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High efciency electrical energy storage using a methaneoxygen solid oxide

cell

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David M. Bierschenk, James R. Wilson and Scott A. Barnett*

Received 20th September 2010, Accepted 19th November 2010
DOI: 10.1039/c0ee00457j
Reversible solid oxide cells (SOCs) are potentially useful for electrical energy storage due to their good
storage scalability, but have not been seriously considered due to concerns over round-trip efciency.
Here we propose an SOC storage chemistry where the fuel cycles between H2OCO2-rich and CH4H2rich gases. The unique feature is the formation of CH4 during electrolysis, a less endothermic process
than the usual H2- or CO-forming reactions, enabling improved efciency. Thermodynamic
calculations and preliminary experiments show that the CH4-rich storage chemistry is produced during
SOC operation at reduced temperature (600  C) and/or increased pressure (10 atm). Balance of
plant storage system requirements are discussed briey.

1. Introduction
Electrical energy storage has a number of well-known applications for improving the ability of the grid to efciently respond to
demand uctuations.14 The need for storage is becoming more
acute as increasing amounts of intermittent renewable electrical
sources come on line, making it increasingly difcult to match
uctuations in both supply and demand.1,3 Perhaps the most
challenging problem is storage over relatively long (several hour)
times, requiring the ability to store energy on a large scale.
Currently available methods generally fail to meet at least one of
the key storage-technology targets including cost, efciency,
storage capacity, and widespread availability.13,5 Hydroelectric
water pumping and underground compressed air storage are well
established but limited to specic naturally occurring geographic
sites. Secondary batteries and ultracapacitors currently have
limitations for storing large amounts of energy cost effectively.
Flow batteries may provide more scalable storage, although
electrolyte volume and cost scale with energy stored.6,7
Department of Materials Science and Engineering, Northwestern
University, Evanston, 60208, Illinois, USA. E-mail: s-barnett@
northwestern.edu

Reversible fuel cells have received only limited consideration

for energy storagealthough they have potential for large-scale
storage, round-trip efciency is expected to be relatively low.8,9
Most of the work has focused on regenerative proton exchange
membrane (PEM) cells,811 or PEM fuel cells combined with
alkaline electrolyzers.12,13 In both cases, relatively high overpotentials are required to achieve acceptable current densities,
leading to relatively low efciencies. Reversible solid oxide cells
(SOCs) have not been widely explored for electrical energy
storage. On the other hand, SOCs have received considerable
attention as electrolyzers for fuel production from renewable
electricity,1418 and of course as fuel cells for electricity production.19
Here we discuss the fundamental limitations on round-trip
efciency of reversible SOCs and propose a storage chemistry
that can potentially yield efciencies competitive with the storage
technologies discussed above. The new storage chemistry, which
cycles between H2OCO2-rich and CH4H2-rich gases, is enabled
by SOC operation at reduced temperature (600  C) and/or
increased pressure (10 atm). The CH4-forming electrolysis
reactions require less heat energy input than the usual H2- or

Broader context
Large-scale electrical energy storage is becoming increasingly necessary due to the continued growth of intermittent renewable
sources such as wind and solar. However, currently available methods generally fail to meet at least one of the key storage-technology targets including cost, efciency, storage capacity, and widespread availability. Reversible solid oxide cells have many
desirable attributes for this application, but have not been widely considered due to their relatively low round-trip efciency. Here we
show a reversible solid oxide cell storage chemistry where the fuel cycles between H2OCO2-rich and CH4-rich gases, enabled by
operating at reduced temperature and/or increased pressure. The CH4-forming electrolysis reactions require less heat energy input
than the usual H2- or CO-forming reactions, thereby allowing a much-improved round-trip efciency.
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CO-forming reactions, allowing improved round-trip storage

efciency.

