Shannon Boettcher Seminar

Electrochemical Energy Storage: Design
Principles for Oxygen Electrocatalysts

and Aqueous Supercapacitors
Shannon W. Boettcher
Asst. Prof. of Chemistry
University of Oregon
Eugene, USA
Boettcher Solar Materials and

Electrochemistry Laboratory
Shannon Boettcher Electrochemical Energy Storage
Motivation: Powering the planet

Global power
consumption:
~18 TW
3 TW
Worldwide potential*:
Wind < 4 TW
Biomass < 5 TW
Hydro < 1.5 TW
Geothermal < 1 TW
Solar ~ 120,000 TW
*Lewis, MRS Bulletin, (32) 808 2007.
Solar is the only renewable source capable of

providing 20-50 TW of power worldwide.
Solar Energy Challenges

Solar Electricity > 11 per kWh (sunny climate, large installation)
Industrial Electricity ~ 5-10 per kWh
Cost of solar energy must be reduced.

We must store that energy.
Solar Materials and Electrochemistry Lab

Fe
solar fuels
O2
2H2O
Ni
electrochemical capacitors
OER active site design?
interface theory
scalable III-V semiconductors for PV
aq. low-T synthesis of functional films

precise
precursors
Solar fuels synthesis using semiconductors

and electrocatalysts
solution n-type SC
solution p-type SC
Walter, M.; Warren, E.; McKone, J.; Boettcher, S. W.; Qixi, M.; Santori, L.;
Lewis, N. S. Solar Water Splitting Cells. Chem. Rev. 2010, 110, 6446-6473.
Oxygen electrocatalysis has broad

importance
solar water splitting
fuel-cells (ORR)
large scale electrolysis
air-breathing batteries
http://protononsite.com/
Need for well-defined systems

and clean measurements
O2
h+
Smith, R.D.L. et al. Science, 2013, 340, 60.
Designed for maximum

current per geometric area
Dark colored poorly suited
for integrating in solar fuels
systems
What is the role of composition,
conductivity, and porosity?
What is the surface-active
component?
Complicated!
From Wang et al., Electrochimica Acta,

2005, 50, 20592064
How do we design well-defined

catalysts? What determines their
activity?
James Ranney
Team Catalyst
c. 2011
Kerisha Williams
(Dr.) Lena
Trotochaud
Solution-processed ultra-thin film

catalysts
Advantages for
fundamental study:
Catalyst electrical
conductivity (largely) irrelevant
Film composition controlled
exactly by precursor solution
Mass known
Surface area controlled
Facile gas and ion transport
~50 wt% surfactant

~ 0.05 M metal nitrate
ethanol
E-QCM
= Film
spin-casting
NiOx
100 nm
Trotochaud, L.; Ranney, J.K.; Williams, K.N.; Boettcher, S.W. J. Am. Chem. Soc., 2012, 134, 17253.
Initial target: Ni-Co-O
Mixing Co and Ni oxides reported =

better performance.
electronic? chemical? morphological?
H2O *OH *O + H2O *OOH O2
(see Rossmeisl, Norskov, etc.)
* Indicates bonded to the surface
1. Trasatti, S.; Lodi, G. In Electrodes of Conductive Metallic Oxides; Trasatti, S., Ed.; Elsevier: Amsterdam, 1981; Vol. B, p 521-626.
2. Rasiyah, P.; Tseung, A. C. C. A mechanistic study of oxygen evolution on NiCo2O4 J. Electrochem.Soc. 1983, 130,2384-2386.
10
Oxygen evolution with NixCo1-xOy films

Teff = 2-3 nm
Performance
increases
with increasing Ni
content.
No synergistic
effect apparent.
Apparent activity
of plain NiO very
high.
NiCo2O4
20 m
film,1
pH 14
- steady-state (> 15-30 min/step), 1 M KOH (99.999%)

-Hg|HgO 1 M KOH reference
(0.929 V vs. RHE at pH 14 or 0.112 V vs. NHE)
- Rs 2-3 via AC impedance
Why?
1Rasiyah,
P.; Tseung, A. C. C. A mechanistic study of

oxygen evolution on NiCo2O4 J. Electrochem.Soc.
1983, 130,2384-2386.
11
Samples containing NiO evolve as a

function of time
NiOx
?
in-situ formation of a NiOOH?
0.3 V vs. Hg|HgO
1M 99.999% KOH, 20 mV s-1
Corrigan, D. A.; Bendert,. J. Electrochem. Soc. 1988, 135, C156-C156.
12
XPS analysis confirms transition to

