Study on the preparation and properties of novolac epoxy/graphite composite bipolar plate for PEMFC

In this study, the graphite/polymer composite bipolar plate was manufactured by a bulk-molding compound process. Low-cost novolac epoxy was chosen to compound with natural graphite and black carbon. The electrical properties and mechanical properties of composite bipolar plate were studied. The aging behavior was characterized according to the changes in property before and after the immersion test. The results show that the composite bipolar plates have good corrosion resistibility in the simulated solution of 0.005 mol L⁻¹ H₂SO₄ + 2 × 10⁻⁶ mol L⁻¹ HF. TGA result shows that the novolac epoxy/NG composite has excellent thermal stability. The optimum processing conditions for preparing composite bipolar plate are: resin content about 15 wt.%; molding pressure 200 MPa; curing temperature 180 °C; graphite particle size −200 mesh. Under the optimum conditions, the composite bipolar plates have been produced, the electrical conductivity can attain to 120 S/cm and flexural strength is higher than 38 MPa.     

Performance of an aluminate cement /graphite conductive composite bipolar plate

Aluminate cement/graphite conductive composite bipolar plates were prepared by mould pressing at room temperature. The effects of the graphite content, the mould pressing pressure and mould pressing time on the electrical conductivity and the flexural strength of composite are discussed. The electrical conductivity and the flexural strength of the composite bipolar plates with 60 wt.% graphite content, prepared with a mould pressing pressure of 5 MPa for 10 min, is >100 S cm⁻¹ and 20 MPa, respectively and can be improved by optimizing the mould pressing conditions, especially mould pressing time. The water content of the composite bipolar plate with different graphite contents was also investigated. The water content of the composite bipolar plate is about 6 wt.% with a graphite content of 60 wt.%. This composite bipolar plate contains capillary pores and has hydrophilicity, which is different from other composite bipolar plates. Therefore, it possesses an inner humidifying function and can use the water produced at the cathode for humidifying the proton exchange membrane during the operation of a PEMFC. In addition, the H₂ permeability of the composite bipolar plate is low.     

Preparation and properties of carbon nanotube-reinforced vinyl ester/nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

Novel multiwalled carbon nanotubes (MWNTs) were prepared using poly(oxypropylene)-backboned diamines of molecular weights M_w 400 and 2000 to disperse acid-treated MWNTs, improving the performance of composite bipolar plates in polymer electrolyte membrane fuel cells. A lightweight polymer composite bipolar plate that contained vinyl ester resin, graphite powder and MWNTs was fabricated using a bulk molding compound (BMC) process. Results demonstrate that the qualitative dispersion of MWNTs crucially determined the resultant bulk electrical conductivity, the mechanical properties and the physical properties of bipolar plates. The flexural strength of the composite bipolar plate with 1 phr of MWNTs was approximately 48% higher than that of the original composite bipolar plate. The coefficient of thermal expansion of the composite bipolar plate was reduced from 37.00 to 20.40 μm m⁻¹ °C⁻¹ by adding 1 phr of MWNTs, suggesting that the composite bipolar plate has excellent thermal stability. The porosity of the composite bipolar plate was also evaluated. Additionally, the bulk electrical conductivity of the composite bipolar plate with different MWNTs types and contents exceeds 100 S cm⁻¹. The results of the polarization curves confirm that the addition of MWNTs leads to a significant improvement on the single cell performance.     

Development of preform moulding technique using expanded graphite for proton exchange membrane fuel cell bipolar plates

A preform moulding technique using expanded graphite is developed to manufacture composite bipolar plates for proton exchange membrane fuel cells (PEMFCs). The preform is composed of expanded graphite, graphite flake and phenol resin. Preforms utilizing the tangled structure of expanded graphite are easily fabricated at a low pressure of 0.07–0.28 MPa. A pre-curing temperature (100 °C) slightly above the melting point of phenol powders (90 °C) induces moderate curing, but also prevents excessive curing. After the preform is placed in a steel mould, compression moulding is carried out at high pressure (10 MPa) and temperature (150 °C). The fabrication conditions are optimized by checking the electrical conductivity, flexural strength and microstructure of the composite. The optimized electrical conductivity and flexural strength, 250 S cm⁻¹ and 50 MPa, respectively, met the requirements for PEMFC bipolar plates.     