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2. Reversible solid oxide cell efciency

Fig. 1 shows schematically one possible embodiment of
a reversible SOC storage device. The SOC is operated in electrolysis mode (dashed arrows) to store energy in a fuel in one
tank, and then in fuel cell mode (solid arrows) to convert that
stored fuel back to electricity, producing a gas mixture that is
stored in a second tank. In electrolysis mode, pure oxygen is
produced by the SOC. A likely scenario, as shown in Fig. 1, is to
store the pure oxygen in a third tank to be consumed in fuel cell
mode, although the atmospheric air could also be employed.
Similar schemes have been proposed for reversible PEM cells.10,11
The round-trip efciency (h) for reversible cells has been
described previously.9,14 When parasitic and heat transfer losses
are neglected, the ideal efciency is the quotient of energy
supplied during discharging and energy consumed during
charging (eqn (1))
h VFCQFC/VELQEL

(1)

where energy is the product of the cell potential (V) and charge
(Q) supplied or consumed.14 The effects of parasitic losses and
heat losses to the environment are discussed in Section 5.2. Note
that the reversible system in Fig. 1 is closed, unlike a conventional fuel cell where fuel/oxidant enters and exhaust leaves the
device. Thus, fuel utilization efciency is not a factor in determining system efciency. If the coulometric efciency is 100%,
i.e. the electrolyte does not have a leakage current due to mixed
conductivity and none of the reactants are lost due to gas
leakage, QFC QEL and eqn (1) reduces to:
h VFC/VEL

(2)

Therefore, in order to maximize h, VFC and VEL should be as

close as possible.

Fig. 1 Schematic diagram of a simplied reversible SOC system. Electrical energy is stored by electrolyzing a H2OCO2-rich mixture (dashed
arrows) and electricity is produced (solid arrows) in fuel cell mode
utilizing the resulting H2CH4-rich fuel. Pure oxygen is produced during
electrolysis and is stored for use during fuel-cell operation.

Energy Environ. Sci.

Fig. 2 Potential versus current density at 800  C for an SOC with 50%
H250% H2O or 25% H225% CO250% H2O at the fuel electrode, and
air at the oxygen electrode. Data are presented for operation in both
electrolysis mode (negative current) and fuel cell mode (positive
current).14

In order to determine h, the specic cell reactions and cell

characteristics must be considered. An SOC performs electrolysis
by extracting oxygen from H2O (or CO2) across an oxygen-ionconducting electrolyte:
H2O / H2 + (1/2)O2, DH (800  C) 248.3 kJ mol1,

(3)

CO2 / CO + (1/2)O2, DH (800  C) 282.4 kJ mol1,

(4)

or

nominally producing a H2 (CO) enriched fuel gas and pure O2.

These reactions are reversed in fuel cell mode. Fig. 2 shows
typical results for the potential versus current density of an SOC
operated at 800  C in 50% H250% H2O or 25% H225% CO
50% H2O at the fuel electrode, with air at the oxygen electrode.14
VEL must be maintained above the open-circuit potential VOC
(approximately equal to the Nernst potential E) in order to drive
a current through the cell and thereby produce H2 and/or CO via
electrolysis. For the H2H2O fuel gas and air oxidant used in the
SOC in Fig. 2, VOC 0.97 V. Imposing a potential VEL VOC +
0.1 V yields an electrolysis current density of 0.5 A cm2,
whereas decreasing the potential to VFC VOC  0.1 V yields
a fuel cell current density of +0.5 A cm2. Using these potentials
in eqn (2) yields h 0.87 V/1.07 V 81%. For the cell operating
on the CO2H2H2O mixture, overpotentials of 0.1 V gave
currents of 0.45 A cm2. That is, typical SOCs satisfy a key
requirement for a reversible device: sufciently low resistance to
allow technologically useful current densities at low overpotentials consistent with high efciency. Note that the low
resistance, along with the ability to work with carbon-containing
fuels (including providing expected Nernst potentials20) and
catalyze desired reactions, are key reasons for using SOCs in
electrical storage.
While the above arguments suggest that high h should be
possible, there is another factor that usually requires a higher
VEL, and thereby limits h. That is, the thermal energy DH
If the current density is too small, then the device active area required to
store/produce energy at the required power level becomes too large, such
that the device becomes excessively large and expensive.

