Chapter 3 – Batteries and Fuel Cells

Batteries and Fuel Cells
“You can start me up” -The Rolling Stones

3.1 Introduction

Unlike the previous two chapters where the alternative energy sources solar and nuclear were discussed, the topic of batteries and fuel cells does not meet the criterion of “alternative”. A battery can only be used for so long before it has to be recharged and the energy for recharging must come from somewhere. Similarly the “fuel” in a fuel cell is obtained through the consumption of energy. Nevertheless, batteries/fuel cells do play a very significant role in the fight against global climate change, particularly in the area of transportation. A nuclear powered automobile is a far fetched idea, a solar powered car is less so, but still is a long way from commercialization. Therefore, if alternative energy sources become viable and economically competitive with fossil fuels, we still have the problem of gasoline consumption in cars. A high energy density battery design can solve, or at least help alleviate, the thorny issue of CO2 emissions from vehicles, provided of course the energy for recharging the automotive battery is derived from alternative energy sources.

Although most everyone on the planet knows what a battery is, it is useful to define some terms before discussing in more detail the physics behind the operation of a battery. A battery is a device which converts energy from a chemical reaction into electrical energy. The battery consists of several electrochemical cells, connected in series to produce a desired output voltage. A so-called primary battery is not easily recharged and is intended for a single use. A secondary battery is equivalent to a rechargeable battery. Note, a battery in use is being discharged, whereas charging refers to the application of a current in the reverse direction to the battery to restore it to its original state. A reserve


Chapter 3 – Batteries and Fuel Cells battery is one in which the electrolyte (typically) is isolated from the rest of the battery prior to use. A fuel cell is an electrochemical cell that does not use consumable electrodes, but instead feeds fuel continuously into the anode and cathode sides.

3.2 The electrochemical cell

As mentioned above, a battery consists of several electrochemical cells, also called galvanic cells, which are hooked together in series in order to increase the total power. Therefore to understand how a battery operates it is sufficient to consider just the electrochemical cell. Much like a solar cell, a battery supplies electrons to drive some external load. However in the case of a galvanic cell the electrons are produced by a chemical reaction. From thermodynamics we know that the work done by the electrochemical cell comes at a cost, which in turn implies that the chemical reactions taking place within the cell must lead to a decrease in free energy. In fact for a reversible process at constant temperature and pressure the maximum work done by the system, W, is equal the free energy change − ∆G . The work performed when transporting an electric charge e with units of coulombs through a potential difference E in volts is simply the product of eE. Now let’s switch to a per mole basis. The total charge carried by one mole of positively charged ions of valency +1 is 96,487 coulombs and this number, denoted by F, is known as Faraday’s constant. Thus, the work produced by the electrochemical cell is:
W = − ∆G = nFE


where n is the valency of the ions produced in the chemical reaction (more on this below). The electric potential difference across the cell electrodes, E, is also known as the electromotive force, or EMF, of the cell. Equation 3.1 tells us how much “juice” we


Chapter 3 – Batteries and Fuel Cells can get from a battery. Clearly to get the most bang for the buck we would like to find reactions with the highest driving force − ∆G . The electrochemical cell consists of three main components: the anode, the cathode and the electrolyte. To understand the role of each it is best to refer to a specific example and, following the lead of D. R. Gaskell in his text “Introduction to Metallurgical Thermodynamics”, let us investigate the so-called Daniell cell. The anode of the Daniell cell is an electrode of pure Zn immersed in a compartment containing an aqueous solution of ZnSO4. The chemical reaction that takes place when Zn is introduced into solution is known as a half cell reaction and is written as: Zn=Zn2+(in aq.soln.)+2eHere the reaction is written such that reading from left to right corresponds to the favorable direction, ie. the free energy decreases when dissolving a Zn2+ ion. Zn is referred to as the anode because the reaction taking place there is an oxidation reaction, meaning the Zn loses electrons. Notice the valency of the reaction is n=2 and the two electrons produced flow through the Zn electrode and into the external circuit.

The cathode in a Daniell cell is also a pure metal electrode, in this case Cu. It too is immersed in an aqueous solution, but now containing CuSO4. The half cell reaction is: Cu2+(aq. Soln.) + 2e- = Cu

which is a reduction reaction since the Cu is gaining electrons. The cathode then refers to the electrode where reduction takes place.


Ions diffuse from side of the cell to the other across a porous separator.jpg The electrochemical cell is now complete. The electrolyte in the process is the medium through which ionic conduction is occurring. Electrons produced at the anode flow through our device and arrive at the Cu cathode.1 Schematic depiction of the Daniell cell. In the meantime positively charged ions are moving in the opposite direction. Figure from http://www.Chapter 3 – Batteries and Fuel Cells Fig. In the case of the Daniell cell the 4 . Electrons flow from the pure Zn anode to the Cu cathode. 3. At the same time Zn 2+ ions are dissolved from the anode and Cu 2+ is plated is plated onto the Zn2+ diffuses away from the Zn electrode into solution and Cu ions are plated onto the Cu electrode.chem-is-try.

