ARTICLES

PUBLISHED ONLINE: 14 AUGUST 2011 | DOI: 10.1038/NCHEM.1112

Measuring oxygen reduction/evolution reactions

on the nanoscale
Amit Kumar1 *, Francesco Ciucci2, Anna N. Morozovska3, Sergei V. Kalinin1 * and Stephen Jesse1

The efficiency of fuel cells and metal–air batteries is significantly limited by the activation of oxygen reduction and
evolution reactions. Despite the well-recognized role of oxygen reaction kinetics on the viability of energy technologies,
the governing mechanisms remain elusive and until now have been addressable only by macroscopic studies. This lack of
nanoscale understanding precludes optimization of material architecture. Here, we report direct measurements of oxygen
reduction/evolution reactions and oxygen vacancy diffusion on oxygen-ion conductive solid surfaces with sub-10 nm
resolution. In electrochemical strain microscopy, the biased scanning probe microscopy tip acts as a moving,
electrocatalytically active probe exploring local electrochemical activity. The probe concentrates an electric field in a
nanometre-scale volume of material, and bias-induced, picometre-level surface displacements provide information on local
electrochemical processes. Systematic mapping of oxygen activity on bare and platinum-functionalized yttria-stabilized
zirconia surfaces is demonstrated. This approach allows direct visualization of the oxygen reduction/evolution reaction
activation process at the triple-phase boundary, and can be extended to a broad spectrum of oxygen-conductive and
electrocatalytic materials.

T
he broad implementation of electric and hybrid vehicle tech-
nology, development of distributed energy sources, and
optimization of mobile electronic devices requires a significant
increase in the energy and power densities of batteries and fuel cells,
ideally approaching that of hydrocarbon fuels1,2. The use of atmos-
pheric oxygen as an active component of the cathode in fuel cells3
and lithium–air batteries4,5 directly addresses this challenge by
making use of the oxidizer present in the atmosphere. A compara-
tive analysis of the individual contributions to the overall perform-
ance of fuel cells and related systems suggests that one of the most
significant limiting factors is the activation of oxygen reduction
and evolution reactions (ORR and OER)6. Similarly, large charge–
discharge hysteresis (and therefore low efficiencies and lifetimes)
in lithium–air systems is largely related to ORR/OER activation7,8.
Classical solutions for improving ORR kinetics include the use of
electrocatalytic materials, including (most prominently) platinum
and its alloys3, and some transition-metal oxides2,3. The need for
an expensive electrocatalyst is perhaps the most important factor
limiting the large-scale introduction of fuel-cell systems, and is
therefore driving a huge R&D effort in the United States and world-
wide3. Despite the well-recognized role of ORR/OER kinetics on the
viability of energy technologies, the underpinning mechanisms
remain elusive and until now have been amenable only to macro-
scopic studies. The fundamental reason for this dearth of infor-
mation is the complex geometry of active regions such as the
three-phase junction between the gas phase, catalyst/cathode and
electrolyte9, which hinders both structure and property studies
and the development of macroscopic model systems. On the meso-
scopic level, this complexity largely precludes phenomenological
optimization of the material architecture, because the target micro-
structural parameters defining cathode functionality are unknown.
On the atomic level, this lack of structural information limits the
potential impact of first-principle density functional theory
studies, which have already demonstrated their potential in energy
storage10–12 and catalytic systems13.
Here, we demonstrate that ORR/OER phenomena on oxygen-
conductive surfaces can be probed and mapped on the scale of
several nanometres, well below the limit of microcontact measure-
ments14,15, allowing for direct identification of local electrochemical
reactivity and providing insight into local kinetic parameters. This
scanning probe microscopy (SPM)-based approach is based on
the detection of electrochemical strain associated with ionic and
vacancy movement during bias-induced ORR/OER in a process
called electrochemical strain microscopy (ESM). The SPM tip con-
centrates an electric field in a nanoscale volume of material, result-
ing in the injection/annihilation of oxygen vacancies, and
subsequent vacancy transport and migration induced by the bias,
as illustrated in Fig. 1. The vacancy movement results in localized
strain under the tip, detected through dynamic surface displace-
ment. This strain-detection approach enables volumes to be
probed that are 1 × 106 to 1 × 108 times smaller than those accessi-
ble using current-based electrochemical methods16–18.
Dynamic ESM of ORR/OER
ESM probing of ORR/OER reactivity is illustrated in Fig. 1a. The
SPM tip is brought into contact with the surface, and application
of an electric bias shifts the electrochemical potential of mobile
oxygen vacancies at the tip–surface junction compared to the
bulk. At sufficiently high probe bias, the potential drop at the junc-
tion activates the ORR/OER process, resulting in the generation or
annihilation of vacancies depending on the sign of the bias. The
vacancies diffuse and migrate through the material under the com-
bined effect of the electric field and concentration gradient. The
associated changes in molar volume19 result in electrochemical
strains, and associated dynamic surface deformation is detected by
a scanning probe microscope (SPM) at the 2–5 pm level. Note