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required for the endothermic electrolysis reactions (3) and (4)

must be supplied from some source. Otherwise, the device will
uncontrollably cool below its operating temperature and cease
functioning. Some studies have envisioned using an external
high-temperature heat source, such as a nuclear reactor, for this
purpose.17 More typically, however, the energy is supplied by the
electrical energy input zFVEL (F is Faradays constant and z is the
number of electrons transferred). Assuming that the electrical
input must match or exceed DH yields the thermal neutrality
condition:

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VEL $ VTN DH/zF,

(5)

where VTN is the thermo-neutral voltage. For reaction (3),

VTN,H2 1.29 V and for reaction (4) VTN,CO 1.48 V; z 2 for
both reactions. In the case of renewable fuel production, where
the SOC is used exclusively as an electrolyzer, this is not
considered to be a disadvantage since all of the electrical input is
being used to produce H2 or CO fuel, and the high potentials
produce desirably large current densities.15,16 For the case of
reversible energy storage, where achieving high round-trip efciency is important, the high VTN values are a serious limitation.
For example, using the previous value of VFC 0.87 V with VEL
$ VTN yields h # 67% for reaction (3) and #58% for reaction (4).
For comparison, other storage methods such as hydroelectric
water pumping, compressed air storage, and Li-ion batteries can
yield h $ 80%.1

3. Thermodynamic predictions
The present method is a means of reaching higher h by reducing
VTN and thereby allowing lower VEL. This is achieved by
selecting the fuel gas compositions, operating temperature (T),
and pressure (P) such that the electrolysis reactions are less
endothermic. The fuel compositions are conveniently represented
on the CHO composition map in Fig. 3a. In order to illustrate
the concept, a specic set of gas compositions was selected,
shown as the dashed line at a constant H : C ratio of 7.7 between
pts 1 and 2 in Fig. 3a. Pt 1 (8.2% C, 63.1% H, 28.7% O) is the gas
composition in the feedstock storage tank in Fig. 1, whereas pt
2 (10% C, 77% H, 13% O) is that of the fuel storage tank.
Moving to the right between pts 1 and 2 represents addition of
oxygen (fuel cell mode), whereas moving to the left represents
removal of oxygen (electrolysis mode). Fig. 3a also shows the gas
composition limits for the reversible cycle. The H2OCO2 tie-line
on the right shows completely oxidized fuel. The solid carbon
formation boundary curves vary with T and P, bounding the
composition space on the left. Carbon formation must be avoided because it will shift the gas H : C ratio out of the desired
range and also damage the SOC.21 The criteria for selecting
optimal storage-cycle gas compositions include factors such as
SOC performance and system considerations, and are beyond
the scope of this paper.
Fig. 3b and 47 summarize the predicted gas constitutions
equilibrated in an SOC operated at various conditions. Fig. 3b
shows the CH4 fraction versus oxygen content for various SOC
operating conditions. For conventional SOC electrolyzer
conditions (T 750  C and P 1 atm), the CH4 content is low.
Reducing T to 600  C shifts the gas constitution substantially,
This journal is The Royal Society of Chemistry 2011

Fig. 3 (a) CHO ternary composition diagram section. The carbon

(graphite) forming boundaries are indicated for T 600 and 750  C at
P 1 and 10 atm. (b) CH4 content at T 600 and 750  C at P 1 and 10
atm as a function of oxygen fraction.