ions are allowed to dissolve in the water. but there are other possibilities such as the polymer membranes and the solid oxide materials. How many volts does the Daniell cell produce or equivalently what is the cell EMF? Equation 3. but for most cells the electrolyte is one the same as the reaction: Zn(s) ⇔ ZnSO4(s) where the s notation emphasizes the fact that the free energy change can be computed based on the reaction in the solid state.1 tells us how to proceed. The half cell reaction of Zn=Zn2+ (in standard state)+2e. but what about the electrolyte? Consider the following procedure. Then take the saturated aqueous solution and use it as the electrolyte (more specifically the anolyte) in the cell. from a free energy change point of view. From this qualitative discussion of the electrochemical cell it is clear that two important features are required for an effective electrolyte. The dissolution process will continue until the water is saturated with ions or equivalently when the chemical potential of the ions is equal to the chemical potential of the ZnSO4 solid. yet a poor electrical conductor. The construction just described results in a standard state. Aqueous solutions are a popular choice for electrolytes.Chapter 3 – Batteries and Fuel Cells electrolyte consists of two separate compartments containing an anolyte (ZnSO4) and a catholyte (CuSO4). By similar reasoning the cathode half cell reaction can be written as CuSO4(s)=Cu(s). Both the cathode and the anode consist of pure metals and thus Zn and Cu occur in their standard states. Clearly we need the free energy of the total cell reaction and to determine this free energy change we must first find the free energy when all the species involved are in their standard states at the standard temperature of 298K. In any electrochemical cell the total reaction is found by simply adding the two half cell reaction. It must be a good ionic conductor. that is: Zn(s)+CuSO4(s)=ZnSO4(s)+Cu(s) 5 . Water is placed in contact with pure ZnSO4 and Zn2+ ions and SO42.

104 Volts From the above discussion it should be clear that the cell EMF will be different if the concentration of ions in the electrolyte is something other than the standard saturated values.040 Joules and. Eventually the cell will need to be recharged. the standard EMF for the cell is: E o =1.2 where a ZnSO4 and a CuSO4 are the activities of ZnSO4 and CuSO4 respectively in the two electrolyte compartments. The Nernst equation provides the necessary correction. For the specific case of the Daniell cell. Zn will then precipitate on the anode and Cu will dissolve from the cathode. At the anode Zn ions increase in concentration and at the cathode Cu ions are depleted. Equation 3. Imagine for example if instead of pure Cu and pure Zn electrodes.2 refers specifically to the Daniell cell. makes sense from a thermodynamic point of view. From the Nernst equation it is clear that the cell EMF decreases over time. The imbalance leads to a flow of Zn from anode to cathode across the porous medium and a reverse flow of sulfate ions. but it can be generalized quite easily. The decrease of SO4 and Cu in the catholyte means the activity a will decrease and by similar reasoning the activity term will increase. it is given by: E = Eo − RT  a ZnSO4 ln 2 F  a CuSO4      3. The recharging process involves applying a reverse voltage of sufficient strength – greater than E o – such that the cell reaction moves in the opposite direction. When the two electrodes are introduced into the electrolyte the battery begins to discharge. which. alloys containing Zn 6 . from Eq. of course.Chapter 3 – Batteries and Fuel Cells The standard free energy change for the above reaction is ∆G o =-213. 3.1.

7 .2 which plots the cell EMF vs the current. From Ohm’s law the IR loss contribution increases linearly with the operating current. As we saw in the case of solar cells there are processes that will rob the system of available voltage and decrease the efficiency.3 The Daniell cell is capable of supplying 1. we’re up to 6. There are three main sources of voltage loss. is the internal resistance of the cell and it includes resistance from flow through the two electrodes. through the electrolyte and any resistance associated with interfaces between phases. If we wire up 6 such cells in series. Some of these processes are illustrated in Fig.1 Volts.Chapter 3 – Batteries and Fuel Cells and Cu were utilized. The first. Then the activities of these reacting species are no longer unity and the Nernst equation must be rewritten as: For any cell reaction given by: aA + bB = cC + dD the cell EMF is E = Eo − c d RT  a C a D ln a b nF  a A a B      3. But can we realistically expect to generate the theoretical cell EMF? The answer of course is no.6 Volts. 3. labeled IR.

nickel-metal hydride batteries. Although there is a free energy gain during this process there is also. activation overpotential and concentration overpotential. 3. The η a term reflects the decrease in cell voltage due to the activation overpotential that must be supplied. Our interest here is to discuss 8 . The curve labeled activation polarization is a little trickier to understand.4 where a and b are constants and b is known as the Tafel slope. The concentration overpotential reflects this diffusion mechanism. Thus there is an overpotential associated with the half reactions at both the cathode and anode. silver oxide batteries. 3. which is slow.Chapter 3 – Batteries and Fuel Cells Fig. in general. At low currents positive ions are produced at the anode (Zn2+ in the Daniell cell) and transported through the electrolyte at rates such that the concentration is more or less uniform. etc. The third factor that decreases the voltage of an electrochemical cell is the concentration polarization. We have seen above that the electrons flowing in one direction from the battery is compensated by a net flow of ions within the electrolyte. such as: Nickel-cadmium batteries. But as the current increases there is a build up of ions at the electrode and now the ionic conduction will contain a contribution.3 The lead acid battery The Daniell cell can deliver around 1 Volt – we can do better. nickel-zinc batteries. from diffusion in the aqueous solution. Consider once again the Daniell cell. At the cathode Cu ions from solution will precipitate on the pure Cu electrode. The mathematical relationship between η a and the current is known as the Tafel equation and is given by: η a = a + b ln(i ) 3.2 The voltage delivered by a cell is reduced by IR losses. an activation barrier for the atomic process. Indeed there are many superior batteries available.