1
The Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, USA, 2 Heidelberg Graduate School of
Mathematical and Computational Methods for the Sciences, Institut für Angewandte Mathematik, Ruprecht-Karls-Universität Heidelberg, Im Neuenheimer
Feld 293, 69120 Heidelberg, Germany, 3 Institute of Semiconductor Physics, National Academy of Science of Ukraine, 41, pr. Nauki, 03028 Kiev, Ukraine.
* e-mail: ka7@ornl.gov; sergei2@ornl.gov

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ARTICLES
a relaxation of the ESM signal is fit to the phenomenological
O2 e–
[O]
b c d
Figure 1 | ESM technique for measurement of activity on the nanoscale.
a, ESM approach for probing ORR/OER reactivity. The SPM tip is brought
into contact with the surface, and application of an electric bias shifts the
electrochemical potential of mobile oxygen vacancies at the tip–surface
junction compared to bulk. b–d, Evolution of field structure for the tip at
different separations from a platinum nanoparticle. With the tip over the
particle (d), the field intensity is reduced due to the large particle size. Away
from the particle (b), the field geometry is determined by the tip–surface
contact radius. At intermediate tip–particle spacing (c), the field is enhanced
in the gap, and the electrocatalytic effect of the particle additionally activates
a local ORR/OER process.
that in ESM the tip plays a dual role of mobile electrode and electro-
catalytic nanoparticle, allowing for systematic comparison of
electrochemical activity with different combinations of tip materials
and regions on a surface. If the reaction/diffusion process is revers-
ible and involves only generation/annihilation and transport of
vacancies, but not ordering and/or mechanical failure of the
material, the measurements can be performed in the imaging
mode, in which responses are measured over a grid of closely
spaced locations across the surface.
To differentiate vacancy transport and the ORR/OER activation
process and provide insight into both the kinetics and thermodyn-
amics of the process, we introduce the dynamic ESM (D-ESM)
mode, as illustrated in Fig. 2. The sample is probed, and ionic move-
ment under the tip is activated using a set of pulses (50 ms) ampli-
tude-modulated by a slowly varying (0.05 Hz) triangular
waveform (Fig. 2a). Differential detection in the band excitation
(BE) mode20 is used to detect the dynamic (300 kHz) electroche-
mical strain, constituting the ESM signal. A train of BE waveforms is
applied after each d.c. bias pulse to detect the time relaxation of the
signal, similarly to potentiostatic intermittent titration (PITT) in
classical electrochemistry21. A two-dimensional (2D) ESM spectro-
gram representing the response as a function of frequency and time
obtained after each bias pulse is shown in Fig. 2b. These 2D data
describe the position- and voltage-dependent resonance of the can-
tilever coupled with the surface22 and driven by electrochemical
strains. Practically, use of the BE method allows one to compensate
for the effects of the position-dependent tip–surface resonances
(topographic crosstalk) that are inevitable in classical single-fre-
quency SPM measurements, and capture any effects that tip bias
might have on the mechanical properties of the substrate (which
are found to be negligible in yttrium-stabilized zirconia, YSZ).
The response amplitude provides information on the electrochemi-
cal strain activity.
The D-ESM response shown in Fig. 2c can be plotted versus the
magnitude of the applied voltage pulse to obtain ESM loops at suc-
cessive time delays t after the pulse (Fig. 2f ). Alternatively, the
708
© 2011 Macmillan Publishers Limited. All rights reserved
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1112
exponential decay model R(V,t) ¼ R0(V ) þ R1(V)exp(2t/t (V)),
where R0(V) is a static (non-relaxing) response, R1(V ) is a relaxing
amplitude and t (V ) is the relaxation time. The hysteretic voltage
dependence of dynamic relaxation parameters is shown in
Fig. 2d,e. Note that hysteresis loops for R0(V ) and R1(V) are signifi-