Efficient composite bipolar plate reinforced with carbon fiber and graphene for proton exchange membrane fuel cell

The composite bipolar plates are developed using natural graphite, carbon black, and carbon fiber, along with 1% graphene with phenol formaldehyde (resole) resin. The graphene is developed by thermo-chemical exfoliation of natural graphite and characterized by XRD, Raman, FESEM, and AFM analyses. The synthesized graphene is monolayer graphene with a minimum thickness of 1 Å. The bipolar plates are developed using compression molding technique and thoroughly characterized considering stringent benchmarks (US-DOE and Plug Power Inc.) for PEMFC viz., electrical conductivity, flexural strength, deflection at mid-point, and corrosion current density. The composite bipolar plate showed excellent corrosion resistance to the rigorous fuel cell environment. All the required properties are achieved by the developed composite bipolar plate for PEMFC application. The fuel cell is fabricated with the developed bipolar plate and the performance of the fuel cell is studied. The incorporation of graphene has improved the fuel cell performance significantly.     

Solvent-assisted graphite loading for highly conductive phenolic resin bipolar plates for proton exchange membrane fuel cells

A highly conductive polymer-based bipolar plate is fabricated using phenolic resin and graphite for proton exchange membrane fuel cells (PEMFCs). In order to load graphite fillers up to 90 wt% and minimize the void volume, the wetting properties of the graphite and phenolic resin are key factors for ensuring high electrical conductivity of the bipolar plates through good contact and uniform dispersion of graphite fillers. Since the surface free-energies of the phenolic resin and graphite are significantly different at 107.77 and 43.3 mJ m⁻², respectively, to give a high contact angle of 87.1°, methanol with 19.6 mJ m⁻² of surface energy is incorporated to decrease the contact angle between the matrix and graphite to 11.2°. By adjusting the surface energy of the matrix system, the conductivity of a composite containing 90 wt% of graphite reaches 379 S cm⁻¹. The air permeability of the composite containing 80 wt% of graphite is less than 5 × 10⁻⁶ cm³ cm⁻² s without open pores. The flexural modulus ranges from 6700 to 11000 MPa for graphite loads between 60 and 80 wt%, respectively.     

Coated 316L stainless steel with CrxN film as bipolar plate for PEMFC prepared by pulsed bias arc ion plating

Three different kinds of Cr_xN films on 316L stainless steels were prepared by pulsed bias arc ion plating as bipolar plates for proton exchange membrane fuel cell (PEMFC). The interfacial contact resistance, corrosion resistance and surface energy of the bipolar plate samples were investigated. Among the three samples, the 316L stainless steel coated with Cr_0.49N_0.51 → Cr_0.43N_0.57 gradient film (sample 2) exhibited the best-integrated performance. The contact resistance between sample 2 and Toray carbon paper was 6.9–10.0 mΩ cm² under 0.8–1.2 MPa. The bipolar plate sample also showed improved corrosion resistance in simulated PEMFC environments. Either in the reduction environment or in the oxidation environment 25 °C and 70 °C, the corrosion current densities of sample 2 were about one to two orders of magnitude lower than those of the base metal. In addition, the open circuit corrosion potential of sample 2 was also the highest in 0.5 M H₂SO₄ + 5 ppm F⁻ solution at 25 °C. The treated bipolar plate had high surface energy; and the contact angle of sample 2 with water was about 90°, which is beneficial for water management in fuel cell.     

Study on the mesocarbon microbeads/polyphenylene sulfide composite bipolar plates applied for proton exchange membrane fuel cells