can be used to power automobiles. The most popular battery is the one that starts your car every morning. The half cell reaction at the anode is Pb=Pb 2+ + 2e- and is combined with the Pb ion reaction with the electrolyte: Pb 2+ + SO4 2. Fig 3. grooves are machined into the lead to greater increase the effective surface area. In order to understand the materials requirements for electric vehicle applications it is perhaps best to start by describing the most popular battery type and ask if it is up to the task. Examples of lead acid battery grid anode grid designs. as shown in Fig.3. eventually.3. Conventional (left) and radial (right). 3.Chapter 3 – Batteries and Fuel Cells battery materials and designs that. where the grid material provides mechanical support. the lead acid battery. the pure Pb is typically alloyed with 4-6 weight percent Antimony to increase the strength via solid solution strengthening. It should come as no surprise that the anode in a lead acid battery is lead. In addition. Pure lead is a very soft material and therefore the anode usually consists of Pb plated on a grid. In order to increase the number of electrons produced per unit area of anode grid.= PbSO4 9 .

85-2. In each case the oxide is not stoichiometric and a more accurate description of the structure would be PbOx with x varying from approximately 1.047 Volts. Although two crystalline oxides are present in the cathode. Lead oxide PbO2 is the cathode material in a lead acid battery. The half cell reaction at the cathode can be written as: PbO2 +4H+ + 2e.01V.= PbSO4 The overall cell reaction then is: Pb + PbO2 + 2H2SO4 = 2PbSO4 + 2H2O The Nernst equation applied to the lead acid batteries reads: E = 2. The standard cell EMF for the lead acid design is 2. is sulfuric acid H2SO4 at a concentration of roughly 6molar (37% by weight).047 − RT  a H 2O ln F  a H 2 SO4      Notice. during discharge the battery produces water and depletes the amount of sulfuric acid. the difference in half cell potential for each phase amounts to just . the source of sulfate ions. The cathode is fabricated in the form of a highly porous structure to increase the active surface area. Two crystalline forms of the oxide are present: a rhombohedral phase denoted alpha-PbO2 and a tetragonal (rutile) form designated as the beta phase. 10 .= Pb2+ + 2H2O Pb2+ + SO4 2.05.Chapter 3 – Batteries and Fuel Cells In the lead acid battery the electrolyte. which is a factor of two larger than the Daniell cell.

The sulfuric acid electrolyte. In most other industrial applications the trend in recent years has been toward lead free materials.4 plots the energy density and specific energy for various battery types. but more important is the use of lead itself. Currently lead acid batteries power small vehicles such as golf carts and fork lifts. Lead acid batteries were discovered in 1860 and the nearly 150 year head start in research and development over modern battery designs has resulted in batteries that are low cost. With respect to materials selection there are two ways to increase the specific energy of battery: materials leading to higher cell EMF can be chosen and lighter materials can be used. very reliable. low maintenance and available in a variety of designs and sizes. As we will see below. Pb is a toxic heavy metal and even in very small concentrations can cause health concerns in children. requires care when handling. 11 . of course. To scale up from a golf cart to a conventional road vehicle will require a substantial number of lead acid cells in series and therefore a large increase in weight. lead acid batteries are an environmental nightmare. Figure 3. The information is plotted as boxes to illustrate the variation in performance under different operating conditions.Chapter 3 – Batteries and Fuel Cells The large open circuit voltage is one of the main advantages of the lead acid battery.hours/liter. in both instances. The battery industry has instead relied on recycling. the remaining discarded batteries is cause for concern. But it is doubtful the lead acid design will be the battery of choice for automobiles in the future and the main reason is known to anybody who has actually installed a car battery – they are heavy. It is clear that significant weight and space savings can be realized by moving away from the traditional lead acid battery. >95%. but there are others. there is no better choice than Li. A closely related quantity is the energy density Watts. A factor of roughly two in performance can be gained by utilizing batteries of the Zn/MnO2 design and a factor of almost four can be achieved with batteries based on lithium. On the negative side. Although recycling rates are quite high. such as lead free solders in electronics packaging. An important figure of merit for a battery is the specific energy given in units of Watts.hours/kg.

3. The energy density and specific energy for various battery materials. Since we add and subtract reactions it is valid to reference all oxidation reactions to some standard reaction and the standard reaction in most common use is: H2 = 2H+ + 2e- 12 .Chapter 3 – Batteries and Fuel Cells Fig. Notice battery designs involving Li offer the best performance in terms of weight and space savings.4 Li ion batteries As illustrated above.4. in order to find the cell EMF we can add the free energy of the oxidation half reaction at the anode and then subtract the oxidation reaction at the cathode (or add the reduction reaction). 3.

