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Journal of Power Sources: Piotr Forysinski, Colin Oloman, Sona Kazemi, Tirdad Nickchi, Ashwin Usgaocar T
Journal of Power Sources: Piotr Forysinski, Colin Oloman, Sona Kazemi, Tirdad Nickchi, Ashwin Usgaocar T
Keywords: Mixed-reactant fuel cells are unconventional electrochemical power sources which use a thermodynamically
Mixed-reactant unstable mixture of fuel and oxidant. In the work described here a 2-phase mixture of alkaline potassium formate
Fuel cell (liquid)/oxygen(gas) is the fuel/oxidant combination used in the “flow-by” mode with mixed-reactant fuel cells,
Formate developed in the laboratory from a 10E-4 m2 single cell to a bipolar stack of nineteen 35E-4 m2 cells. With Pd/Ag
Electric scooter
anode/cathode catalysts, operating at 500 kPa(abs), 80 °C the single cell with a Pd load of 0.054 kg m−2 reaches
a superficial power density of 4,000 W m−2 at 10,000 A m−2. Tests of the 19 cell stack with a Pd load of
0.036 kg m−2 at 300 kPa(abs), 60 °C give power output up to 120 W, with a corresponding volumetric power
density about 400 kW m−3. To demonstrate the fuel cell performance three nominally 100 W 19 cell stacks are
wired in parallel to a 250 W electric motor to drive a modified electric scooter, with on-board fuel, oxidant and
an adult passenger, for about 15 minutes at 10 km h−1. To our knowledge this is the first time mixed-reactant
fuel cells have been used alone to power a vehicle.
Corresponding author.
∗
E-mail addresses: pforysinski@yahoo.com (P. Forysinski), coloman@intergate.ca (C. Oloman), sona.kazemi@gmail.com (S. Kazemi),
tirdadn@gmail.com (T. Nickchi), ashwin.usgaocar@gmail.com (A. Usgaocar).
https://doi.org/10.1016/j.jpowsour.2018.12.081
Received 28 July 2018; Received in revised form 22 December 2018; Accepted 28 December 2018
Available online 16 January 2019
0378-7753/ © 2019 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/BY/4.0/).
P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
result that one or both electrodes present a mixed-potential that lowers chamber” and “separator-free” fuel cells the simple configuration of
the voltage and energy efficiency of the fuel cell. In practical applica- MRFCs has inspired many investigations into their performance and
tions this loss of fuel cell performance may be compensated by reduced applications, as summarized in published reviews [1,2] and illustrated
complexity, size, weight and cost of mixed-reactant vs. separate-re- in Table 1. The examples in Table 1 include fuel/oxidant mixtures
actant systems. ranging from H2/O2 to CH3OH/H2O2 and CH3OH/Fe+3, with catalyst
Under alternative names such as “membrane-less”, “single- such as Pt, Pd, Au, Ag, RuSe, Os and FeCo, operating at temperatures
Table 1
Notable MRFC results.
Reactants Electrodes Conditions Peak performance Separator Reference
−2
kPa (abs) °C Am W m−2
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
below 100 °C and generating superficial power densities up to about respectively [1.2M NaHCO2 + 1.6M NaOH] and [0.7 M
2,000 W m−2 [3–10]. Single-chamber solid oxide fuel cells (SCSOFC) NaHClO + 1.6 M NaOH] in a LFFC showed an open circuit voltage of
operating above 600 °C have delivered superficial power densities up to 1.4 V and delivered a superficial power density of 520 W m−2 under
7,500 W m−2 [11]. Partial reaction selectivity in these fuel cells was ambient conditions [29].
obtained by manipulating the intrinsic kinetics, hydrophobicity and The present paper records a pioneering development of mixed-re-
conditions in the electrodes, giving open-circuit potentials up to about actant flow-by fuel cell stacks and their use to power an electric scooter.
