにカットし、そしてその後、触媒被覆膜（catalyst coated membrane、ＣＣＭ、Dupont社から市販されているE71913）と組み合わせて３層からなる膜／電極接合体（ＭＥＡ）を作製した。これら接合体を燃料電池試験モジュール中に封入した。テフロン（登録商標）ガスケットによりその気密性を確認した後、燃料電池の試験を行った。
Example 5 (Fuel cell test)
Samples from Examples 1 to 4 were cut to a size of 5 cm x 5 cm and then combined with a catalyst coated membrane (Calyst coated membrane, CCM, E71913 commercially available from Dupont) in three layers of membrane / electrode A joined body (MEA) was produced. These assemblies were sealed in a fuel cell test module. After confirming its airtightness with a Teflon (registered trademark) gasket, the fuel cell was tested.
アノードの燃料（１Ｍ メタノール）の流量は１．８３ｓｔｐｍ、およびカソードのガス（Ｏ2）の流量は３００ｃｃ／ｍｉｎとした。試験温度は６０℃に設定した。燃料電池に０．４Ｖを印加し、その電流密度およびメタノール遮断能（methanol-blocking ability）を測定した。実施例１の試料を使用した燃料電池の電流密度は５５ｍＡ／ｃｍ2であり、メタノール遮断能は０．５７７Ｖであった。実施例２の試料を使用した燃料電池の電流密度は５７ｍＡ／ｃｍ2であり、メタノール遮断能は０．５８４Ｖであった。実施例３の試料を使用した燃料電池は耐圧性が不十分であったため、測定は不可能であった。実施例４の試料を使用した燃料電池の電流密度は６０ｍＡ／ｃｍ2であり、メタノール遮断能は０．５９４Ｖであった。このように、実施例４の炭素複合構造を使用した燃料電池は、実施例１〜３の単層からなる炭素ナノ繊維網または炭素マイクロ繊維網を使用した燃料電池と比較して、より高い電流密度およびより高いメタノール遮断能を有していた。 The flow rate of anode fuel (1M methanol) was 1.83 stpm, and the flow rate of cathode gas (O 2 ) was 300 cc / min. The test temperature was set to 60 ° C. 0.4V was applied to the fuel cell, and its current density and methanol-blocking ability were measured. The current density of the fuel cell using the sample of Example 1 was 55 mA / cm 2 , and the methanol blocking ability was 0.577V. The current density of the fuel cell using the sample of Example 2 was 57 mA / cm 2 , and the methanol blocking ability was 0.584V. Since the pressure resistance of the fuel cell using the sample of Example 3 was insufficient, measurement was impossible. The current density of the fuel cell using the sample of Example 4 was 60 mA / cm 2 , and the methanol blocking ability was 0.594V. Thus, the fuel cell using the carbon composite structure of Example 4 has a higher current compared to the fuel cell using the carbon nanofiber network or carbon microfiber network composed of a single layer of Examples 1 to 3. It had a density and higher methanol blocking ability.
一実施形態では、図１に示されるように、炭素複合構造は燃料電池のガス拡散層１５とすることができる。図１において、プロトン伝導膜１１は、２つの触媒層１３、２つのガス拡散層１５、２つのバイポーラプレート１７、２つの電流コレクタ１８、および２つのエンドプレート１９の間に挟みこまれている。 In one embodiment, the carbon composite structure can be a fuel cell gas diffusion layer 15, as shown in FIG. In FIG. 1, the proton conducting membrane 11 is sandwiched between two catalyst layers 13, two gas diffusion layers 15, two bipolar plates 17, two current collectors 18, and two end plates 19.
開示された実施形態に各種修飾および変更を加えてもよいことは、当業者には明らかであろう。明細書および実施例は例示的なものと見なされるように意図されており、本発明の開示の真の範囲は以下のクレームおよびそれらの均等物により示される。 It will be apparent to those skilled in the art that various modifications and variations can be made to the disclosed embodiments. It is intended that the specification and examples be considered as exemplary, with the true scope of the present disclosure being indicated by the following claims and their equivalents.
１１ プロトン伝導膜
１３ 触媒層
１５ ガス拡散層
１６ デバイス
１７ バイポーラプレート
１８ 電流コレクタ
１９ エンドプレート
２０ 炭素複合構造
２１ 炭素ナノ繊維網
２２ 炭素マイクロ繊維網
DESCRIPTION OF SYMBOLS 11 Proton conductive membrane 13 Catalyst layer 15 Gas diffusion layer 16 Device 17 Bipolar plate 18 Current collector 19 End plate 20 Carbon composite structure 21 Carbon nanofiber network 22 Carbon microfiber network
Claims (4)
酸化ポリマーナノ繊維網および酸化マイクロ繊維網を提供する工程、
前記酸化ナノ繊維網および前記酸化マイクロ繊維網を積層して積層構造を形成する工程、
前記積層構造を樹脂中に含浸する工程、
前記樹脂を酸化する工程、ならびに
前記酸化ナノ繊維網、前記酸化マイクロ繊維網および前記酸化した樹脂を炭化して炭素複合構造を形成する工程、
を含む方法。 A method for producing a carbon composite structure comprising:
Providing an oxidized polymer nanofiber network and an oxidized microfiber network;
Laminating the oxidized nanofiber network and the oxidized microfiber network to form a laminated structure;
Impregnating the laminated structure in a resin;
Oxidizing the resin, and carbonizing the oxidized nanofiber network, the oxidized microfiber network, and the oxidized resin to form a carbon composite structure;
Including methods.
ポリマー溶液を提供する工程、および
前記ポリマー溶液を紡糸して複数のポリマーナノ繊維を形成する工程であって、前記ポリマーナノ繊維が積み重ねられて前記ポリマーナノ繊維網が形成される工程、
を含む請求項１記載の方法。 Providing the oxidized polymer nanofiber network comprises:
Providing a polymer solution; and spinning the polymer solution to form a plurality of polymer nanofibers, wherein the polymer nanofibers are stacked to form the polymer nanofiber network;
The method of claim 1 further comprising.
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| WO2018062622A1 (en) * | 2016-09-27 | 2018-04-05 | 가드넥 주식회사 | Gas diffusion layer comprising porous carbonaceous film layer for fuel cell |
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| JP2007099551A (en) * | 2005-10-03 | 2007-04-19 | Bridgestone Corp | Carbon-based composite material and its manufacturing method, electrode for solid polymer type fuel cell and solid polymer type fuel cell |
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