. and hence the battery power. In order to maximize the cell EMF.Chapter 3 – Batteries and Fuel Cells Table I below lists several half cell reactions with their corresponding EMF with the standard reaction involving hydrogen appearing in the middle and assigned an EMF of zero.045 when oxidizing to Li ++e. And look what element is found at the very top. 13 . Not only does Lithium produce a large voltage of 3. anode materials near the top of the list should be combined with cathode materials near the bottom. but Li is the third lightest element in the universe! Given these two properties of Li it is not surprising that Li based battery designs are the most promising in terms of specific energy.

and in each layer the carbon atoms form very strong 2sp2 hybrid bonds with three neighboring atoms. The use of polymer films.Chapter 3 – Batteries and Fuel Cells Lithium has the electronic structure 1S22S1. For example in Lithium/Manganese Disulfide (Li/MoS2) batteries the electrolyte is LiAsF6 salt dissolved in a 50:50 mixture of propylene carbonate and ethylene carbonate. diethyl carbonate and ethylmethyl carbonate. but the extreme reactivity of Li also makes it difficult to work with. Other choices for organic electrolyte solutions are equally unpronounceable: dioxolane. Consider the crystal structure of graphite as shown in Fig. The structure is a hexagonal ABAB stacking of sheets. 14 .5. for rechargeable high power applications. Pure Li metal is so violently reactive with air that it must be stored in oil. as the electrolyte material has thus far not resulted in any improvement in conductivity. The major drawback of organic electrolytes is the fact that the ionic conductivity is roughly two orders of magnitude lower than typical aqueous solutions and the low conductivity severely limits the current (or rate of discharge). 3. battery designs based on Li metal do not look promising. Although disposable Li batteries are in common use in consumer electronics. It is this property which places Li at the top of the chart in table I. one layer is often referred to as graphene. In the Lithium/Titanium Disulfide (Li/TiS2) design the electrolyte is again LiAsF6 but now dissolved in 2-methyl tetrahydrofuran and tetrahydrofuran. A critical materials feature of the Li ion battery is the use of so-called intercalation compounds for the electrodes. Bond angles are 120o within the layers. Graphite is used as pencil “lead” because it is easy to shear and fracture the material along the basal planes. rather than liquids. The lone electron occupying the 2S state means that Li really wants to lose an electron. There is a possible solution however and it is the Li ion battery. The extreme reactivity of Li severely limits the choice of electrolyte materials or non-aqueous solutions in rechargeable batteries. The distance between successive layers of grapheme sheets is fairly large and the interaction between layers is characterized by weak van der Waals attraction. such as electric vehicles.

The hexagonal crystal structure of graphite. are observed. In a particular layer Li can be inserted until the point where there are six carbon atoms for every Li and the compound is denoted LiC6. But the behavior of Li in an individual layer does not tell the whole story. Since the bonding between AB layers in graphite is so weak it is fairly easy. or stages. K and of interest here of course Li. 15 . As the concentration of 1/6 Li is reached the stacking sequence of the top and bottom graphene sheets changes to AA. but each Li atom has no neighbor within any of the adjacent six hexagons. 3. Rather than a smooth curve between voltage and composition as would be predicted by the Nernst equation. whereas the interlayer bonding is characterized by weak van der Walls attraction. The Li atoms occupy the center of the carbon hexagons. In the case of graphite popular choices for the intercalant species are Ca. to insert other atoms in between the layers. a series of plateaus. in the thermodynamic sense. Fig.5.6 shows the voltage during the discharge of a LixC6 intercalation material as a function of the Li content denoted by x. 3.Chapter 3 – Batteries and Fuel Cells Fig. There is strong interatomic within each of the “grapheme” layers. forming what is called an intercalation compound.

stage 2. 3. 3. A schematic of the staging behavior of a graphite intercalation compound.Chapter 3 – Batteries and Fuel Cells Each level portion of the curve represents a two phase equilibrium where each of the phases can be labeled stage 1. (In the 2Lto 2 stage. Fig.7. The phases themselves are shown schematically in Fig. That is. Each of the plateaus in the curve represents a different phase. but there is a random arrangement of filled vs unfilled rings.6. 16 .) Fig.7. Stage 3 for example refers to a structure where every third layer consists of the 1/6 Li arrangement. The voltage vs composition of Li in a graphite intercalation compound. etc. 3. as shown in Fig. the L refers to liquid-like or disordered arrangement of Li within the layer.7. 3. or stage. Li still occupies the center of 6 member carbon rings.