Thermoplastic/graphite composite bipolar plates based on polyphenylene sulfide (PPS) and mesocarbon microbeads (MCMB) were prepared by compression molding at a pressure of 40 MPa and 400 °C. Electrical conductivity, bulk density, flexural strength, water and ethanol absorption were determined as function of PPS content. The influences of molding time, actived carbon and carbon fiber on the properties of the composite bipolar plates were investigated, the cross section of the composite plates were analyzed by scanning electron microscope (SEM). We found that the optimized PPS content is 20 wt% and the required molding time is 30 min. In particular, the composite plates containing 20 wt% PPS demonstrated in-plane conductivity as high as 133.7 S cm⁻¹, through-plane conductivity 21.37 S cm⁻¹, in addition to showing the value of density, flexural strength, water and ethanol absorption as 1.98 g cm⁻³, 38.82 MPa, 0.0409 and 0.352 g cm⁻³. The addition of actived carbon degraded all the performance of the bipolar plate, while addition of carbon fiber improved almost all the performance of bipolar plate except bulk density and through-plane conductivity. The performances of fuel cell with this composite bipolar plate were tested, no distinct variation occurred after the composite plates operating in fuel cell. These data indicates the chemical and mechanical stability of the composite plates and their potential application in fuel cell.     

High performance polyvinylidene fluoride/graphite/multi-walled carbon nanotubes composite bipolar plate for PEMFC with segregated conductive networks

Composite bipolar plates (BPs) are preferred to graphite BPs and metal BPs, in proton exchange membrane fuel cells (PEMFC), due to their pronounced advantages. However, facile and high-efficiency fabrication of high performance composite BPs, remains a challenge. In this study, high performance polyvinylidene fluoride (PVDF)/graphite/multi-walled carbon nanotubes (MWCNTs) composite BPs with segregated conductive network are prepared by structural design and compression molding. Due to the “brick-mud” structure formed in composite BPs by structural manipulation, its conductivity of low filler content is greatly improved. In addition, segregated synergistic conductive networks are observed in composite BPs after adding MWCNTs. The composite BP (5 wt% MWCNTs and 35 wt% graphite) exhibited electrical conductivity of 161.57 S/cm and area specific resistances of 7.5 mΩ cm². Moreover, the composite BPs have good flexural strength, excellent hydrophobicity and corrosion resistance. In summary, our work provides a simple and feasible strategy for manufacturing high performance composite BPs with low fillers.     

Ag–polytetrafluoroethylene composite coating on stainless steel as bipolar plate of proton exchange membrane fuel cell

Forming a coating on metals by surface treatment is a good way to get high performance bipolar plate of proton exchange membrane fuel cell (PEMFC). In our research, Ag–polytetrafluoroethylene (PTFE) composite film was electrodeposited with silver-gilt solution of nicotinic acid by a bi-pulse electroplating power supply on 316 L stainless steel bipolar plate of PEMFC. Surface topography, contact angle, interfacial conductivity and corrosion resistance of the bipolar plate samples were investigated. Results showed that the defects on the Ag–PTFE composite coating are greatly reduced compared with those on the pure Ag coating fabricated under the same condition; and the contact angle of the Ag–PTFE composite coating with water is 114°, which is much bigger than that of the pure Ag coating (73°). In addition, the interfacial contact resistance of the composite coating stays as low as the pure Ag coating; and the bipolar plate sample with composite coating shows a close corrosion resistance to the pure Ag coating sample in potentiodynamic and potentiostatic tests. Coated 316 L stainless steel plate with Ag–PTFE composite coating exhibits well hydrophobic characteristic, less defects, high interfacial conductivity and good corrosion resistance, which shows a great potential of the application in PEMFC.     

Preparation and properties of thin epoxy/compressed expanded graphite composite bipolar plates for proton exchange membrane fuel cells

Although the composite bipolar plates prepared by the method of the vacuum resin impregnation in compressed expanded graphite (CEG) sheets have been applied in the KW-class stacks, there have been few investigations of the preparation and properties of them so far. In this research, the influences of the microstructure on the physical properties of the thin epoxy/CEG composites (the thickness is 1 mm) are investigated for the first time and the optimum preparation conditions are obtained. Results demonstrated that the mechanical property and the impermeability of the composites increases evidently with the resin content changing from 4% to 30%, while the electrical properties keep nearly constant. It can be attributed to the continuous expanded graphite (EG) conductive network of the raw CEG sheet. The epoxy (30 wt.%)/CEG composite is shown to be the optimum composite, displaying in-plane conductivity of 119.8 S cm⁻¹, through-plane resistance of 17.13 mΩ cm², density of 1.95 g cm⁻³, gas permeability of 1.94 × 10⁻⁶ cm³ cm⁻² s⁻¹ and flexural strength of 45.8 MPa. The alcohol scrubbing is the optimum method of surface post-processing. The performance of a single cell with the optimum composite bipolar plates is tested and demonstrated to be outstanding. Above all, the composite prepared by resin vacuum impregnation in the CEG sheet is a promising candidate for bipolar plate materials in PEMFCs.     