90% of values in the corresponding separate-reactant fuel cells. In Based on principles of electrochemistry and fluid dynamics the 18
mixed-reactant systems the fuel and oxidant may be delivered in flow- month project proceeded in three overlapping phases:
through or flow-by mode as a single or multiphase mixture to one or
both electrodes (anode & cathode). A separator such as an ion-exchange i. Conception, fabrication and testing of single cell MRFBFCs with
membrane, porous diaphragm or plastic screen is typically installed to fuel/oxidant mixtures of [alkaline potassium formate/oxygen gas],
prevent electronic contact between anode and cathode. Laminar flow ultimately delivering superficial power densities up to
fuel cells (LFFC), where fuel and oxidant are separated in space by 4,000 W m−2.
microfluidic flow phenomena, and single-chamber microbial fuel cells ii. An unprecedented scale-up and assembly of 19 cell 100 W bipolar
are technically not mixed-reactant systems but are included in Table 1 MRFBFC “filter press” stacks.
as membraneless devices [12–14]. iii. Use of the MRFBFC stacks to drive an electric scooter with a nom-
Formic acid and alkali formate salts have been recognized for many inal power of 300 W.
decades as electrochemical fuels in both batteries and fuel cells [15,16].
More recently the search for carbon-neutral energy systems has sti-
mulated work on direct formate fuel cells (DFFCs) in association with 2. Guiding principles
the electroreduction of CO2 [17,18]. The DFFC fuels typically contain
1–4 M KHCO2 with 1–4 M KOH. Notably, the formate electro-oxidation The mixed-reactant flow-by fuel cell (MRFBFC) has novel features
kinetics depend on pH (9–14), so operation without KOH roughly not encountered in conventional “separate-reactant” fuel cells. The
halves the peak superficial power density, as does replacing O2 by air paradigm change required for the development and practical applica-
[19]. tion of the MRFBFC was guided by the principles outlined below in
Separate-reactant single-cell DFFCs with anion membranes operated reference to Fig. 1.
at ambient pressure and 60 °C have achieved superficial power densities Fig. 1 shows a conceptual cross-section of a single fuel cell unit used
about 3,000 W m−2 with oxygen and 5,900 W m−2 with hydrogen in this work. In a bipolar stack the anode and cathode current feeders
peroxide as the oxidant [18,20–25]. Mixed-reactant DFFCs have had are replaced respectively by the adjacent cathode and anode in the
less attention, although recent work on a membraneless DFFC with a series. This figure indicates a vertical orientation but the fluid flow
fuel/oxidant mix of [KHCO2+KOH]/O2 at 300 kPa(abs), 50 °C de- regime is such that with proper attention to end effects the unit can
monstrated superficial power densities around 900 W m−2 at 1,700 operate in any disposition with respect to gravity. Further, both the
A m−2 [26,27]. Earlier, a DFFC was operated with fluid flow orthogonal hydraulic and electric connections between multiple cells can be in
to current as a “mixed-reactant flow-by fuel cell” (MRFBFC) with a fuel/ series or in parallel. In the work reported here vertical cells were con-
oxidant mix of [2M NaHCO2+2M NaOH]/O2 at 130 kPa(abs), 60 °C to nected hydraulically in parallel and electrically in series (i.e. bipolar).
generate a superficial power density of 1,200 W m−2 at 2,400 A m−2 All components of the fuel cell, except the separator, are electronically
[28]. Formate has also been tested as fuel in LFFCs fed with separate conductive with desirable low contact resistances.