This low temperature phase does not perform well in battery applications and exhibits large hysteresis upon intercalation and de-intercalation. For LiCoO2 synthesized at low temperatures (~400oC) the spinel crystal structure is formed. 3.Chapter 3 – Batteries and Fuel Cells Upon charging of a Li ion battery the Li is incorporated into the anode via the staging process.8. but let us examine in more detail the most popular choice: LiCoO2. The unit cell of LiCoO2. 3. LiNiO2 and LiMn2O4. Therefore we are now in a position to write down the half cell reaction at the anode: LixC = C + xLi+ + xeNow what about the cathode? In order to avoid the use of pure Li metal anywhere in the battery design.8 below. There are a few cathode materials in use such as the compounds LiCoO2. Fig. an intercalation compound for the cathode is again a good choice. whereas during discharge the reverse atomic transport occurs. Therefore the phase formed at higher temperatures (~800oC) is preferred and its crystal structure is shown in Fig. 17 .

A schematic depiction of the Li ion battery is shown in Fig. In the range of concentration between . region is observed. Fluorinated polymers.9. As in the case of Li metal batteries. liquid electrolytes consist of some organic solvent.Chapter 3 – Batteries and Fuel Cells Notice the structure is similar to that of graphite in that it can be viewed as a stacking of hexagonal planes of atoms. Four types of electrolytes have been used. for . Because the Li moves back and forth between the two intercalation compounds – the anode and cathode – the design is often referred to as a “rocking chair” battery. Finally. Much like the graphite anode the cathode material undergoes a series of phase transitions as the Li is intercalated into the LiCoO2. usually a carbonate.88V.51 another single hexagonal phase H2 is stable.45. H1 plus H2.78<x<. such as 18 . 3. Here the Li layers are intercalated between the oxygen layers.78 a two phase. but suspiciously absent front the schematic diagram above is the electrolyte. plus a Li salt. For x in range . The half cell reaction at the cathode can be written as: Li 1-xCoO2 + x Li+ + xe.9 to 1 a single hexagonal phase denoted H1 is stable whereas for . A second option is a gel electrolyte which is a salt and a solvent dissolve in a high molecular weight polymer.51<x<.= LiCoO2 For an overall cell reaction of: LixC + Li1-xCoO2 = LiCoO2 + C And now for the good news: the cell voltage for the LiCoO2 battery is a huge 3.45 a monoclinic distortion associated with Li ordering is the thermodynamically favored structure.9 and . If we again let x represent the Li atom fraction within the intercalation compound then the useful range of compositions is 1>x>. We have succeeded in choosing an anode and cathode material such that pure Li metal does not exist within the battery.

does not use an anode and cathode material that is consumed during discharge.5 The hydrogen fuel cell As mentioned in the introduction a fuel cell. J. 3. Fig. From P. Universiteit Twente.Bouwman “Lithium Intercalation in preferentially oriented submicron LiCoO2 films”. 2002. In addition to liquid and gel electrolytes.9. PhD thesis. as opposed to a battery.Chapter 3 – Batteries and Fuel Cells polyvinylidene+hexafluoropropene (PVDF-HFP) combined with LiPF6 salt and a carbonate solvent are a typical choice. Schematic depiction of the Li ions in a Li ion “racoking chair” battery. In a hydrogen fuel cell H2 gas is introduced at the anode whereas oxygen O2 gas is introduced at the cathode 19 . 3. polymer and ceramic films have also been considered for use in Li ion batteries. Instead the “fuel” is continuously fed into both the cathode and anode ends of the cell.

The H2 gas flowing through the anode end undergoes the following oxidation reaction: H2(g) = 2H+ +2eNotice this is simply the standard hydrogen electrode reaction. without any actual electrode material. 20 . 3.10. The reaction product in this electrochemical process is water and therein lies the attraction of the hydrogen fuel cell for energy applications. The overall cell reaction is thus: H2 (g) + 1/2 O2 = H2O (l) The standard cell potential is 1. As will be discussed in more detail below a catalyst is introduced into the PEM design to aid in breaking the H2 molecule into two protons (H+ ions). but the abbreviation. (Interestingly the cell is often called a proton exchange membrane fuel cell. but the use of gaseous fuel. is the same!) A schematic diagram of the PEM fuel cell is shown in Fig. PEM. Harmful greenhouse gases are produced nowhere in the reaction cycle. As with the anode side a catalyst is again required to assist the reduction reaction. The most popular design choice of the hydrogen fuel cell is the polymer electrolyte membrane or PEM cell.23V.Chapter 3 – Batteries and Fuel Cells side.23V is not great. As we now know 1. means reasonable energy densities are possible.= H2O(l) The liquid water formed must be removed from the cell. Air or more specifically O2 gas flows into the cathode side where it then reacts according to: 1/2 O2 (g) +2H+ + 2e.

Chapter 3 – Batteries and Fuel Cells Fig. there are several problems. generates power and produces nothing but water as a bi-product.10.supelec. So what’s the problem? Why aren’t we all driving hydrogen PEM fuel cell automobiles? Well. First and foremost is a very general concern: where do we get the hydrogen gas? Hydrogen is not very plentiful in the atmosphere and thus needs to be generated from some chemical process. From http://www. as is done currently. There are ongoing research efforts to utilize the power generated from solar 21 .lss. The PEM fuel cell uses nothing but oxygen and hydrogen gas. A schematic of the polymer electrolyte membrane (PEM) hydrogen fuel cell. then we have done nothing to alleviate the problem global greenhouse gas emissions. Note he catalysts on both side of the electrolyte film. If the production of H2 involves the burning of hydrocarbons.

