Introduction

Polymer electrolyte membrane (PEM) water electrolysers are a promising

technology for hydrogen production. The catalysts required for water oxidation
at the anode and hydrogen evolution at the cathode are typically based on
iridium/ruthenium oxide and platinum, respectively. Degradation mechanisms
of these catalysts under typical electrolyser operating conditions are poorly
understood, hindering informed catalyst design for extended lifetimes and more
economical loadings.
Here we demonstrate the use of a novel reference electrode for in situ
measurement of electrode potential during power cycling and its application
to the study of catalyst degradation.
Reference electrode
A hydrogen reference electrode (Hydrofex)
was attached to the electrolysis cell via a Nafon
tube salt bridge flled with sulphuric acid and
sealed with Nafon. The salt bridge makes
contact with the back of the Pt cathode, which
was used as the working electrode in this study.
Electrode potential
The reference electrode enables separation of
the anode and cathode contributions to cell
voltage during electrolysis as shown in the
polarisation curve (Figure A).
When current is switched of (Figure B), after
the initial drop in cell voltage to the open
circuit value (~ 1.4 V), a second slow decay in
cell voltage was observed, which was found to
be due to oxidation of the Pt (cathode) surface.
This implies that this electrode is susceptible to
degradation from power cycling. Accordingly,
an accelerated degradation test was devised,
involving repeated on-of cycling of the cell.
Power cycling
A short stack was cycled between 1 A cm
-2

(10 mins) and open circuit (1 min), with a
3 s ramp, for 18400 cycles. For a simulated
cycle in the instrumented single cell,
the measured electrode potentials
are plotted here.
Electrochemical surface area
Electrochemical surface area (ECSA) of Pt
catalysts can be measured via integration of
the charge associated with Pt-H underpotential
deposition. For the frst time, this has been
carried out in a water electrolyser in situ using
the NPL reference electrode, with the IrRuOx
electrode acting as a counter electrode (CE). The
potential of the CE was monitored and found to
stay within safe limits during the measurement.
Power cycling in a stack over 18400 on/of cycles
was found to cause ~ 60% loss of ECSA at the
cathode in this study.
Microstructural analysis
Focused ion beam (FIB) milling was used to examine the cross-section of unused
and degraded sample catalyst layers and membranes. The observed loss of
ECSA correlates with a thinning of the catalyst layer by around 90%. This may be
due in part to compression of the porous catalyst but mostly to dissolution or
delamination of bulk Pt. Elemental analysis found no trace of Pt migration into
the membrane.
Conclusions
nIn situ reference electrode enables separation of anode and cathode potentials
in a PEM electrolyser.
nSurface oxidation of Pt occurs when the electrolyser is at open circuit, resulting
in a decrease in cell voltage.
nMeasurement of Pt ECSA in situ has been carried out for the frst time in
an electrolyser.
nPower cycling led to a signifcant loss of Pt in the cathode.
Implications
nPower cycling can be used as an accelerated durability test protocol.
nThis work will lead to catalysts with improved durability and more economical
precious metal loadings.
www.npl.co.uk
In situ characterisation of
PEM water electrolysers
using a novel reference electrode
E. Brightman
1
, E. Payne-Johnson
2
, N. Van Dijk
2
, G. Hinds
1
1
National Physical Laboratory, Hampton Road, Teddington, Middlesex TW11 0LW, UK
2
ITM Power, 22 Atlas Way, Shefeld, S4 7QQ, UK

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Acknowledgements
The authors gratefully acknowledge Helen Jones at NPL for carrying
out the microstructural analysis.
This work was funded by the National Measurement Ofce under the
IRD Programme (Project no. 117479).
Reference
Electrode
Salt bridge
H
2
(gas)
Anode
E
+
+1.4 - 2.0 V
Cathode
E
-
0.0 V
e
-
Ir
x
Ru
1-x
O
2
Pt-B or Pt/C
H
2
O
O
2
(gas)
Polymer membrane
(e.g. Nafon)
H
+
Aged sample FIB milled cross section of Pt catalyst layer.
Catalyst layer ~1m
Unused sample FIB milled cross section of Pt catalyst layer.
10 m
Summary of electrochemical surface area estimated from in situ CV.
Cyclic voltammogram (CV) of Pt electrode in a
PEM electrolyser cell, highlighting the features
used to estimate ECSA.
A
CV of unused (black, solid) and aged (red, dashed) Pt electrodes in situ.
Scan rate = 100 mV/s.
B