solutions of formate and an oxidant. For example, fuel and oxidant of
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
2.1. Electrochemistry effects may be examined in terms of the values set out in Table 3.
The electrode reactions for the formate/oxygen system used in the Bo = gd2/ Bond number (2)
present work are summarized in Table 2. Ca = µV/ Capillary number (3)
Since both reactants can be present in the anode and the cathode the p = 2 cos /r Laplace Capillary pressure (4)
electrodes set up mixed-potentials whose values depend on the re- dL/dt = r cos /(4µL) Washburn Liquid penetration rate (5)
spective competitive reaction rates. Conceptually the interaction be-
tween intrinsic kinetics and mass transport biases the mixed-potentials Values of the Bond and Capillary numbers show that capillary forces
at the electrodes to favour formate oxidation at the anode (rxn 1) and are more significant than gravity in all components, while being com-
oxygen reduction at the cathode (rxn 2). The primary anode reaction 1 parable to viscous drag in the distributor and dominating in the anode,
consumes 1 mole of HCO2− and 2 moles of OH−, supplying 2 Faradays cathode and separator. The capillary pressures indicate that, under
of charge to the primary cathode reaction 2 which consumes 0.5 mole static conditions, aqueous electrolyte solutions fully wet the porous Pd
O2 and generates 2 moles OH−. In this simplified scenario the OH− anode, are strongly rejected by the hydrophobic surface layer of the
consumed at the anode is balanced by that transferred through the cathode and are absorbed in the separator which then presents sub-
separator from the adjacent cathode to give a full-cell equilibrium po- stantial resistance to penetration by gas. However, reactant contact
tential of 1.22 V at 25 °C (rxn 3) with zero net consumption of H2O. In with the electrodes under dynamic conditions in an operating fuel cell
practice the mixed-potentials lower the open-circuit voltage to a degree is more complex and depends on the two-phase flow regime in the
depending on the effectiveness of the electrodes, while excess hydro- distributor coupled to the rates of fluid penetration to the electro-active
xide tends to raise the cell voltage by converting HCO3− to CO3−with zones of the electrodes. Electrolyte solution can move rapidly into the
the resulting overall cell reaction 4. The simple stoichiometry of Table 2 anode and out of the cathode by capillary effects but this desirable
belies complex processes in which the rates of transport of formate, condition can be upset by excessive gas flux and pressure gradient in
hydroxide and oxygen into the electrodes and across the separator the distributor, which displaces liquid fuel from the anode and/or
would control the electrode potentials and/or kinetics [19,30]. drives it into the cathode.
Intrinsic selectivity of the respective anode and cathode reactions 1
and 2 is desirable but not necessary here [31]. Both electrode reactions
can occur on the nominal anode and nominal cathode. In the mixed 2.3. Fluid distribution and cell performance
formate/oxygen system these reactions are each intrinsically fast on
palladium with specific activities about 30 A m−2 Pd at 25 °C [32–34]. Apart from providing a flow path for the reactants the distributors
Reactions 1 and 2 are respectively intrinsically fast (50 A m−2 Ag) and function to provide an ionically insulated electronic connection be-
relatively slow on silver [35,36]. However reaction 2 is suppressed on tween bipolar cells. Ionic insulation is critical for bipolar operation and
the nominal anode (Pd) by the constraint on oxygen mass transfer is approached with a gas-continuous 2-phase flow regime through the
through the wetted porous hydrophilic electrode, while transport of distributor, which prevents liquid ionic paths forming between opposed
fuel to the bulk cathode (Ag) is prevented by an electronically con- electrodes. The 2 mm thick expanded metal distributor mesh presents a
ductive porous hydrophobic layer between the cathode and fluid dis- “microchannel” flow path for the liquid/gas mixture with an effective
tributor. Fuel solution can penetrate the hydrophilic micro-porous se- hydraulic diameter about 1 mm. Although many factors, such as the
parator to reach the face of the cathode which is intrinsically selective feed mixer geometry, interfacial tensions and liquid/solid contact an-
for reaction 2 over reaction 1. An ion membrane separator would be gles affect fluid dynamics in the distributor the 2-phase flow regimes
needed here if the cathode did not intrinsically favour reaction 2. called “churn”, “slug-annular” and/or “annular” may be expected in the
This configuration can be modeled as a continuous plug-flow elec- present situation, where gas/liquid superficial velocity ratios range
trochemical reactor, using four simultaneous non-linear voltage bal- from about 10 to 50 [40]. In any case proper operation of the MRFBFC
ances, one for each anode-cathode couple [30]. stack requires careful attention to the disposition of the feed nozzle(s)
Ecell = Eoc,y – Eoa,y + ηc,y – ηa,y – iR* (1) and distribution of fluids over the bipolar cells.