with CH4 increased to 14.3% at pt 2. Fig. 4 shows all the major

gas constituents versus oxygen content for this case, showing that
CH4, H2, and CO all increase, and H2O and CO2 decrease, as
oxygen is extracted. Pressurization to P 10 atm at 750  C yields
a similar increase in the CH4 content in Fig. 3b to 15% at pt 2,
while P 10 atm and T 600  C yield a higher CH4 content of
27.6% at pt 2.
Fig. 5 shows the gas constitution at pts 1 (a) and 2 (b) versus T
for P 1 atm. Fig. 5a shows that at pt 1 and 600 to 800  C, the
gas consists of 40% H2O, 40% H2, 1114% CO2, <10% CO,
and a trace of CH4. At typical SOC electrolyzer conditions (T $
750  C and P 1 atm), the equilibrium gas becomes enriched
primarily in H2 and CO on going from pt 1 to pt 2. That is, the
overall electrolysis process is essentially a combination of the
reactions (3) and (4). At lower T, there is increased CH4 and H2O
production at the expense of H2 and CO. Fig. 6 shows the gas
constitution at pts 1 (a) and 2 (b) versus T for P 10 atm.
Comparison of Fig. 6a and 5a shows that pressurization of the
feedstock (pt 1) increases the H2O and CH4 contents at lower T.
Comparison of Fig. 6b and 5b shows that pressurization of the
fuel (pt 2) increases H2O and CH4 at the expense of H2 and CO.
This trend, also shown in the plot of gas constitution versus P in
Fig. 7, is consistent with Le Ch^
ateliers principle given that the
CH4H2O-rich gas has fewer total moles.
The increase in CH4 content upon decreasing T or increasing P
results in a lower DH/zF for the net electrolysis reaction, such
that VTN in eqn (5) is decreased. Fig. 8 and 9 show VTN versus T
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Fig. 4 Equilibrium gas constitution versus oxygen content at T 600  C

and P 1 atm for an H : C ratio of 7.7.

Fig. 6 Equilibrium gas constitution at pt 1 (a) and pt 2 (b) for P 10

atm from T 500 to 800  C.

Fig. 7 Equilibrium gas constitution at pt 2 for T 750  C from P 1 to

20 atm.
Fig. 5 Equilibrium gas constitution at pt 1 (a) and pt 2 (b) for P 1 atm
from T 500 to 800  C. The exhaust constitution measured by gas
chromatography, after owing a gas mixture containing 79% H2, 14%
CO, and 6% CO2 (pt 2) over a 0.6 g NiYSZ electrode (closed symbols), is
also shown in (b).

and P, respectively, calculated for a gas at pt 1 electrolyzed to pt

2. At 750  C and 1 atm, VTN 1.272 V. With T reduced to 600  C
and P 1 atm, VTN is reduced to 1.073 V. For P 10 atm and T
< 750  C, VTN stays in a narrow range from 1.041.07 V. High
efciency is obtained by using VEL relatively close to VFC (eqn
(2)), and hence both must be near the Nernst potential E. Thus, E
values for the gas compositions ranging from pt 1 to pt 2 have
been included in Fig. 8 and 9 as shaded areas. Fig. 8 shows that it
is possible to achieve VTN z E for T # 600  C and 1 atm, or P
10 atm and T # 750  C. In this case, when a VEL value > E is used
Energy Environ. Sci.

to produce a net electrolysis current, there is also net heat

produced (proportional to the difference VEL  VTN); as discussed further below, this excess heat will be important for offsetting thermal losses. The reduced VTN also impacts fuel cell
mode, since the excess heat produced is proportional to the
difference VTN  VFC. That is, less heat is produced under the
proposed operating conditions than under more conventional
SOC conditions. Note that the present CH4-containing fuel
composition (pt 2) is similar to that used in internal reforming,
a well-known strategy for reducing the heat production in solid
oxide fuel cells.22
Finally, note that the proposed approach is very different than
previously described strategies where H2 + CO is rst produced
from H2O + CO2 in an SOC, and then converted to CH4 or other
hydrocarbons in a separate lower-temperature catalytic
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Fig. 8 Thermal-neutral potentials versus T at P 1 atm and 10 atm for

a cell operating over a fuel composition range from pt 1 to pt 2 (Fig. 3).
Shown for comparison are the Nernst potential ranges for fuel compositions from pt 1 to pt 2 and oxygen at the other electrode at P 1 atm
(light grey) and 10 atm (dark grey).

contained no CH4. A typical SOC Ni8 mol% yttria-stabilized

zirconia (YSZ) electrode (0.6 g) was exposed to this mixture at
a ow rate of 22 sccm from T 500 to 700  C. The measured
exhaust gas constitution, shown in Fig. 5b, matched the equilibrium prediction within the experimental error for gas chromatography. That is, the NiYSZ electrode was an effective
catalyst, which is not surprising given that Ni is a common
catalyst for the reforming and Sabatier reactions.23,24
Preliminary experimental validation was obtained using
anode-supported SOCs similar to those reported previously.25
Since pressurized testing capabilities were not available, the cell
testing was done at T 600  C and P 1 atm. The cells provided
limited current at 600  C (such cells normally operate at T $ 750