Thermal and electrochemical durability of carbonaceous composites used as a bipolar plate of proton exchange membrane fuel cell

Thermal and electrochemical durability of carbonaceous composite plates, which are made from graphite powders and a resin for use as bipolar plates of PEMFC (proton exchange membrane fuel cell), were investigated. The thermal durability was investigated by TG (thermal gravimetry) coupled with DTA (differential thermal analysis) technique under air up to 600 °C. A weight loss was significant over 300 °C, but the hydrophobicity was decreased after heated at 80 °C for 192 h.The electrochemical durability was investigated in 10 μmol dm⁻³ of hydrochloric acid solution under nitrogen or oxygen atmosphere by means of potential holding test from 0.8 to 1.5 V against RHE (reversible hydrogen electrode) at 80 °C. During the potential holding tests, CO₂ production due to the corrosion was quantified by a GC (gas-chromatography) and the production was detectable above 1.3 V irrespective with atmosphere; on the other hand, it was clarified from the contact angle measurements that the hydrophobicity was changed below 1.3 V. The results of this study showed that the carbonaceous composite plates were electrochemically degraded under PEMFC condition and were seriously degraded in URFC (unitized regenerative fuel cell) condition.     

Effect of manufacturing conditions on the corrosion resistance behavior of metallic bipolar plates in proton exchange membrane fuel cells

Metallic bipolar plates are one of the promising alternatives to the graphite bipolar plates in proton exchange membrane fuel cell (PEMFC) systems. In this study, stainless steel (SS304, SS316L, and SS430), nickel (Ni 270), and titanium (Grade 2 Ti) plates with an initial thickness of 51 μm were experimented as bipolar plate substrate materials in corrosion resistance tests. In addition to unformed blanks, SS316L plates were formed with stamping and hydroforming processes to obtain bipolar plates under different process conditions (stamping force, hydroforming pressure, stamping speed, hydroforming pressure rate). These bipolar plates, then, were subjected to corrosion tests, and the results were presented and discussed in detail. Potentiodynamic polarizations were performed to observe corrosion resistance of metallic bipolar plates by simulating the anodic and cathodic environments in the PEMFC. In order to determine the statistical significance of the corrosion resistance differences between different manufacturing conditions, analysis of variance (ANOVA) technique was used on the corrosion current density (I_corr, μA cm⁻²) values obtained from experiments. ANOVA for the unformed substrate materials indicated that SS430 and Ni have less corrosion resistance than the other substrate materials tested. There was a significant difference between blank (unformed) and stamped SS316L plates only in the anodic environment. Although there was no noteworthy difference between unformed and hydroformed specimens for SS316L material, neither of these materials meet the Department of Energy‘s (DOE) target corrosion rate of ≤1 μA cm⁻² by 2015 without coating. Finally, stamping parameters (i.e. speed and force levels) and hydroforming parameters (i.e. the pressure and pressure rate) significantly affected the corrosion behavior of bipolar plates.     

Carbon film-coated 304 stainless steel as PEMFC bipolar plate

Carbon film-coated stainless steel (CFCSS) has been evaluated as a low-cost and small-volume substitute for graphite bipolar plate in polymer electrolyte membrane fuel cell (PEMFC). In the present work, AISI 304 stainless steel (304SS) plate was coated with nickel layer to catalyze carbon deposits at 680°C under C₂H₂/H₂ mixed gas atmosphere. Surface morphologies of carbon deposits exhibited strong dependence on the concentration of carbonaceous gas and a continuous carbon film with compact structure was obtained at 680 °C under C₂H₂/H₂ mixed gas ratio of 0.45. Systematic analyses indicated that the carbon film was composed of a highly ordered graphite layer and a surface layer with disarranged graphite structure. Both corrosion endurance tests and PEMFC operations showed that the carbon film revealed excellent chemical stability similar to high-purity graphite plate, which successfully protected 304SS substrate against the corrosive environment in PEMFC. We therefore predict CFCSS plates may practically replace commercial graphite plates in the application of PEMFC.     