The electrolyte of choice in current PEM designs is Nafion. In addition. 3. there are several others. The current PEM electrolyte of choice in fuel cells has the trade name Nafion and is from a class of polymers known as perfluoro-sulfanated acids (PSFA).5.11. The key feature being the long narrow channels formed when the sulfonic acid functional groups self organize into hydrophilic water channels. The water channels created are fairly wide.12 shows the microstructure of Nafion. on average 24 A. Biological routes to produce hydrogen gas. y=1. the present designs are too expensive for hydrogen to compete with traditional fossil fuels. 3. Recall. Through the photosynthesis of algae. The repeat unit does not tell the full story of why Nafion is a good ionic conductor. The chemical structure of a PSFA is shown in the schematic of Fig. Fig. yet be electrically insulating. which is characterized by m=1. Unfortunately the rate of H2 production is low and it is safe to say that the technique requires further development. so-called biohydrogen.5. The repeat unit of a perfluoro-sulfanated acid (PSFA). y=1. The hydrogen source is only one major hurdle to be overcome in creating a cost effective hydrogen PEM fuel cell. have also been proposed. CO2 gas and H2O are used in the generation of H2. At the same time. 22 . Fig. As a first point of discussion consider the electrolyte itself. n=2 and x in the range 5 to 13. an effective electrolyte will exhibit high ionic conductivity.11 and for Nafion the repeat units are m=1. the sidewalls of the channels provide mechanical and thermal stability for the film. like other photovoltaic cell applications. n=2 and the long chain backbone is in the range x=5-13. But.Chapter 3 – Batteries and Fuel Cells cells to produce hydrogen through the electrolysis of water. 3. desirable properties of the electrolyte include good thermal and hydrolytic stability and the ability to form the material into thin films. such that ions can pass readily.

where hydrogen in molecular form can diffuse through the electrolyte to the cathode side. the water in the pores of the Nafion film give rise to the good ionic conductivity. Nature Materials. Therefore. Schematic diagram of the molecular structure of Nafion showing wide hydrophilic channels. what is the problem? Again there are a few. The H2 can then directly react with O2 to 23 . but not at a sufficiently high rate such that the electrolyte dries and its resistance increases. An effective fuel cell electrolyte membrane must conduct protons. The problem is compounded at high temperatures. 3. Chen. The cell reaction to produce water is quite exothermic and relatively high operating temperatures are to be expected. During the operation of a hydrogen fuel cell the water being produced must be continually removed. However. yet it must keep separate the two components of the fuel – ie. 7. Nafion also suffers from a problem known as hydrogen crossover. 75 (2008) Since Nafion seems to fit the bill. has to do with water management. H2 and O2 gas. Schmidt-Rohr and Q. water must be wicked away from the cathode. If the temperature exceeds 100oC. From K. however.Chapter 3 – Batteries and Fuel Cells Fig.12. Nafion is expensive to produce and a considerable amount of research is now being conducted to find a lower cost alternative. The first is cost. A more important problem. then evaporation of water from the Nafion will occur and a dramatic drop in the ionic conductivity will follow.

Notice in Fig. Nafion is not the only problem facing the development of hydrogen PEM fuel cells. various estimates have suggested that. for PEM fuel cell technology to be cost competitive in large scale automotive applications. Instead a fundamental break through is required and there is hope! 24 .Chapter 3 – Batteries and Fuel Cells form undesirable peroxides. A fairly obvious scheme to decrease the Pt content is to fabricate particles as small as possible. meaning carboxylic. As you may guessed by now. the most effective catalyst known is platinum. The functional groups act as anchoring sites for the catalyst particles and aid in the deposition of Pt. thereby creating more surface catalytic sites per unit volume of the precious metal. phenolic or carbonyl groups are absorbed on the carbon surface. It is more expensive than gold or silver and is several orders of magnitude more costly than steel. thicker Nafion films will increase the overall film resistance and decrease the power of the cell. Although Pt catalysts have been improved over time by altering the carbon support.10 that catalysts are included in the cell design. However. It is not obvious that Nafion is a relatively expensive polymer material. In recent years. The catalyst design in current use consists of a graphite support decorated with small particles of Pt. 3. To put the catalyst problem in perspective. Unfortunately. but it is pretty clear platinum is expensive. which at the time of this writing is priced at roughly $40 (US) per gram. it is difficult to imagine these incremental changes overcoming the five fold decrease in Pt required for the widespread use of hydrogen vehicles. several research groups have investigated the use of carbon nanotubes as a support material to further decrease the Pt particle size. the current densities of a hydrogen fuel cell would be too low for any practical application. A seemingly simple solution to the cross over problem is to fabricate thicker electrolyte films to decrease the H2 flux. The more difficult reaction occurs at the cathode side. Without a catalyst accelerating the two half reactions. This reaction is fairly easy to catalyze. Typically the carbon surface is functionalized. Pt is a precious metal. anhydride. the amount of Pt currently used in the fuel cell stacks must be reduce by a factor of five! The splitting of H2 into ions of hydrogen at the anode side of the cell is not the problem.