C), such that it was not possible to span the full composition
range from pt 1 to pt 2. The test was done with a gas containing
79% H2 and 21% CO2, located between pts 1 and 2, and the cell
was operated in both fuel cell and electrolysis modes. Fig. 10
shows the measured exhaust constitution versus cell current. The
gas constitution variation with oxygen content (the latter determined from the cell current and the gas ow rate) was in
reasonable agreement with the thermodynamic prediction in
Fig. 4, including an increase in CH4 content from 2 to 8% on
going from fuel cell to electrolysis mode. The H2, CO, CO2, and
H2O trends also matched the equilibrium prediction.

5. Discussion

Fig. 9 Thermal-neutral potentials versus P at T 750  C for a cell

operating over a fuel composition range from pt 1 to pt 2 (Fig. 3). Shown
for comparison are the Nernst potential ranges for fuel compositions
from pt 1 to pt 2 and oxygen at the other electrode.

reactor.15 In the present case, the heat of CH4 formation is

utilized to make the overall cell reaction less endothermic; when
a separate lower-temperature reactor is used, the cell reaction
remains highly endothermic for syngas production.

The above results show a promising pathway to achieving high

efciency SOC electrical energy storage. A number of factors
must be addressed to design the storage system and establish the
desired characteristics of its components. These will ultimately
determine system characteristics including efciency, power
capacity, energy storage capacity, and lifetime. A few key
issuesSOC performance and durability, system design, and
thermal lossesare discussed briey below; a more detailed
analysis is beyond the scope of this paper.
5.1 Cell performance
SOC performance requirements are discussed briey here. For
purposes of illustration, we assume a target ideal efciency h of

4. Experimental results
Kinetic processes within the SOC will not necessarily produce the
equilibrium products predicted thermodynamically. For
example, the fastest fuel-electrode reaction during electrolysis is
expected to be reduction of H2O to H2.14 The production of the
predicted equilibrium CH4-containing gas compositions thus
requires catalytic reactions in the H2-enriched gas, such as the
CH4-forming Sabatier23,24 or reverse-reforming reactions. The
fuel electrode must provide both electrochemical and catalytic
activities. Experiments were thus carried out to determine if the
NiYSZ electrode commonly used in SOCs provides the desired
catalytic activity. A gas mixture containing 6.2% CO2, 14.4%
CO, and 79.4% H2 (pt 2 in Fig. 3) at 1 atm was used. Compared
to Fig. 5b, this was not the equilibrium constitution, as it
This journal is The Royal Society of Chemistry 2011

Fig. 10 Measured exhaust gas constitution as a function of cell current

from an SOC operated at T 600  C and P 1 atm on a gas containing
79% H2 and 21% CO2 (between pts 1 and 2) supplied at a ow rate of 30
sccm.

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80%, a value competitive with other electricity storage methods.1