Surface modification and performance of inexpensive Fe-based bipolar plates for proton exchange membrane fuel cells

A reforming pack chromization with rolling pretreatment process is utilized to develop inexpensive and high-performance Fe-based metal bipolar plates (SS 420, SS 430, and SS 316 stainless steels) for PEMFC systems. Rolling process is previously performed to reduce the chromizing temperature and generate a coating possessing excellent conductivity and corrosion resistance on the steels during chromization. The power efficiencies of rolled-chromized and simple chromized bipolar plates are compared with graphite bipolar plates employed in PEMFCs. The results show that the rolled-chromized bipolar plates have a corrosion current (I_corr) of 7.87 × 10⁻⁸ A cm⁻² and an interfacial contact resistance of 9.7 mΩ cm². Moreover, the power density of the single cell assembled with rolled-chromized bipolar plates is 0.46 W cm⁻², which is very close to that of graphite (0.50 W cm⁻²), in the tested conditions of this study.     

Preparation,electrical, mechanical and thermal properties of composite bipolar plate for a fuel cell

A novel composite bipolar plate for a polymer electrolyte fuel cell has been prepared by a bulk-moulding compound (BMC) process. The electrical resistance of the composite material decreases from 20 000 to 5.8 mΩ as the graphite content is increased from 60 to 80 wt.%. Meanwhile, the electrical resistance of composite increases from 6.5 to 25.2 mΩ as the graphite size is decreased from 1000 to 177 μm to less than 53 μm. The thermal decomposition of 5% weight loss of composite bipolar plate is higher than 250 °C. The oxygen permeability of the composite bipolar plate is 5.82×10⁻⁸ (cm³/cm² s) when the graphite content is 75 wt.%, and increases from 6.76×10⁻⁸ to 3.28×10⁻⁵ (cm³/cm² s) as the graphite size is longer or smaller than 75 wt.%. The flexibility of the plate decreases with increasing graphite content. The flexural strength of the plate decreases with decrease in graphite size from 31.25 MPa (1000–177 μm) to 15.96 MPa (53 μm). The flexural modulus decreases with decrease of graphite size from 6923 MPa (1000–177 μm) to 4585 MPa (53 μm). The corrosion currents for plates containing different graphite contents and graphite sizes are all less than 10⁻⁷ A cm⁻². The composite bipolar plates with different graphite contents and graphite sizes meet UL-94V-0 tests, and the limiting oxygen contents are higher than 50. Testing show that composite bipolar plates with optimum composition are very similar to that of the graphite bipolar plate.     

Preparation and properties on the graphite/polypropylene composite bipolar plates with a 304 stainless steel by compression molding for PEM fuel cell

Graphite/polymer composites have high corrosion resistance, low contact resistance and low fabrication cost but low cell efficiency and mechanical strength. This study examined the electrical and mechanical properties of graphite/polypropylene composite bipolar plates. Carbon nanotubes (CNTs) were used to improve the electrical properties of the graphite/PP composites. Although the electrical properties increased when excess conducting filler was added to the composite, the mechanical strength decreased significantly. 304 stainless steel (304 SS) plates with different thicknesses were used as the support material of a graphite/PP composite bipolar plate. The 304 SS-supported graphite/PP composite bipolar plate had an optimum CNTs/graphite/PP composite composition of 1.2, 83 and 17 wt.%, respectively. The flexural strength of the 304 SS-supported graphite/PP composites increased from 35 to 58 MPa with increasing 304 SS thickness from 0.5 to 1 mm. The power density of the graphite bipolar plate and 304 SS-supported graphite/PP composite bipolar plate were 968 and 877 mW cm⁻², respectively. The 304 SS complemented the mechanical strength of the graphite/PP composite bipolar plate as well as the cell efficiency.     