When capillary and fluid dynamic effects in the MRFBFC bring re-
[N.B. All quantities are defined in the Nomenclature] actants to their respective electrodes the performance of the fuel cell
will depend on behaviour in the three-dimensional (3D) electrodes.
Since the reactor design does not allow cooling a model should in-
With fast intrinsic kinetics [31–35], an anode specific surface of about
clude coupled material and energy balances to follow the reactant
4,000 m−1, cathode ECSA ≈ 50 m2g-1 Ag, 1 M formate, oxygen at
conversion and temperature through the cells under adiabatic condi-
300 kPa(abs) and ΔV = 0.1 V the mass transfer limiting anode and
tions. In practise such a model would engage three-dimensional elec-
cathode superficial current densities at 25 °C, estimated from equations
trodes and involve the numerical solution of coupled partial differential
(6)–(8) are respectively about 8,000 and 10,000 A m−2. These values
equations [37] with many parameters of unknown value. That complex
would change with temperature as it affects practically every property
analysis is beyond the scope of the present work but useful information
and parameter in an operating MRFBFC.
for design of the MRFBFC can be found in simple equations associated
with interfacial phenomena [38] and electrochemical engineering [39].
Table 2
2.2. Capillarity Stoichiometry in the alkaline formate/oxygen MRFBFC.
Rxn Stoichiometry Eo, 298 K, dEo/dT
Capillary phenomena are exploited in the MRFBFC to suppress the pH = 14
transfer of fuel and oxidant to their respective counter-electrodes and to
V SHE V K−1
prevent ionic short circuits between bipolar cells. Two-phase flow of the
fuel/oxidant mixture through the fluid distributors delivers both fuel 1 Anode HCO3− +H2O + 2e− ← HCO2− + −0.82 -2E-4
(liquid) and oxidant (gas) to the exposed “outside” surfaces of the 2OH−
anode and the cathode. Access of the reactants to the “inside” electro- 2 Cathode 1/2O2 + H2O + 2e− → 2OH− +0.40 -1E-3
3 Overall HCO2− + 1/2O2 → HCO3− +1.22 -5E-4
active fields of the 3D electrodes is determined primarily by the ca-
4 Overall HCO2− + OH− + 1/2O2 → +1.33 (excs -8E-4
pillary pressures, rates of fluid penetration in the porous electrodes [38] CO3−- + H2O OH−)
and the distributor flow regime. The significance of these capillary
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
Table 3
Capillary effects in porous media with aqueous solutions vs. oxygen gas – see Table 4.
Item Material Thickness Porosity Pore Bo Ca ΔP dL/dt
jL = nFKCb mass transfer limiting real current density (6) In all tests the fuel cells were oriented vertically and suspended by
= (2 V/aRjL )0.5 effective electro (7) nickel rods inside a cylinder fabricated initially from 4 inch clear PVC
and later 4 inch stainless steel pipe, with an outlet throttle valve for
active thickness in 3D electrode
pressure control. A 3D-printed shroud in ABS plastic was used to pre-
iL = jL a mass transfer limited superficial current density (8)
vent the fuel/oxidant mixture from bypassing the stack. In tests with a
single cell the liquid fuel was dripped from a manifold to the top of the
2.4. Temperature cell while the multi-cell stacks were fed by a conical spray misting
nozzle [42], as in Fig. 3. The MRFBFC stack has no provision for cooling
The effect of temperature on performance is particularly significant except via sensible heat, heat of vaporization of the 2-phase reactant
in a bipolar mixed-reactant fuel cell stack. With no provision for in- stream and heat transfer through the container wall.
ternal cooling a bipolar stack operates under nearly adiabatic condi- In laboratory operation the liquid fuel was fed from a calibrated
tions in which stack performance depends on complex interactions peristaltic pump, whereas for the scooter (described below) the fuel was
among several variables. This situation is illustrated in Fig. 2 by the driven from the fuel tank by compressed oxygen. Oxygen gas was de-
relation between temperature, current density and reactant conversion livered either through the spray nozzle or at the top of the vessel ad-
estimated from a material balance coupled with an energy balance in an jacent to the fuel in the case that separate liquid and gas feeds were
idealised adiabatic process at steady state. required for individual flow control.