Using eqn (2) and assuming a Nernst potential E 1.0 V, h z
80% is obtained for VFC 0.9 V and VEL 1.1 V, i.e., when the
overpotentials in both modes are 0.1 V. In order to provide
a practically useful current density $ 0.5 A cm2 at these relatively low overpotentials, the SOCs should have an area-specic
resistance RAS # 0.2 U cm2. Note that 0.5 A cm2 is used here
since it is typical of current solid oxide fuel cell system technologies that are at a near-commercial level of development.26,27 If
the cell resistance is higher, then either the current must be
decreased, lowering the power capacity of the device, or the
overpotentials increased, decreasing the efciency.
Reaching the RAS target should be feasible for one of the
proposed conditions, P z 10 atm and T z 750  C, using
conventional solid oxide fuel cells (SOFCs). Anode-supported
SOFCs are typically designed to operate at T $ 750  C.2830 They
utilize 10 mm thick yttria-stabilized zirconia (YSZ) electrolytes
with a resistance of 0.05 U cm2 at 750  C,31 well below the target
cell resistance. Thus, the electrode resistances combined should
be #0.15 U cm2. Current anode-supported solid oxide fuel cells
used in stack demonstrations are close to meeting the proposed
cell resistance criteriontwo different reports showed overpotentials of 0.15 V at 0.5 A cm2 when operated at 750  C,26,27
corresponding to 0.3 U cm2. Furthermore, pressurization of the
gases and the use of pure oxygen will signicantly improve
electrode performance.3235 Although the dependence of electrode polarization resistance (RP) on reactant (O2 or H2) pressure
is relatively weak at high pressure, e.g., RP f p0.25,36 a pressure
increase from P 1 to 10 atm decreases RP by a factor of 0.56.
The other proposed condition is T z 600  C and P 110
atm, where it is more challenging to make cells with RAS # 0.2 U
cm2. It is well known that SOFC resistance increases rapidly with
decreasing temperature T. The resistance of a 10 mm thick YSZ
electrolyte at 600  C is 0.3 U cm2, larger than the cell target
value. Thus, alternative electrolyte materials must be used. Ceria
electrolyte cells have been studied for reduced-temperature
operation, e.g., yielding a total cell resistance of RAS z 0.2 U cm2
at 600  C,37 but they are probably not suitable for this application because their mixed conductivity results in leakage currents
that would reduce coulometric efciency. Sc-stabilized zirconia
(SSZ) and La0.9Sr0.1Ga0.8Mg0.2O3d (LSGM) are promising
candidates: 10 mm thick layers of SSZ or LSGM have resistances
< 0.1 U cm2 at 600  C,31 consistent with the RAS target. Electrode
resistances also increase rapidly with decreasing T, such that
achieving suitably low RP is challenging even with a performance
boost from pressurization. Nonetheless, there are some promising results. An SSZ tubular cell has been reported that showed
a substantial increase in power density, to 1.48 W cm2 at 650  C,
with pressurization to P 6.9 atm, although RAS values were still
relatively large.38 In one report, an LSGM electrolyte cell yielded
RAS z 0.15 U cm2 at 600  C.39 Oxygen electrodes with RAS # 0.1
U cm2 at 600  C have been reported.40,41
Good durability of the SOCs is an important requirement.
Solid oxide fuel cell durability has been studied extensively, and
cells have been successfully operated for tens of thousands of
hours.42,43 SOCs operated as electrolyzers have also been studied
recently; while good durability has been reported in some cases,
there does appear to be a stability issue for cells operated at VEL
$ 1.3 V,4447 where oxygen electrode delamination is often
Energy Environ. Sci.

observed after sustained operation.44,48 Interestingly, the lower

VEL values discussed here should substantially reduce, and
perhaps eliminate, such degradation. Little is known about the
durability of SOCs when operated reversibly, and studies in this
area will be important.
5.2 Thermal and parasitic losses
As noted in Section 3, during electrolysis VEL should exceed VTN
by enough to provide sufcient heat to overcome thermal losses
to the surroundings. Similarly, VFC < VTN is needed to provide
excess heat during fuel cell operation. Thus, thermal losses
dictate an upper limit on the ideal efciency (VFC/VEL) and,
therefore, are discussed briey below. A more complete and
quantitative analysis is beyond the scope of this paper, as it
would require detailed systems analysis combined with experimental measurements on a full-scale system. However, there is
a considerable knowledge base on the similar solid oxide fuel cell
technology, where methods have been developed to produce
thermally efcient systems.27 The key components of heat loss
are (1) heat lost by raising the temperature of the fuel and oxidant
gases from the storage tank temperature to the cell operating
temperature, (2) heat lost from the storage tanks, and (3) heat
lost through the thermal insulation surrounding the stack. Note
that the present discussion assumes that the reactants are stored
in gaseous form, requiring tank temperatures of 100 to 200  C
chosen to avoid condensing liquid H2O. Recuperative heat
exchangers would be used to minimize (1). Tank heat losses are
offset by excess heat in the incoming gases due to heat exchanger
inefciency. The heat loss from (2) and (3) will depend on
component geometry, size, insulation type, and insulation
thickness. The heat lost through the tank insulation, normalized
to the amount of energy stored, decreases with increasing tank
size. The heat lost through the stack insulation, normalized to the
storage power level, decreases with increasing stack size. Thus,
larger systems can potentially be more efcient.
Finally, parasitic losses must be considered. Electrical pumps
and blowers used to distribute or compress the gases consume
a portion of the electricity generated and thereby decrease the
efciency. By analogy with solid oxide fuel cell systems, which
are quite similar to the proposed systems and are sometimes
pressurized as proposed here,32 these losses typically represent at
most a few percent of total system power.27
5.3 Balance of plant
The simplied schematic in Fig. 1 shows one possible
embodiment of the storage system including some balance of
plant components, i.e., two fuel storage tanks and an oxygen
tank, but omitting others such as pumps/blowers and heat
exchangers. An initial estimate was made of the gas storage
tank volume required to store a given amount of energy,
assuming gas-phase storage. For a cell operating between gas
compositions at pt 1 and pt 2 at T 600  C and P 1 atm, 12
Wh of electricity is stored per mole of gas (including oxygen).
Using conservative conditions for the storage tank of P 17
atm at T 177  C (conditions that will keep H2O in the gas
phase), the resulting energy storage density is 5.3 kWh m3,
including all three tanks shown in Fig. 1. This system
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conguration is only one possibility and is certainly not

