Alternative Energy: Direct Methanol Fuel Cell In Focus

U.A. Hasran, S.K. Kamarudin, W.R.W. Daud, B.Y. Majlis, A.B. Mohamad
Universiti Kebangsaan Malaysia Malaysia cghu@eng.ukm.my

Abstract The Direct Methanol Fuel Cell (DMFC) is a threephase electrochemical reactor that can generate electrical energy based on the electrochemical oxidation of methanol and reduction of oxygen in an environmentally friendly and low temperature process of <100C. It started as a military-funded research due to immediate necessity and grows into a commercial product ideally as consumer goods in the portable market such as mobile phones, digital cameras or laptops. Various laws, codes and standards and regulations have been introduced that will have an impact on the future prospects of DMFC systems. This becomes a booster factor for DMFC and its growth in the global market is predicted to be at an increase in terms of future sales and revenue. Index Terms Fuel cell, DMFC, energy, global market.

oxygen in an environmentally friendly, low temperature process.

I. INTRODUCTION TO FUEL CELL Malaysias final energy consumption is projected to grow at an annual rate of 4.9% from 2000 to 2030. From the base year of 2000, Malaysia would require triple the amount of energy reaching up to 128 Mtoe in year 2030, as shown in Fig. 1. However, the energy requirement would still rely heavily on fossil fuels. It is therefore prudent and timely to embark now on renewable sources of energy for energy security, reliability and ecological preservation [1]. Hydrogen has been identified as one of the most viable and long term renewable alternatives to fossil fuel. The Ministry of Science, Technology and Innovation (MOSTI) in Malaysia has identified hydrogen and fuel cells as priority research with fund allocation from 2002 to 2007 of up to RM7 million (USD 2 million) for the development of hydrogen production and storage technologies and RM34 million (USD 9.7 million) for the national fuel cell research and development from 1996 to 2007. This is because the applications of fuel cells are viewed to be one of the more important energy conversion devices in the future [2]. The Proton Exchange Membrane Fuel Cell (PEMFC) technology that uses hydrogen as fuel can be adapted for the Direct Methanol Fuel Cell application in portable devices. It is a solid polymer electrolyte-based technology that typically operates at relatively low temperatures (<100C) with methanol as its vapor or liquid fuel [3]. It also acts as a three-phase electrochemical reactor involving simultaneous mass, charge and energy transfer and can generate electrical energy based on the electrochemical oxidation of methanol and reduction of
Fig. 1. Malaysias final energy consumption (ktoe) [1]

II. CHRONOLOGICAL PROGRESS OF DMFC In 1801, Humphry Davy demonstrated the principle of what were to become fuel cells and this was followed by the pioneering work of scientist Christian Friedrich Schnbein in 1838. Another German physical chemist, Friedrich Wilhelm Ostwald, also provided much of the theoretical understanding on fuel cell operation and he experimentally determined the interconnecting roles of the various components of the fuel. Sir William Robert Grove, a chemist, physicist and lawyer, is generally credited with inventing the fuel cell in 1839 but his invention did not produce enough electricity to be useful. Around 1889, William White Jaques coined the term 'fuel cell' and decades forward in time, a Russian scientist named Oganes Davtyan made a fuel cell in 1947 that oxidized CO with oxygen from air at 700C and could operate for days. Willard Thomas Grubb and Leonard Niedrach at General Electric succeeded in developing solid ion-exchange hydrogen fuel cells in 1955 and this was later used by NASA in the Gemini spacecraft. Afterwards, they invented the polymer electrolyte membrane and the term solid polymer electrolyte fuel cells were subsequently changed to proton exchange membrane fuel cells. In the 1960s, General Electric produced the fuel cell-based electrical power system for NASA's Gemini and