cantly different, suggesting that thermodynamic and kinetic
phenomena can be separated in this fashion. To further illustrate
this behaviour, a plot of relaxing ESM hysteresis loops collected at
each time step is presented in Fig. 2f. Delay times of the order of
250 ms are generally sufficient for relaxation to complete. Note
that in the D-ESM imaging mode, data sets similar to those depicted
in Fig. 2 are acquired at each spatial location over a dense grid (typi-
cally 1 × 103 to 1 × 104 pixels), providing information on the local
variability of thermodynamic and kinetic electrochemical behaviour.
Mechanism of hysteretic loop formation in ESM
To explore the mechanisms of ESM hysteresis loop formation, a
series of loops with increasing maximum voltage (Vdc,max) were col-
lected on a (100)-oriented single-crystal YSZ surface using a plati-
num-coated tip as shown in Fig. 3a. As Vdc,max increases, the
hysteresis loop evolves from a closed non-hysteretic response, to
partially open, to a fully formed and saturated loop, similar in pro-
gression to that of polarization-voltage hysteresis in ferroelectrics.
The nucleation voltages (corresponding to the inflection points on
the forward and reverse curves23) do not depend on bias Vdc,max.
The fact that Vdc,max does not affect nucleation strongly suggests
an interpretation in terms of rate-independent (thermodynamically
limited) nucleation-like phenomena.
To establish the role of tip–surface interaction in ESM measure-
ments, hysteresis loops were acquired on several surfaces, including
oxygen conducting materials (YSZ and samarium-doped ceria,
SDC), mixed electronic–ionic conductors (LaxSr1–xCoO3), inert
materials (glass), and metals (gold) using platinum- and gold-
coated tips. Some representative hysteresis loops are shown in
Fig. 3b. The hysteresis loop is closed (that is, the area under the
loop is close to zero) on glass and clean gold surfaces (not
shown). On oxygen electrolytes and mixed ionic-electronic conduc-
tors (MIECs) (not shown), strongly hysteretic responses are univer-
sally observed. For YSZ, SDC and low-voltage imaging of MIEC,
no permanent deformation of surfaces is detected after the many
(104–105) voltage sweeps, suggesting a fully reversible nature of
the process. For YSZ and SDC (not shown), the hysteresis loop
opening is more pronounced for the platinum-coated tip than the
gold-coated tip. This comparison illustrates that both the tip
coating material and oxygen ion conductivity of the surface are
essential for the hysteretic ESM response to appear.
Based on these observations, we interpret the observed dynamic
hysteretic behaviour in terms of a tip-induced reaction-transport
process. Indeed, the observation of an electromechanical response
of the surface in contact mode per se indicates the presence of piezo-
electricity and/or bias-induced ionic motion. Electrostatic tip–
surface force effects must be taken into account, but are in general
weaker, and are largely obviated if the response is measured in the
field-off state as shown in Fig. 2a (see Supplementary
Information). A hysteretic response to slow (20 s) bias sweeps is
consistent with either ferroelectric polarization switching, electro-
chemical reaction, or the presence of slow ionic or structural relax-
ation processes. The fact that YSZ is cubic (in bulk) rules out piezo-
and ferroelectric phenomena, leaving ion dynamics as the primary
explanation for the observed behaviour. A comparison with ioni-
cally non-conductive substrates (glass) and the role of tip coating
further substantiates this picture, because platinum is a much stron-
ger electrocatalytic material than gold.
In this model, the bias and time evolution of the hysteresis loop is
naturally explained by the reaction/transport mechanism presented
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NATURE CHEMISTRY DOI: 10.1038/NCHEM.1112 ARTICLES
a

Applied voltage (V)

20

–20

b
262 40
Resonance (kHz)

response (a.u.)
264

Cantilever
266 20
268
270 0

c
10
ESM response (a.u.)