optimal with regards to storage volume. For example, the
oxygen tank could be eliminated, reducing system size and cost,
by utilizing atmospheric air at the oxygen electrode. On the
other hand, pure oxygen has the advantage of improving
oxygen-electrode kinetics due to the 5 increase in oxygen
partial pressure compared to air. Higher-density storage might
be achieved by reducing the feedstock storage tank temperature, such that steam (the predominant component as shown in
Fig. 5a and 6a) is condensed to liquid water. This alteration
would best be combined with a catalytic reactor operated at
a lower temperature than the SOC, 400 to 500  C, inserted
between the SOC and fuel storage tank for use during electrolysis. This would increase the CH4 fraction in the product,
thereby increasing the fuel storage tank energy density and also
producing sufcient heat to boil the water being supplied from
the feedstock storage tank.
The proposed SOC storage method possesses a unique
advantage, relative to other electrochemical storage devices such
as batteries, that could further reduce storage tank requirements.
That is, the storage media are rich in CH4, H2O, and CO2, all
widely available. The option of connecting the SOC to an
external natural gas network, effectively using it as extended gas
storage, would allow much-reduced tank sizes. During an
extended period of high electrical demand relative to supply,
when a relatively small fuel tank would be emptied, an external
natural gas supply could be used to continue providing power.
On the other hand, during an extended period of high electrical
supply relative to demand, when a relatively small fuel tank
would become full and the feedstock tank emptied, the H2CH4
rich fuel mixture could be more completely converted to CH4 in
the above-mentioned catalytic reactor and exported into the
natural gas network (note that this would also require an external
supply of H2O and CO2). That is, the proposed SOCs can
provide a means for transparently exchanging between electrical
and natural gas energy supplies. The recent proposed use of
SOCs for renewable fuel production,14,15,49,50 solid oxide electrolysis of H2OCO2 mixtures at 800  C to rst produce H2 +
CO, followed by a lower-temperature catalytic reaction to
produce CH4, is similar to the electrolysis portion of the present
storage cycle. However, the present approach, where signicant
CH4 is produced within the SOC versus in a separate reactor, has
signicant efciency benets.

6. Experimental
6.1 Equilibrium gas calculations
The equilibrium gas constitutions and coking conditions were
calculated with Thermocalc using the substance database
SSUB3. Gases were assumed to behave ideally under all conditions calculated. Graphite was assumed to be the solid carbon
phase.
6.2 Thermal neutral and Nernst Potential calculations
The Nernst potential at each condition was calculated using the
effective oxygen partial pressure as determined by the gas
constitution predicted with Thermocalc. Using the expression for
an oxygen concentration cell, the Nernst Potential is:
This journal is The Royal Society of Chemistry 2011



RT
pO2 pos electrode
ln
4F
pO2 neg electrode

(6)