The two-phase fuel/oxidant mixture flowed downward through the
0 = Hin H out IEcell adiabatic energy balance (9)
fuel cell to be discharged from the bottom of the containment vessel
The intuitive understanding of fuel cell performance is made diffi- into a phase separator which also served to hold the spent fuel. Exhaust
cult here by the many interacting factors affecting the non-linear gas was passed through a de-misting filter and released. The internal
system. pressure and temperature were measured respectively by a Bourdon
Power density in the MRBFFC typically increases with the tem- gauge and by a thermocouple attached to one nickel end-plate. A load
perature, which is determined primarily by Joule heating versus the bank (BK Precision 8514) was used in the laboratory to record the
sensible plus latent heats exchanged with the flowing fluids, and is MRFBFC polarisation curves for a variety of operating conditions. Apart
limited by the durability of reactor materials. Depending on the elec- from the MRFBFC stack only nickel, stainless steel 304, ABS, PVC,
trolyte composition, oxidant gas flow and pressure, at temperatures polypropylene, epoxy resin, EPDM and Teflon were used in this
above 80 °C the endothermic latent heat of vaporization of water con- equipment.
tributes a large “cooling” affect in the energy balance, which predicts The fuel and oxidant used in the tests recorded here were respec-
temperatures approaching 130 °C in 4 M electrolytes under 300 kPa tively an aqueous solution of [2M NaHCO2 or KHCO2 + 2 M NaOH or
(abs) at 12,000 A m−2. With robust reactor materials such high tem- KOH] and [99 vol % O2 gas], with flow rates of approximately
peratures may substantially improve the MRFBFC performance relative 0.01–0.2 L min−1 and 0.4–5 SL min−1 respectively, per vessel. Pressure
to that recorded in the present work where the temperature is limited to in the containment vessel was manually controlled up to 500 kPa(abs),
80 °C. with temperatures up to 80 °C. For some laboratory tests the fuel was
The principles outlined above were used to guide the experimental recycled and/or preheated, whereas operation of the scooter involved a
work described below.
3. Experimental methods
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
Table 4
Components of a nominal 100 W MRFBFC stack.
Item Material Dimensions Porosity/pore size Catalyst Source
-2
H x L x T mm %/mm kgm
H height, L length, T thickness. NA = not available. Active superficial area per cell = 35E-4 m2 (35 cm2).
Bolted nickel end plates served as the anode and cathode current collectors.
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
temperature of the reactant mixture. The strong effect of temperature is Superficial power density = [Current][Stack voltage] / {[Superficial
recorded in Fig. 7, which shows the superficial power density at 3,500 anode area per cell][Number of cells in stack]}
A m−2 increasing from about 1,200 W m−2 to 2,200 W m−2 as the
Volumetric power density = [Current][Stack voltage] / [Stack volume,
temperature rises from 23 to 60 °C, with a peak power density ex-
excluding end plates]
ceeding 3,500 W m−2 at 80 °C. With the “extra Pd” loading on the
anode (0.054 kg m−2) at 80 °C the results of Figs. 6 and 7 show the With superficial power density up to about 4,000 W m−2
possibility of obtaining superficial current and power densities from the (400 mW cm−2) at 10,000 A m−2 (1,000 mA cm−2) the single cell re-
MRFBFC respectively exceeding 10,000 A m−2 and 4,000 W m−2 sults of Figs. 6 and 7 compare favorably with previously published
(1,000 mA cm−2 and 400 mW cm−2). The high catalyst loads recorded values for both conventional separate-reactant fuel cells fuelled with
in Figs. 6 and 7 (0.036–0.054 kg Pd m−2) result from a few months of alkaline formate [18,23] and with mixed-reactant fuel cells using var-
trial and error experimentation with a simple electro-less deposition ious fuels [1]. Based on a stack alone, the single cell MRFBFC peak
process. No attempt was made to optimize the anodes with respect to volumetric power density in Fig. 7 (60 °C, extra Pd) extrapolates to
the interacting effects of Pd load, thickness, pore size and porosity that about 950 kW m−3 (950 W L−1) which approaches that obtained from
determine its performance. Further work with the catalyst support and contemporary PEM hydrogen/air fuel cells, albeit with a high catalyst
morphology may be expected to give a substantial reduction in Pd load load and oxidant of 99 vol% oxygen at 300 kPa(abs). Tests with the
on the anode [32]. actual 19 cell stack of Table 4 at 80 °C with fuel and oxidant flows re-
The full power parabolas were not recorded in many of the tests due spectively 150 ml min−1 and 5 SL min−1 give a peak power of about
to limitations in the load bank and/or internal shorts from “burn-out” of 120 W, corresponding to a volumetric power density of 400 kW m−3
the polypropylene separators above 80 °C, along with time constraints (400 W L−1), with an internal resistance from about 20 to 200 mi-
that made testing beyond peak power a low priority. croOhm m2. The lower stack power is probably due to inter-cell mis-
In Figs. 6 and 7 and the discussion below the performance metrics matches such as those caused by a non-uniform distribution of reactants
are estimated as: between cells, with consequent variation in local operating conditions
[43].