0 50 100 150 200 (ms) 256 (ms)

0
2 4 6 8 10 12 14 16
Time (s)
e 4 f
d 8 10 0 50 100 150 200(ms)
7 2 ESM response (a.u.) 8
Ro(V) (a.u.)

R1(V) (a.u.)

6 6
0
5 4
–2
4 2
3 –4 0
–30 –20 –10 0 10 20 30 –30 –20 –10 0 10 20 30 20 10 0 –10 –20 –30
Applied voltage (V) Applied voltage (V) Applied voltage (V)

Figure 2 | Dynamic ESM—separating local kinetics from thermodynamics. a, Tip bias waveform in a D-ESM measurement. Each voltage pulse is followed
by train of band excitation waveforms to detect the relaxing electrochemical strain. b, 2D spectrogram of D-ESM response as a function of frequency and
time. Only the data in the bias-off states are shown. c, Time dependence of the ESM amplitude response averaged over frequency space. The relaxation after
each bias pulse is clearly seen. The colour code in c corresponds to the delay time after the pulse. d,e, The response after each pulse is fit to a relaxation
model and the bias dependence of R0(V) and R1(V) are shown in d and e, respectively. f, ESM loops as a function of time delay illustrating phenomenological
relaxation dynamics. Colour scale as in c.

in Fig. 1. For low d.c. tip biases, the potential drop in the tip–
surface junction is small, and the local surface overpotential is
insufficient to activate ORR/OER. The bias-induced vacancy
motion is limited to redistribution of the oxygen vacancies in
the volume of material below the probe, and is responsible for gen-
erating the ESM response signal. However, the hysteresis loop is
closed because d.c. bias pulses do not change the total number
of vacancies. For higher bias windows, the ORR/OER at the tip–
surface junction is activated (as indicated by the inflection
points in the ESM loops), resulting in large changes in oxygen
vacancy concentration and thus large changes in ESM amplitude.
After the bias pulse has been removed, a subsequent slow diffusion
in the material takes place. The kinetics of this process is controlled
by the diffusion times of the vacancies, and is therefore expected to
be relaxational in nature. To estimate the corresponding relaxation
time, we use D(T ) ¼ D0exp(–Ea/kT), where D0 ¼ 2 × 1025 m2 s21
(ref. 24) and Ea ¼ 0.62 eV for nanocrystalline YSZ25 (note that for
bulk material, Ea ¼ 1.09 eV). For diffusion lengths of L ≈ 5–10 nm
(comparable to the tip–surface contact radius) the diffusion times
are then tD ¼ L 2/D(T ) ≈ 0.13 s, comparable with those observed
experimentally. The nucleation biases on the hysteresis loops are
then identified with the critical biases required to activate
ORR/OER. Note that the potential drop is divided between the
tip–surface junction and the material, so the actual overpotential
(or local polarization) is significantly smaller than the tip bias.
Finally, the hysteresis loop shape is controlled by relaxation kin-
etics (see Fig. 2 and the evolution of curves in Fig. 3a). The
static hysteresis loop R0(V ) then describes the thermodynamics
of the process, whereas R1(V ) and the corresponding relaxation
times describe the kinetics of vacancy redistribution. The response
saturates once the diffusion length becomes larger that the
detection volume, which in ESM is controlled by the tip–surface
contact area26.
Numerical modelling of the tip–surface junction
The critical potentials measured in ESM are significantly larger
than those expected in classical electrochemical experiments.
This behaviour can be readily rationalized by considering that the

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ARTICLES NATURE CHEMISTRY DOI: 10.1038/NCHEM.1112

a –2 b
5V 8 YSZ Pt tip
15 V YSZ Au tip
–4
30 V Glass Pt tip

ESM response (a.u.)

ESM response (a.u.)