which is known as “coarsening”.Chapter 3 – Batteries and Fuel Cells Before proceeding however a few more problems associated with the catalyst are worth discussing. For the 111 surface the activity increases by over an order of magnitude. However. Carbon monoxide molecules absorbed at the Pt surface can greatly reduce the performance of the catalyst. Fig 3. The problem can be alleviated to some extent through the use of Pt-Ru alloys where Ru at the surface more strongly attracts a CO molecule. But the story gets better. Catalysts can be evaluated based on their activity. at a 111 exposed surface the Pt. The effect is quite dramatic with only ppm levels of CO within the oxygen gas stream having a substantial effect on performance. for energetic reasons. We need not describe in detail the reaction occurring by suffice it to say the activity measured is proportional to the oxygen reduction reaction taking in a PEM cell. The surface. is not an easy task. An encouraging development in the quest for improved and less expensive PEM catalyst is the intermetallic compound Pt3Ni. It is pretty clear the results are striking. The activity here is a bit complicated. In a bulk specimen each 111 plane consists of 25% Ni atoms. As noted above the optimal catalyst consists of a very high surface to volume ratio of Pt. the larger particles in the collection will grow whereas the smaller particles in the distribution will shrink and eventually disappear. Pt-Ru is not exactly a low cost alternative and. Another troubling aspect of the Pt catalyst is poisoning. looks like pure Pt.13 shows the results for Pt3Ni vs conventional Pt catalysts. The crystal structure of the compound can be viewed as an FCC unit cell with the corner atoms being Ni and all the face atoms Pt. which is some measure of how much faster a reaction proceeds in the presence of the catalyst. Over time at elevated temperatures the collection of Pt particles will tend to decrease the overall surface area. a situation which is thermodynamically unfavorable. however. The effect is less for the 100 and 110 25 . but the overall Pt content has been reduced by 1/4. where the catalytic reaction takes place. It is expressed in terms of a current flux at constant voltage of the catalyst contained in a . tends to be enriched in the topmost plane such that a pure Pt layer is formed. Slowing or stopping this process. The Pt skin structure also changes the electronic band structure of the material in such a way that the catalyst performance is dramatically improved. moreover. the total amount of Pt needed remains unchanged.1M HClO4 solution. Thus we can see immediately a benefit of Pt3Ni.

P. Fowler. Markovic. N. Science. Fig. Lucas and N. A. 26 . Are we then ready to roll a hydrogen vehicle off the assembly line and sell it to the public? The answer is no. Stamenkovic. There is still the very sticky problem of how to deliver the H2 gas to the fuel cell on-board the vehicle. Mun. The activity of Pt3Ni catalysts vs pure Pt catalyst for three low index surfaces. especially for the (111) surface. C. Wang. B. S. but a substantial increase is observed nevertheless. The increase in activity is very large. From V.13. yet highly active. we have found an attractive alternative to Nafion for an electrolyte material in a PEM fuel cell and we have stumbled upon a low cost. M. Ross. 3. 1. catalyst. Catalyst improvement through alloy design appears to be the promising route to developing a low cost fuel cell for widespread automotive use. 493 (2007). B. R. 315. G.Chapter 3 – Batteries and Fuel Cells surfaces.6 Hydrogen storage Let’s assume we have developed some method to produce large quantities of H2 gas cheaply.

Another very crucial concern is how much hydrogen the material. In other words if the ratio H:Pd is equal to one then the stoichiometry of PdH is reached. Office of Efficiency and Renewable Energy. A final problem with the cylinder design is one of safety. a traffic accident. If the nozzle to a highly pressurized canister is fractured during. the report lists a goal of 6% by weight for an on-board hydrogen storage system by the year 2010. Thus. but their formation often involves a very exothermic reaction and the strong free energy gain means the reverse reaction of pulling hydrogen out of the storage material is very difficult. as part of the FreedomCAR program. The y axis in the diagram is also a departure from what we’re use to. Shown in Fig. Department of Energy. a 6wt% goal represents a daunting challenge. To understand just how difficult this task is consider the case of the Pd-H system. The PdH system offers a seemingly attractive alternative. It is the ratio of H atoms to Pd atoms in the hydride. The US. say. has published a list of technical targets for required for viable designs of future hydrogen vehicles. Since hydrogen is the lightest element in the universe. the simple solution of using pressurized gas cylinders to store the H2 gas on board will result in a tank heavier than gas tanks in automobiles. The material of choice should be able to absorb hydrogen quickly during “filling” and must desorb hydrogen rapidly during the operation of the vehicle. The isotherms on the diagram illustrate.Chapter 3 – Batteries and Fuel Cells Hydrogen has a very high energy density by weight but is much worse than hydrocarbons (gasoline) on a per volume basis. for each temperature listed.024 atm is shown in parenthesis). 3. Among other factors. Many metal (M) hydrides exist at a stoichiometry as high as MH.14 is the Pd-H phase diagram where the x axis is not the usual atom or mole fraction. In addition pressurizing the gas costs energy such that the net efficiency gain from a hydrogen vehicle is diminished. then the cylinder becomes a very dangerous high energy projectile. Here it the pressure of hydrogen in atmospheres (the conversion to mmHg for . the path in composition space the sample will follow as the pressure 27 . An alternative solution to the fuel delivery problem is a metal hydride material for safely and economically storing hydrogen. can absorb. by weight.