Apollo space capsules while Walther Grot at DuPont discovered a better polymer electrolyte material in the form of sulfonated tetrafluorethylene copolymer, also called Nafion. This inevitably led to the usage of the first fuel cell prototype in the NASA Space Fuel Cells for the moon expedition in 1968. The oil crisis in the 1970s pushed the development of alternative energy technologies onward. Several German, Japanese and US vehicle manufacturers and their partners began to experiment with FCEV. In 1989, Perry Energy Systems, which is a division of Perry Technologies, worked with Ballard to demonstrate that it is possible to power a submarine with a PEMFC. The very next year, the California Air Resources Board (CARB) made a move to introduce the Zero Emission Vehicle (ZEV) Mandate, which is the first vehicle emissions standard in the world, and predicated on the use of alternative powertrains instead of on the improvement of the internal combustion engine (ICE). Ballard Power Systems once again came through and demonstrated their fuel cellpowered buses, while Energy Partners, which is the successor of Perry Energy Systems, demonstrated the first passenger car running on PEMFC in 1993. By mid-2000s, tens of fuel cell buses were deployed as part of the HyFleet/CUTE project in Europe, China and Australia and in 2007, fuel cells started to be sold commercially as APU and for stationary backup power to end-users with written warranties and service capability to meet the codes and standards of the markets in which they were sold. Up to 2010, total shipments of fuel cells grew by 40%, reaching a new high of almost 230,000 units. Portable fuel cells accounted for 95% of this total and over 97% of fuel cells sold worldwide used PEMFC technology [4][7]. Dr. Lawrence H. DuBois of the U.S. Department of Defense and the Defense Advanced Research Projects Agency (DARPA) envisioned the development of a fuel cell that could operate on various types of liquid hydrocarbons (such as methanol and ethanol) for energy-efficient, non-polluting military and consumer applications. This led to a DARPAfunded collaboration from 1989 to 1998 with Dr. Surya Prakash, a world-renowned super acid specialist, and Dr. George A. Olah, a Nobel laureate from the Loker Hydrocarbon Institute, University of Southern California (USC). Further collaborative effort by USC with S. Surampudi, S. R. Narayanan, E. Vamos, H. Frank, and G. Halpert at California Institute of Technology (Caltech)-Jet Propulsion Laboratory (JPL) were carried out to invent the direct oxidation of liquid hydrocarbons subsequently coined as 'DMFC', which refers to the Direct Methanol Fuel Cell Technology. Additional contributions to the developments were made by Q. Wang, M. Smart and A. Atti at USC, and by A. Kindler and T. Valdez at JPL. The DMFC-related patents on their inventions were first filed in 1997 [8][10]. A survey conducted specifically on DMFC patents that are available in the Freepatentsonline (FPO) site up to 2011 shows the trend in Fig. 2 [11]. After the invention of DMFC, the progress was relatively slow during the first 5 years. This took a turn during the 2003 invasion of Iraq, as the military ran out of batteries. Even though supply managers took batteries out of every other location worldwide and battery companies worked

around the clock, they still could not produce the quantities required. Three days of batteries were on hand when the war ended and the military had to build a micro fuel cell substitute for batteries [12]. The DMFC research was further boosted by the discovery of new types of membranes and catalysts. This raised the research profile and a peak in patent publication is observed in 2006. However, the profile shows a decline from there on and the pattern has not picked up in 2011. This dip in trend is probably a part of the global decline of patent filing due to the 2008 doldrums experienced by world economies. Historically, patent filing suffers during periods of economic difficulty due to the fewer resources available for investment in the innovation cycle. The patenting activity is expected to recover once the economic cycle improves [13][14].

Fig. 2. Published DMFC patents from the US, European, Japan, German and World Intellectual Property Organization.

III. PROSPECT OF DMFC IN THE GLOBAL MARKET Fuel cell technology is still being refined. In many applications, applied research and technology development remains a vitally important part of the industry. There are three main markets for fuel cell technology: stationary power, transportation power, and portable power. Stationary power applications includes any application in which the fuel cells are operated at a fixed location, either for primary or for backup power, or for combined heat and power (CHP). Transportation power applications include motive power for cars, buses and other fuel cell vehicles (FCV) and auxiliary power units (APUs) for highway and off-road vehicles, as well as specialty vehicles (e.g. forklifts). Portable power applications include the use of fuel cells not permanently installed or fuel cells installed in a portable device. The term portable used here is the market segment that includes units clearly intended to be moveable and not used for powering a vehicle or moving contraption. Some product group examples are [15][17]: Consumer electronics, chargers and generators for portable market [0.5-2 kW] Residential units for stationary market [0.5-5kW] Light duty vehicles, specialty vehicles and APU for transportation market [1500kW] Distributed generation (DG) or central power plants [5kW-10 MW]