Superficial current density = [Current] / [Superficial anode area per
Temporal stability in operation is important for any fuel cell and is
cell]
relevant to the MRFBFC. A drop in power output from an MRFBFC over
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
Fig. 6. MRFBFC polarization curve. Conditions: Single cell, 10E-4 m2 (10 cm2), fuel [2 MKCHO2 + 2 M KOH] @ 50 ml min−1, oxidant O2 @ 0.4 SLmin−1, pressure
500 kPa(abs), temperature 80 °C, Pd load 0.054 kg m−2 (5.4 mg cm−2).
transportation. In principle the range could be increased about 10 fold mentioned above. That question can only be answered by long term
by raising the fuel concentration and oxidant tank pressure (e.g. to 10 M tests not yet done. So far a single cell has been operated at a power
and 10 MPa) while reducing the feed rates to approach 80% conversion density around 1,000 W m−2 for intermittent 2–3 h stretches to total
of the reactants. However, the utility of mixed-reactant fuel cells in about 10 h, which is far from the thousands of hours expected of con-
transportation is ultimately limited by the relatively low energy effi- temporary hydrogen/air fuel cells.
ciency of the reactor and energy density of aqueous fuels, making the Along with power density and temporal stability any practical ap-
MRFBFC system described here better suited to stationary than mobile plication of an MRFBFC would consider the reactant cost and conver-
applications [17]. sion, the energy efficiency, product disposal, parasitic power losses and
At this early stage of development of the MRFBFC there is a major complexity of the balance of plant. With merchant prices respectively
question about its durability and useful lifetime. In any application the around 100, 60 and 3 US$ kmol−1 the [KHCO2, KOH]/O2 is a costly
longevity of the fuel cell will be determined by the operating conditions fuel/oxidant combination, although the liquid reaction product could
and consequent stability of the electrodes and separator, particularly potentially be used in an electrosynthetic regeneration of a KHCO2/
with respect to the degradation of capillary properties and catalysts KOH mixture [17,46]. For comparison, conventional H2/air fuel cells
Fig. 7. Superficial power and current densities in a single cell MRFBFC. Conditions: Single cell 10E-4 m2, fuel [2 M KHCO2+2 M KOH] @ 50 ml min−1, oxidant O2 @
0.4 SL min−1, pressure 300 kPa(abs), temperature 23–80 °C, Pd load 0.036 and 0.054 kg m−2 (3.6 & 5.4 mg cm−2).
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P. Forysinski et al. Journal of Power Sources 414 (2019) 366–376
Fig. 8. Effect of time on the MRFBFC performance. Conditions: MRFBFC stack, 3 bipolar cells each 10E-4 m2, fuel [2M NaHCO2+2M KOH] @ 82 ml min−1, oxidant
O2 @ 2 SL min−1, pressure 300 kPa(abs), temperature 30 °C, OCV 2.73 V, superficial power density ca. 1,000 W m−2 (100 mW cm−2) . 4 L batch of fuel used with
continuous recycle and zero make-up.