Ni(OH)2/NiOOH
Ni 2p
O 1s
NiO
NiO
Ni(OH)2
Ni2O3
Grosvenor, A. P.; Biesinger, M. C.; Smart, R. S.; McIntyre, N. S. New interpretations of XPS spectra of
nickel metal and oxides. Surf. Sci. 2006, 600, 1771-1779.
13
Co substitution suppresses
transformation to oxyhydroxide
# Ni measured with QCM
CV curves collected after 6 hr conditioning:

sample
e- per metal
e- per Ni
CoOx
0.04
n/a
Ni0.25Co0.75Ox
0.07
0.27
Ni0.5Co0.5Ox
0.31
0.63
Ni0.75Co0.25Ox
0.61
0.82
NiOx
1.0
1.0
Alloying with
Co suppresses
formation of Ni(OH)2 /
NiOOH during
conditioning.
1M 99.999% KOH, 20 mV s-1
14
In-situ phase transformation

Active structure:
Rock Salt (NiO)

catalysis limited to surface
X
Brucite/Hydrotalcite (e.g. M(OH)2/MOOH)
catalysis throughout bulk 3D
Spinel (e.g. Co3O4)
catalysis limited to surface
15
Ni(OH)2 electrochemistry studied

extensively for alkaline batteries
Dennis Corrigan:
Ni(OH)2 films cathodically
electrodeposited
Fe increases OER activity

Fe added intentionally
or Fe impurities in
electrolyte
Fe is incorporated into
electrochemically conditioned
NiOOH films
Corrigan, D.A. J. Electrochem. Soc. 1987, 134, 377.
Corrigan, D.A.; Bendert, R.M. J. Electrochem. Soc. 1989, 136, 723.
Electrochemically
Conditioned Sample
EPMA
Fe/(Ni+Co)
XPS
Fe/(Ni+Co)
CoOx
Ni0.5Co0.5Ox
0.034
0.11
NiOx
0.18
0.14
NiOx, electrolyzed
KOH
0.035
0.079
16
Thin-film OER catalyst quantitative

comparison using an EQCM
sample
@J=1
mA cm-2
(mV)
Tafel
Slope
(mV
dec-1)
MnOx
512
FeOx
at = 300 mV
A g-1
TOF
(sec-1)
49 3
1.3
0.0003
409
51 3
4.5
0.0009
CoOx
395
49 1
7.6
0.0016
IrOx
381
42 1
24.2
0.014
Ni0.5Co0.5Ox
321
35 2
273
0.056
NiOx (Fe)
300
29 0.4
773
0.17
Fe0.1Ni0.9 Ox
297
30 1
1009
0.21
(Fe)
2 nm film: 10 mA
= 336 mV
E-QCM
cm-2
TOF = # O2 produced per metal per second
Fe:NiOOH >10x more active an IrO2 and >100x more

active than CoOx
Highest activity OER known in basic media. Why???
Corrigan, D.A. J. Electrochem. Soc. 1987, 134, 377.
Trotochaud, L.; Ranney, J.K.; Williams, K.N.; Boettcher, S.W. J. Am. Chem. Soc., 2012, 134, 17253.
17
The role of Fe in NiOOH

Crystal structure and (dis)order?
Energetics of electronic states,
i.e. d-band position?
Film electronic conductivity?
E(Ni2+/3+)
shifts with
[Fe]
Active site
between the
sheets?
Louie, M.W.; Bell, A.T. J. Am. Chem. Soc., 2013, 135,
12329.
Smith, R.D.L. et al. Science, 2013, 340, 60.
Smith, R.D.L. et al. J. Am. Chem. Soc. 2013, 135, 11580.
Corrigan, D.A. J. Electrochem Soc., 1987, 134, 377.
Corrigan, D.A.; Bendert, R.M. J. Electrochem. Soc. 1989, 136, 723.
18
Minimizing Fe Impurities
X-ray photoelectron spectroscopy
Need to use Mg X-ray source
Activity increase
with each cycle
1500 rpm
Glassy C (GC) rotating disk electrode

Teflon cell, TraceSelect KOH (< 36 ppb Fe)
99.999% Ni(NO3)26H2O
No applied potential required

for Fe incorporation
Corrigan, D.A. J. Electrochem Soc., 1987, 134, 377.
Shannon Boettcher Trotochaud,

Electrochemical
Energy
Storage
L.; Young, S.L.;
Ranney,
J.K.; Boettcher, S.W.
Submitted.
19
Electrolyte Purification
Precipitate Ni(OH)2
TraceSelect KOH and 99.999% Ni(NO3)26H2O
Wash/centrifuge/decant
Add electrolyte and shake
No Fe after
300 CV cycles
Trotochaud, L.; Young, S.L.; Ranney, J.K.; Boettcher, S.W.