45 V 4
–6 60 V
0
–8
–4

–10
–8

–12
–12
–60 –40 –20 0 20 40 60 –40 –20 0 20 40
Applied voltage (V) Applied voltage (V)

Figure 3 | Effects of bias magnitude and tip coating on local ESM. a, Electrochemical strain (ESM) loops obtained on an YSZ (100) surface at different peak
biasing voltages. b, Comparison of ESM loops obtained on YSZ using tips with a platinum and gold coating. A reference loop on a glass surface is also
shown. Error bars indicate standard deviation over 100 locations.

·ΦÒrxn/Vth
a e 2.0 0.9
Tip 1.5
Vtip Vtip 0.8
Reaction
1.0
ΔVs log10 (KΦ/K0) 0.7
0.5
Potential

ΔVb 0 0.6

–0.5 0.5
–1.0 0.4
–1.5
0.3
0 –2.0
0 Coordinate –2 –1 0 1 2
log10 (Kc/K0)

b μ* c Φ d cion/[cion]
500 1.0 500 1.0 500
0.0
400 0.8 400 0.8 498
–0.1
300 0.6 300 0.6 496
z/RD
z/RD

z/RD

–0.2
200 0.4 200 0.4 494
–0.3
100 0.2 100 0.2 492
–0.4
0 0.0 0 0.0 490
0 100 200 300 400 500 0 100 200 300 400 500 0 50 100 150
r/RD r/RD r/RD

Figure 4 | Numerical modelling of electrochemical potentials at the tip–surface junction. a, Potential distribution under the tip, composed of the junction
potential (electrochemically active) and the bulk potential drop. b–d, Normalized electrochemical potential of vacancies (b), electrostatic potential (c) and
vacancy concentration (d) at the tip–surface junction in ESM of YSZ surface at room temperature. e, Normalized electrostatic potential at the TPB region
versus surface reaction rates. For low reactivity, the potential drop in the bulk dominates and the effective driving force for the ORR/OER process is well
below tip bias.

highly localized nature of the SPM tip leads to a potential drop both
at the tip–surface junction (inducing the electrochemical process)
and in the bulk, as schematically illustrated in Fig. 4a. The potential
and vacancy concentration can be analysed using the numerical
model developed by Ciucci et al.27,28, extended here to a purely
ionic conductor for material parameters extrapolated from refs 29,
30 and 31 to room temperature (see Supplementary Information),
as illustrated in Fig. 4b–d. The parametric plot of the effective poten-
tial versus reaction rates in Fig. 4e illustrates that for low reactivity
(inevitable at room temperature) the potential drop at the junction
is reduced compared to the tip potential, resulting in ‘stretching’ of
the voltage axis compared to macroscopic experiments. The positive
nucleation bias (PNB) and negative nucleation bias (NNB) in ESM
thus provide local analogues of macroscopic cathodic and anodic
polarization voltages.
Spatially resolved mapping of electrochemical activity
The ESM approach enables spatially resolved mapping of electro-
chemical activity across a solid surface. In this, the dynamic (Fig. 2)
or standard (Fig. 3) hysteresis loops are acquired over a dense 2D
spatial grid, yielding a 3D (or 4D for D-ESM) array of hysteresis
data. Descriptive parameters such as area inside the loop (reactivity),
remanent response or nucleation biases, can be plotted as 2D maps.
The reactivity map obtained on a 1 mm2 area of a (100)-oriented
single-crystal YSZ surface with a pixel size of 20 nm is shown in
Fig. 5. Clearly discernible variations of response across the crystal
surface are seen, indicating the presence of 100–200-nm-scale inho-
mogeneties in the surface reactivity. The hysteresis loops from selected
areas are shown in Fig. 5c, illustrating the difference in spectroscopic
responses between locations. The contact frequency variation and dis-
persion are shown in Fig. 5d and e, respectively. The frequency map

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NATURE CHEMISTRY DOI: 10.1038/NCHEM.1112 ARTICLES
a (nm) b 6 c

Area under ESM loop (a.u.)

1
0.8 1

ESM response (a.u.)