take fuel at about 10 US$ kmol−1 with an energy efficiency near 40% separators into the electro-active faces of the anodes. Accommodating
and operating cost about 0.4 US$ kWh−1. The 100 W MRFBFC stacks these “separate-reactant” features would call for inter-cell bipolar plates
used in the scooter at 0.4 V per cell give conversions of formate and and gas impermeable separators (Table 1) with attendant cost increases
oxygen respectively about 25% and 20%, without recycle. Based on the that defeat the purpose of the MRFBFC.
energy density of the fuel solution (130 kWh m−3) and cost of the The high operating costs of mixed-reactant fuel cells may be offset
[fuel + oxygen] these values correspond to an energy efficiency around by relatively low capital costs. In this regard the major potential ad-
8% and operating cost about 25 US$/kWh. However, the MRFBFC in vantages of the MRFBFC are the simplicity of its construction and its
these tests is far from being optimized, such that improvements in the balance of plant. There is no need of ion-selective separators or complex
materials, configuration and operating conditions could perhaps raise sealing and flow distribution systems in the fuel cell hardware, along
the energy efficiency at 400 kW m−3 to near 30% with a (fuel depen- with less onerous constraints on operating pressure and temperature
dent) operating cost below 8 US$ kWh−1. than for a conventional separate-reactant fuel cell. As represented in
A more comprehensive examination of the viability of the MRFBFC Figs. 3 and 4 the balance of plant consists of systems for storing the
system would consider the trade-off between capital and operating reactants and controlling their flow to the stack, effluent separation/
costs. There are many factors to consider here, for example the catalyst collection and regulation of the power delivered to the electric motor.
price, electrode durability and fuel cell operating conditions, whose Handling a liquid fuel is straightforward, and humidification and
interactions are crudely summarized in equation (10). cooling are not necessary. Replacing O2 with air or O2 enriched air as an
oxidant is a possibility, although that would decrease the power density
Cost = (catalyst price)(catalyst load) / [(power density)(operating
and engender addition of a compressor to the balance of plant, with
life)] (10)
corresponding parasitic power losses.
The fuel cell operating life in equation (10) will depend primarily on
the catalyst material(s) and the power density. For example, the cost 5. Conclusion
contribution for an anode loaded with 0.03 kg m−2 Pd, operating for
5,000 h at 4,000 W m−2 is estimated as: The work described here is a proof of concept for the mixed-reactant
Pd cost = (4E5 US$ kg −1
)(3E-2 kg m −2 −2
) / [(4 kW m )(5E3 h)] = 0.6 flow-by fuel cell (MRFBFC) and its potential as a mobile or stationary
US$ kWh−1 power source. Without optimization of the reactor design or operating
conditions a fuel/oxidant mixture of [2M K(Na)HCO2 + 2M KOH](aq)/
Platinum is cheaper but is less effective than palladium as a formate O2(g) used in a 10E-4 m2 single cell and in a 35E-4 m2/cell 19 cell bi-
oxidation catalyst [18]. Nonetheless the anode cost might be sub- polar stack, operating at 300 kPa(abs) and 80 °C with superficial current
stantially lowered by manipulating the catalyst morphology and com- densities up to 9,000 A m−2, achieved volumetric power densities of
position, for example with nano-structured alloys of Pt or Pd and less respectively about 950 and 400 kW m−3. As well, two of the 19 cell,
valuable metals [44,45]. Similar cost considerations apply to the fuel 100 W MRFBFC stacks were used alone to motivate an electric scooter
cell cathode, whose lifetime is lowered by contact with liquid in the on a level path with on-board fuel, oxidant and an adult driver in a
reactant mixture. A separate-reactant system could avoid cathode 15 min test run at speeds up to 10 km h−1.
wetting but would require ion barriers between bipolar cells and might At this stage of development, the MRFBFC suffers deficiencies of
introduce pressure differentials driving oxygen across the micro-porous high fuel cost, low energy efficiency, inconvenient effluents and short
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