Corrosion protection of 304 stainless steel bipolar plates using TiC films produced by high-energy micro-arc alloying process

Metallic bipolar plates look promising for the replacement of graphite due to higher mechanical strength, better durability to shocks and vibration, no gas permeability, acceptable material cost and superior applicability to mass production. However, the corrosion and passivation of metals in environments of proton exchange membrane fuel cell (PEMFC) cause considerable power degradation. Great attempts were conducted to improve the corrosion resistance of metals while keeping low contact resistance. In this paper, a simple, novel and cost-effective high-energy micro-arc alloying process was employed to prepare compact titanium carbide as coatings for the type 304 stainless steel bipolar plates with a metallurgical bonding between the coating and substrate. It was found that TiC coating increased the corrosion potential of the bare steel in 1 M H₂SO₄ solution at room temperature by more than 200 mV, and decreased significantly its corrosion current density from 8.3 μA cm⁻² for the bare steel to 0.034 μA cm⁻² for the TiC-coated steel. No obvious degradation was observed for the TiC coatings after 30-day exposure in solution.     

Expanded graphite-based electrically conductive composites as bipolar plate for PEM fuel cell

In this study, expanded graphite-based composite bipolar plates are developed from expanded graphite (EG), which is synthesized by chemical intercalation of natural graphite and rapid expansion at high temperature. The expanded graphite synthesized in this study has an expansion ratio between 75–100 cc/gm. The composite bipolar plate with varying weight percentage of EG gives different bulk density, electrical conductivity, mechanical properties and air tightness. The critical weight percentage of filler content is 50 to achieve the desired electrical conductivity and mechanical properties of bipolar plate as per U.S. DOE targets. The composite bipolar plate with 50 wt% of EG gives bulk density of 1.50 g/cm³, electrical conductivity >120 S/cm, bending strength 54 MPa, modulus 6 GPa and shore hardness 50. I–V characteristic of a cell assembly with EG-based composite plates are similar with the performance of a cell with commercial composite plates. These lightweight bipolar plates reduced the volume and weight of ultimate fuel cell stack and helped in improving the fuel cell performance.     

Preparation and properties of carbon nanotube/polypropylene nanocomposite bipolar plates for polymer electrolyte membrane fuel cells

This study aims at the fabrication of lightweight and high performance nanocomposite bipolar plates for the application in polymer electrode membrane fuel cells (PEMFCs). The thin nanocomposite bipolar plates (the thickness <1.2 mm) consisting of multiwalled carbon nanotubes (MWCNTs), graphite powder and PP were fabricated by means of compression molding. Three types of polypropylene (PP) with different crystallinities including high crystallinity PP (HC-PP), medium crystallinity PP (MC-PP), low crystallinity PP (LC-PP) were prepared to investigate the influence of crystallinity on the dispersion of MWCNTs in PP matrix. The optimum composition of original composite bipolar plates was determined at 80 wt.% graphite content and 20 wt.% PP content based on the measurements of electrical and mechanical properties with various graphite contents. Results also indicate that MWCNTs was dispersed better in LC-PP than other PP owing to enough dispersed regions in nanocomposite bipolar plates. This good MWCNT dispersion of LC-PP would cause better bulk electrical conductivity, mechanical properties and thermal stability of MWCNTs/PP nanocomposite bipolar plates. In the MWCNTs/LC-PP system, the bulk electrical conductivities with various MWCNT contents all exceed 100 S cm⁻¹. The flexural strength of the MWCNTs/LC-PP nanocomposite bipolar plate with 8 phr of MWCNTs was approximately 37% higher than that of the original nanocomposite bipolar plate and the unnotched Izod impact strength of MWCNTs/LC-PP nanocomposite bipolar plates was also increased from 68.32 J m⁻¹ (0 phr) to 81.40 J m⁻¹ (8 phr), increasing 19%. In addition, the coefficient of thermal expansion of MWCNTs/LC-PP nanocomposite bipolar plate was decreased from 32.91 μm m⁻¹ °C⁻¹ (0 phr) to 25.79 μm m⁻¹ °C⁻¹ (8 phr) with the increasing of MWCNT content. The polarization curve of MWCNTs/LC-PP nanocomposite bipolar plate compared with graphite bipolar plate was also evaluated. These results confirm that the addition of MWCNTs in LC-PP leads to a significant improvement on the cell performance of the nanocomposite bipolar plate.