DMFC research and development is about 3-4 years behind that for other fuel cell types. The current DMFCs are limited in the power they can produce but they can store a high energy content in a small space. This enables them to produce a small amount of power over a long period of time and makes them ideal for consumer goods in the portable market such as mobile phones, digital cameras or laptops [18]. Figure 3 shows that DMFC has a fairly good ascending trend for their megawatt (MW) contribution, in keeping with the increase in market demand as time goes on. DMFC is the second most significant type after PEMFC by unit shipments and is mainly found in the portable sector, apart from some niche transport applications [19]. Figure 4 shows that since 2003, there has been a significant year-on-year increase in the number of units installed.

Fig. 3. Shipments and MW by DMFC up to 2010

Fig. 4. Total Number of DMFC Units Installed Globally by Application [20].

There are a number of reasons behind such growth trends, namely: Decreasing barriers to adoption, specifically cost, has enabled the increased production of DMFC units. Companies are working hard to ensure the technology meets customer requirements rather than consumers having to meet the technology requirements. This is of particular importance when working in the consumer portable electronics sector. The industry is operating in a period where a number of complimentary drivers have come together to

create a space in which technology such as DMFC meets both the needs of the adopter now and in the medium term future. Currently there are three main sectors involved in the DMFC industry: commercial, academic and suppliers for components or materials. An overwhelming majority of the sampled fuel cell companies in the DMFC industry describe themselves as being commercial entities despite the fact that major activities in the DMFC sector are either classed as being R&D-based or as manufacturing activity. The suppliers provide the components and materials for commercial purposes or for R&D projects. In Europe, for example, over 100 companies indicated that they are working with fuel cellrelated materials, components and products now or in the near future. Small and medium size companies were predominant and almost half of all the studied companies focused exclusively on fuel cells. However, even though these factors indicate that portable DMFC markets are moving away from the R&D phase and towards a period of commercialization, the fact that commercial and academic business types compose the majority of the sampled DMFC sector would suggest that whilst the industry believes it is operating in a commercial market, there is still a great deal of ongoing R&D activity to produce the next generation products [20]. Critical milestones have been achieved due to the collaborative effort of various institutions including the Methanol Institute, a broad coalition of methanol fuel cell technology, the fuel cell industry, the International Civil Aviation Organization (ICAO) and the U.S. Department of Transportation (DOT). In 2007, the ICAO drafted conditions that allows the transportation and use of fuel cells and fuel cell cartridges using butane, formic acid, direct methanol and reformed methanol fuels on board passenger airlines. The U.S. DOT Pipeline and Hazardous Materials Safety Administration agency published their final rule in 2008 that allows fuel cartridges for fuel cell devices and fuel cell systems, which include methanol, formic acid, butane and specific borohydride formulations, to be transported on board passenger aircraft in carry-on baggage and used in flight [21]. The introduction of various other laws, codes, standards and regulations have an impact on the future prospects of DMFC systems and becomes a booster factor to the global market for DMFC. Its sales are expected to increase to 92,000 in 2016 at a CAGR of about 45.3% for the same period, which is an increase from the 14,200 units shipping it achieved in 2011. 38% of this market is expected to be led by Asia, followed by North America (35%) and Europe (27%) in terms of the delivery of units, while the DMFC revenue is expected to increase from USD 17.5 million in 2010 to USD 109 million [22]. IV. CONCLUSION Fuel cell is one of the more important energy conversion devices and therefore is an alternative source of energy as Malaysia has an increasing trend in its energy consumption that still relies heavily on fossil fuels. The DMFCs are a type of fuel cell that can be operated at low temperature and is capable of storing high energy content in a small space, which makes

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