J. Am. Chem. Soc. 2014.
20
Role of 3D structure?
from Godwin, I.J.; Lyons, M.E.G. Electrochem. Commun. 2013, 32, 39.
Louie, M.W.; Bell, A.T. J. Am. Chem. Soc., 2013, 135, 12329.
Is -NiOOH actually more active?

Previous reports contain Fe?
21
Crystallized Ni(Fe)OOH
aged in 40 C 1M KOH,
CV 10 mV s-1 every 5
min
Peaks shift with crystallization

of -NiOH2 - activity increases
Shannon Boettcher
No significant change in OER

activity with crystallization
Trotochaud, Young, Ranney, Boettcher, S.W. J. Am. Chem. Soc. 2014.

L.; Young, S.L.;
Ranney,
J.K.; Boettcher, S.W. Submitted.
22
Trotochaud,
Electrochemical
Energy
Storage
Fe-Free NiOOH after crystallization
activity
decreases
New peak formation minimal peak shift

No increase in activity
NiOOH very poor OER catalyst without Fe
L.; Young, S.L.;
Ranney,
Electrochemical
Energy
Storage
Submitted.
23
Aging and crystallinity

Aging increases long-range order
Fe co-deposition gives larger inter-sheet spacing
Order and sheet spacing apparently not (strongly) related

to activity.
24
Does Fe change electronic conductivity

under OER conditions?
2 m
bare
I cond w
=
NldV
gap
spacing
film
thickness
# electrodes
electrode
length
For 100 nm NiOOH

film at 10 mA cm-2,
<1 mV drop
Not important mechanism for activity enhancement

L.; Young, S.L.;
Ranney,
Electrochemical
Energy
Storage
Submitted.
25
Other mixed metal oxyhydroxides?

CoOOH
Fe =
FeOOH
(Fe)CoOOH
(Fe)CoOOH
OER onset near conductivity

onset for FeOOH
Michaela Burke
Burke, Kast, Trotochaud, Boettcher, near

submission to JACS 2014.
26
OER mechanism in (oxy)hydroxides

NiOOH bad OER catalyst low activity
FeOOH has low conductivity thus low apparent activity
Fe active site likely; modulated by NiOOH / CoOOH
electrically conductive porous framework
* See also recent theory / XAS from Norskov, Bell
O Ni or OH
Co
Fe
4OH-
O2
Conductive NiOOH/CoOOH = strongly coupled cations;

delocalized electrons
27
A revised volcano plot

Previous Trend:
Ni > Co > Fe > Mn
oxophilicity
of cation
Subbaraman and Markovic, et.
al. Nat. Mater. 2012, 11, 550.
Real Trend:
NiFe > CoFe > Fe > Co > Ni
Exact opposite
-
Chris Gabor
Adam Batchellor
Qui Hui
Jacyln Kellon
Design better catalysts

Integration with AEM
Michaela Burke
Lisa Enman
28
Semiconductor-catalyst interfaces
Fuding Lin
T.J. Mills
b
energy
b,eff
light
position
Lin, Boettcher, Nature Mater. 13 (1), 81, 2014.
different Jo,cat
Mills, Lin, Boettcher Phys. Rev. Lett. 112, 148304, 2014.
29
Part II: Redox-enhanced

electrochemical double layer
capacitors
Galen Stucky
Brian Evanko
David Ji
Xingfeng Wang
Sangeun Chun
30
Traditional electrochemical double-layer

capacitors
electrolyte
+
+
+
+
+
+
+
+
+
target
energy = 1/2CV2
www.maxwell.com
Pros: power, cycle-ability

Cons: carbon cost, flammable electrolyte,
low specific/volumetric energy
Simon, Gogotsi, Nat Mater 2008, 7, 845.
31
Concept: Redox-enhanced supercapacitor
current
collector
+
separator
Merits (vs. EDLC)

electrolyte weight as active component
increased capacity / specific energy
use of aqueous electrolytes with high solubility (limited by low V)
Challenges
self-discharge
maintain cycleability and high power
Lu, Beguin, Frackowiak, Supercapacitor: Materials, Systems and Applications, Wiley, 2013
32
Redox electrolyte design principles
current
collector
+
separator
use aqueous electrolyte (safety, cost)

need different redox processes at negative and positive electrodes
formal potentials near solvent window (energy)
high solubility (energy)
fast kinetics (power)
stable (cyclability)
design for slow self discharge??
Lu, Beguin, Frackowiak, Supercapacitor: Materials, Systems and Applications, Wiley, 2013
33
Potential redox couple species
MV = methyl viologen
Need:
- high solubility
- large V btw. couples
- fast kinetics
- slow self discharge
34
Three electrode cell design