During the flat portion of the isotherm the composition does not involve an increase in pressure. the Pd-H system represents a hydrogen storage system in which hydrogen can be easily and rapidly removed and recharged. As the pressure is decreased and H is depleted from Pd the system will follow the same isotherm in the opposite direction. Because the volume change between phases is fairly large (~10%) a hysteresis is observed between the loading and unloading of H. For example at a temperature of 160oC the concentration will increase from less than .7 as the pressure is increased to 20atm. instead amount of alpha relative to beta is changing. Notice a two phase region between a low volume alpha and a high volume beta phase exists and the miscibility gap ends at a critical point of approximately 295oC and 20atm. 3.14.Chapter 3 – Batteries and Fuel Cells increases.05 H per Pd atom up to roughly . The y axis is atmospheres. Note. the miscibility gap between the low 28 . However. Fig. the absorption and desorption steps are not completely reversible. The pressure-composition phase diagram of the Pd-H system. Nevertheless.

is just 1.66% is achieved – a value which is an order of magnitude less than the DOE target of 6. There is a considerable amount of research now being conducted to identify a suitable storage material and we will discuss a few promising candidates. is only 5.15) where the green spheres represent the Al atoms and red correspond to Na. yet the binding can’t be too strong or we will not be able to pull H from the material to run our vehicle.5%.4 and H.html A quick glance at the periodic table will reveal the problem with Pd-H. Since four H atoms surround each Al and because Na and Al are low density elements the weight percent H in sodium alanate as 7. A close cousin of the sodium alanate is lithium alanate LiAl4.Chapter 3 – Batteries and Fuel Cells volume α and high volume β phases. 3. The materials design criterion for a suitable hydrogen storage system is in some sense contradictory. 29 . The crystal structure of the compound NaAlH4 is shown below (Fig. we need a very light weight H host.7 in the hydride. of course. From http://131.156.4% (the reversible H content however. Therefore if the pressure is sufficiently high to reach a composition of . On top of this delicate balancing act. Surrounding each of the Al atoms is a tetrahedral arrangement of hydrogen atoms. then a weight percent of only 0. A large binding energy between H and the material is required to absorb sufficient amounts. A class of compounds known as the alanates is perhaps the leading contender. The main hurdle with the alanates is the slow desorption kinetics. The structure can be viewed as a packing of layers each consisting of an arrangement of Na and Al-H tetrahedral.0wt%. which boasts an even higher H content of 10.23/Lectures/CHEM_462/462_chapter_1. Several recent studies have shown that catalysts like Ti and Zr can greatly speed up the dissolution rate in NaAlH4.6%). but thus far the rate increase has not been enough and the search for improved catalysts is hampered because the precise role played by Ti in the desorption process is not fully understood.104. The atomic weight of Pd is 106.

2 H atoms per formula unit) at a temperature of 78K.html Another class of materials with the potential for use as on-board hydrogen storage devices is the so-called metal organic framework (MOF) compound. a candidate H storage material.5% (17. 3. Unfortunately the equilibrium H 30 . From http://www. with each one being surrounded by four oxygen atoms. in six places.4-benzenedicarboxylate. The blue tetrahedra represent the Zn atoms.15. With the cube repeated over all space a material is that offers many binding sites for H is formed. Indeed the Zn4O(BDC3) MOF exhibits a fairly high H weight percent of 4. colored in red. The four Zn atoms share a common O atom at the center. the large yellow sphere in below. by the BDC3 group. 3. The atomic structure of the MOF is shown in Fig. 3.ojwang. NaAlH4.Chapter 3 – Batteries and Fuel Cells Fig. One example is the compound with stoichiometry Zn4O(BDC3) where the unit BDC3 represents the organic part of the MOF designation and is the functional group 1.16 shows the available open space in the structure. but the other sides of the tetrahedra are bridged. The unit cell of sodium alanate. The result is a very open cube.

Yaghi. D. M. intercalated graphite and even ammonia. M. From N.16. The yellow sphere represents the large open space in the structure. J. The structure of the metal organic framework (MOF) material Zn4O(BDC3). Fig. T. 300. 3. Vodak. but the two most challenging problems of absorption/desorption kinetics and high H content by weight have not been overcome and it seems safe to conclude that a viable on-board H storage system is many years away. 31 . Rossi. 1127 (2003). Science. J. O’Keefe and O.Chapter 3 – Batteries and Fuel Cells content decreases significantly with increasing temperature and at room temperature is only 1%. Other hydrogen storage materials currently being considered include carbon nanotubes. Eddaoudi. Kim. M. L. Eckert.

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