2 0 2
5.25 3
0.6 5 –1 4
4.50 5
–2 6
0.4 1
–3
3.75
4 6 –4
0.2
200 nm 3 3 –5
0
–40 –20 0 20 40
Applied voltage (V)

d e 0.6 g 7 (V)
f
266 4 (V)
4.5

σ (f ) (kHz)
0.4 1
f (kHz)
265
−2 2.0
264 0.2
−5 −0.5
−8 −3.0
263 0

Figure 5 | Local ESM mapping on an YSZ surface with nanometre-scale resolution. a,b, Topography of the (100) YSZ surface (a) and map of ESM
hysteresis loop area (b, reactivity map). Pixel spacing is 20 nm. c, ESM hysteresis loops extracted from the characteristic spots in b. d,e, Contact resonance
frequency (d) and contact resonance frequency dispersion (e) maps. f,g, Negative (f) and positive (g) ESM nucleation voltage maps.

a 60 (nm) b
15 Pt
60 nm YSZ
TPB 1
10 TPB 2
ESM response (a.u.)

40

0
20

–5

0 –10
–20 –10 0 10 20
Applied voltage (V)

c
Pt
3.5

3.0
ESM activity (a.u.)

TPB 2.5

2.0

1.5

YSZ 1.0

0.5

Figure 6 | Mapping electrochemical activity near a triple-phase boundary. a, Topography of platinum nanoparticles deposited on an YSZ (100) surface.
b, ESM loops collected on YSZ, a platinum particle, and two different positions along the triple-phase boundary (TPB) using a platinum tip. c, Overlay of
electrochemical activity on the topography of the nanoparticles reveals enhancement of activity along the triple-phase boundaries.

illustrates the combined effect of surface topography and elastic prop-
erties. Because the topography is essentially uniform, the contrast indi-
cates the presence of intrinsic inhomogeneities in the material. Maps of
the negative and positive nucleation voltages in Fig. 5f,g illustrate that
only the positive nucleation bias varies across the mapped surface, with
the negative nucleation bias being approximately constant. This
suggests the thermodynamic potential for the activation of OER, but
not ORR, varies across the studied YSZ surface region. The likely
origins of this inhomogeneity are non-uniform dopant distributions
or possible contamination of the surface, for example, by silicon
(epitaxial films of SDC, for instance, do not exhibit these variations)32.
Reactivity mapping near a triple-phase boundary in Pt-YSZ
To illustrate reactivity mapping in more complex structures, we
applied ESM mapping to a platinum-nanoparticle-coated YSZ
surface (Fig. 6). We aimed to probe the triple-phase boundary at