VTN was calculated using eqn (5) and assumes that the fuel and
feedstock gas constitutions reach equilibrium in the SOC due to
their close proximity with the fuel electrode catalyst, and do not
change substantially within the gas feed lines or storage tanks.
6.3 NiYSZ pellet methanation activity
NiYSZ pellets were fabricated with a 5050 wt% mixture of
NiO (J.T. Baker) and YSZ (Tosoh). Tapioca starch (10 wt%) and
PVB were incorporated into the mixture via ball milling in
ethanol. The resulting slurry was dried, sieved (#120 mesh), and
uniaxially pressed into 1.9 cm pellets weighing 0.6 g. The pellets
were calcined at 1400  C for 4 hours in air. For each test, a pellet
(diameter 1.5 cm) was placed in a quartz reactor (ID 1.6 cm)
and supported with quartz wool. Gas containing 6.2% CO2,
14.4% CO, and 79.4% H2 (pt 2 in Fig. 3) at P 1 atm was
supplied with mass ow controllers so that the total ow was 22
sccm. The inlet and outlet (dried) gas compositions were
measured with gas chromatography (Agilent 3000A micro GC)
on a dry basis and the water content was estimated using the
expected carbon to hydrogen ratio in the gas.
6.4 Button cell test
The fabrication and testing conguration of the cells have been
described in detail previously.25 The anode supported SOCs
consisted of a 600 mm thick NiYSZ support with an 20 mm
RhgAl2O3 catalyst layer (AlfaAesar: Rhodium, 1% on alumina
powder), 10 mm NiYSZ anode functional layer, 10 mm YSZ
electrolyte, 20 mm La0.8Sr0.2MnO3d (LSM)YSZ cathode
functional layer, and 20 mm LSM cathode current collector.25
The cell was sealed to an alumina tube with Ag paste (DAD-87,
Shanghai Research Institute of Synthetic Resins), the cell
diameter was 2.5 cm, and the cathode area (2.5 cm2) dened the
active area of the cell. Gas compositions were set with mass ow
controllers to a mixture containing 79% H2 and 21% CO2 at
a total 30 sccm ow rate. The mixture composition is shown as
the dashed line in Fig. 3 with 19% oxygen. The cell exhaust gas
was measured with gas chromatography on a dry basis and the
water content was estimated using the expected carbon to
hydrogen ratio in the gas. The measurements indicated some air
leakage through the Ag seal into the fuel electrode chamber
thus, expected exhaust oxygen contents are not reported.

7. Summary and conclusions

A novel reversible solid oxide cell storage chemistry, where the
fuel cycles between H2OCO2-rich and CH4H2-rich gases, is
proposed. Thermodynamic calculations and preliminary experiments were used to show that methane-containing fuels are
produced during electrolysis operation at reduced temperature
(600  C) and/or elevated pressure (10 atm). The CH4-forming
electrolysis reactions require less heat energy input than the usual
H2- or CO-forming reactions, decreasing the thermal-neutral
voltage and thereby allowing improved round-trip storage efciency. A possible set of operating conditions has been described,
and basic guidelines described as to how gas compositions, T,
Energy Environ. Sci.

View Online

and P impact efciency. The proposed technology poses many

interesting challenges for the solid oxide cell community, in areas
such as SOC performance, system design, and thermal management. Further work will be needed to better assess how storage
system characteristicsincluding efciency, power capacity,
energy storage capacity, and lifetimecompare to other electrochemical storage technologies.

Downloaded by Queens University - Kingston on 31 January 2011

Published on 20 December 2010 on http://pubs.rsc.org | doi:10.1039/C0EE00457J

Acknowledgements
We thank Robert Kee, Robert Braun, Scott Cronin, Gareth
Hughes, Kyle Yakal-Kremski, Ann Call, and Jacob Haag for
useful discussions, and Emma Dutton for assisting with the
Thermocalc calculations. We gratefully acknowledge nancial
support from the National Science Foundation, grant number
CBET-0854223, Department of Energy Basic Energy Sciences,
Award Number DE-FG02-05ER46255, and the Institute for
Sustainability and Energy at Northwestern (ISEN).

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