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ARTICLES
which the catalyst electrode is in contact with the reactants and the
electrolyte, forming a critical unit in a catalysed reaction. The ESM
response was mapped in a 300 nm region containing the nanopar-
ticles. The corresponding ESM hysteresis loops are shown in Fig. 6b.
The reactivity map is overlaid on the topography in Fig. 6c, revealing
increased reactivity close to the triple-phase boundary in compari-
son to the free YSZ surface. Note the relatively weak ESM response
of the particle itself, the sharp increase of reactivity at the triple-
phase junction, and the low reactivity in the YSZ surface.
This behaviour can be readily explained following the logic illus-
trated in Fig. 1b–d. For the tip positioned on the nanoparticle, the
particle is biased as a whole, and the ORR/OER process is activated.
However, because the particle size is much larger than the tip size,
the field within the YSZ (and hence migration motion) is weaker.
For the tip positioned on the YSZ surface, the applied bias is insuf-
ficient to activate the OER/ORR process, so the hysteresis loop is
only partially open. Finally, for the tip positioned on the junction
between the nanoparticle and substrate, the electrocatalytic effect
of the particle is activated and the electric field also penetrates the
material, resulting in an enhanced response. In this manner, an
increased ORR activity is present around the boundary of a single
catalytic nanoparticle.
Conclusions
To summarize, using electrochemical strain detection we have
demonstrated direct measurements of ORR/OER on the nanometre
scale, in volumes six to eight orders of magnitude smaller than is
possible by conventional electrochemical methods. The mapping
of the YSZ surface demonstrated the presence of 100–200-nm-
scale inhomogeneities, presumably associated with surface contami-
nation. The enhanced ORR activity at the triple-phase junction of
Pt-YSZ has been demonstrated, for the first time providing infor-
mation on the local characteristics of the ORR/OER process.
Nanoscale probing of ORR and OER kinetics and oxygen
vacancy diffusion will provide a transformative change in the
ability to explore and control the mechanisms underpinning the
efficiency of air-based fuel-cell systems and metal–air batteries. In
particular, the capability to directly link local structure and electro-
chemical activity will allow for systematic high-throughput studies
of electrocatalysis and will establish the bridge between atomistic
theory and macroscopic electrochemical measurements. Together,
this will allow for knowledge-driven design and optimization of
energy conversion and storage systems. The breakthrough in effi-
ciency of ORR and associated cost reductions can bring back to
the forefront of research the development and commercialization
of multiple fuel-cell technologies. In the situation where renewable
energy technologies are rapidly gaining broad adoption (for
example, 62% of new generation capacity in the EU is renewable33),
the role of large-scale implementation of lithium–air and fuel-cell-
based vehicles and local and grid-storage components is hard
to overestimate.
Methods
Materials. Platinum nanoparticles, 50 nm in size, were deposited on a YSZ (100)
crystal using direct sputter deposition and laser annealing. A thin film (3 nm) of
platinum was deposited on (100)-oriented YSZ single crystals using d.c. magnetron
sputtering. Subsequent laser annealing (single pulse: KrF, 248 nm wavelength,
650 mJ cm22 fluence, 25 ns pulse width) resulted in the melting and dewetting of the
platinum film into regularly spaced (pitch ¼ 50–100 nm), regularly sized (50 nm)
nanoparticles as shown in Supplementary Fig. S1.
ESM. Atomic force microscopy (AFM) and ESM measurements were performed
with a commercial system (Asylum Research Cypher) additionally equipped with a
LabView/MatLab based band excitation controller implemented on NI-5122/5412
fast AWG and DAQ cards. ESM imaging and spectroscopy were performed with a
200–400 kHz 2Vpp band excitation signal applied to a metal-coated tip. The
spectroscopic measurements were performed with an 1 s/pixel waveform with
2 ms for each d.c. voltage step. Mapping of the electromechanical response was
carried out typically on a 50 × 50-point grid with a spacing of 20 nm, although other
712
© 2011 Macmillan Publishers Limited. All rights reserved
NATURE CHEMISTRY DOI: 10.1038/NCHEM.1112
spacings and image sizes were also used. All measurements were performed with the
biased tip in direct contact with the YSZ and Pt-YSZ surface in ambient air and
without any additional protective coating. The implementation and data analysis in
D-ESM are detailed in Supplementary Section II.
Received 18 May 2011; accepted 7 July 2011;
published online 14 August 2011
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Acknowledgements
This research was conducted (A.K., S.J., S.V.K.) at the Center for Nanophase Materials
Sciences, which is sponsored at the Oak Ridge National Laboratory by the Scientific User
Facilities Division, US Department of Energy. F.C. acknowledges support from a Marie
NATURE CHEMISTRY | VOL 3 | SEPTEMBER 2011 | www.nature.com/naturechemistry
© 2011 Macmillan Publishers Limited. All rights reserved
ARTICLES
Curie Reintegration Grant FastCell-256583. The authors are grateful to P. Rack and
J. Fowlkes for deposition of platinum nanoparticles.
Author contributions
S.J. and S.V.K. proposed the concept. S.J. and A.K. designed the experiments, which were
performed by A.K.. S.J. developed the spectroscopic measurement technique and analysis
tools. The semi-analytical calculations were performed by A.N.M., and numerical
modelling of the electrochemical potential was carried out by F.C. The article was written by
A.K. and S.V.K. All authors discussed the results and commented on the manuscript.
Additional information
The authors declare no competing financial interests. Supplementary information
accompanies this paper at www.nature.com/naturechemistry. Reprints and permission
information is available online at http://www.nature.com/reprints. Correspondence and
requests for materials should be addressed to A.K. and S.V.K.
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