Epoxy insulating layer
Ni bar
N2 purge
Glassy carbon
(current collector)
10 mg per electrode, ~220 um thick

- Activated carbon prepared by standard
CO2 activation process
- Electrode pellet - AC (85 %) : PTFE (10
%) : Acetylene black (5 wt.%)
35
Control inert electrolyte

Charging Discharging
1 A/g
1 A/g
C = Q/V
energy = 1/2CV2
36
Halogen electrolytes for positive electrode

3Br- Br3- + 2e-
3I- I3- + 2efaradaic
capacitive
charging at 1 A/g
Three electrode Swage-lock cell used to monitor both electrode
processes simultaneously.
37
Self-discharge dynamics
1M
K2SO4
3Br-
Br3- + 2e-
Weber et. al. J Appl Electrochem 41, 1137-1164 (2011).
I- and Br- show slow self-discharge rate (specific absorption)

Fe(CN)64-/Fe(CN)63- redox couple shows fast self-discharge
Co(bpy)32+/Co(bpy)33+ extremely fast self-discharge (electrostatics)
38
Redox electrolytes for positive electrode
MV = methyl viologen
MV+ specific absorption slowing self-discharge?

39
Combined redox electrolytes

1 M KBr/0.1 M MVCl2
capacitive and faradaic responses evident on both electrodes

potentials separated by ~1.4 V ideal in aq. electrolyte
40
Combined redox electrolytes
HV2+
2Br
N
competitive over short times with non-aqueous

cells
replace methyl with heptyl decreases self
discharge dramatically
41
Power energy stability
enhanced stability
and solubility:
O
O
2Br
N
O
O
Chun, S.; Evanko, B.; Wang, X.; Ji, X.; Stucky, G.D.; Boettcher, S.W. In prep for Nature Communications. 2014.
42
Nernstian electrochemical model
Brian Evanko
symmetric electrodes, no separator

agreement with experimental data
improved performance possible
43
Summary: Redox Supercapactiors
redox-active electrolyte = additional

capacity
electrostatics and specific absorption
critical to prevent internal shunting
record performance of ~15 Wh kg-1 for
aq. redox capacitor
>2000 cycles with heptyl-viologen
useful niche between capacitor and
battery?
Sangeun Chun
Brian Evanko
44
Acknowledgements
Interfaces
Oxygen Catalysis
Michaela Burke (Dr.) Lena Trotochaud
Dr. Fuding Lin
Theory and Simulation
T.J. Mills
Young Professor Program
Interfaces:
Basic Energy Sciences

Solar Photochemistry
OER Catalysis:
CSVT GaAs PV:
Redox Capacitors:
Thin Films:
45

Shannon Boettcher Seminar

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Electrochemical Energy Storage: Design

Principles for Oxygen Electrocatalysts

Boettcher Solar Materials and

Shannon Boettcher Electrochemical Energy Storage

Motivation: Powering the planet

Solar is the only renewable source capable of

Solar Energy Challenges

Cost of solar energy must be reduced.

Solar Materials and Electrochemistry Lab

OER active site design?

scalable III-V semiconductors for PV

aq. low-T synthesis of functional films

Shannon Boettcher Electrochemical Energy Storage

Solar fuels synthesis using semiconductors

Shannon Boettcher Electrochemical Energy Storage

Oxygen electrocatalysis has broad

large scale electrolysis

Need for well-defined systems

Smith, R.D.L. et al. Science, 2013, 340, 60.

Designed for maximum

From Wang et al., Electrochimica Acta,

Shannon Boettcher Electrochemical Energy Storage

How do we design well-defined

Shannon Boettcher Electrochemical Energy Storage

Solution-processed ultra-thin film

~50 wt% surfactant

Shannon Boettcher Electrochemical Energy Storage

Initial target: Ni-Co-O

Mixing Co and Ni oxides reported =

H2O *OH *O + H2O *OOH O2

(see Rossmeisl, Norskov, etc.)

* Indicates bonded to the surface

Shannon Boettcher Electrochemical Energy Storage

Oxygen evolution with NixCo1-xOy films

- steady-state (> 15-30 min/step), 1 M KOH (99.999%)

Shannon Boettcher Electrochemical Energy Storage

P.; Tseung, A. C. C. A mechanistic study of

Samples containing NiO evolve as a

0.3 V vs. Hg|HgO

1M 99.999% KOH, 20 mV s-1

Corrigan, D. A.; Bendert,. J. Electrochem. Soc. 1988, 135, C156-C156.

Shannon Boettcher Electrochemical Energy Storage

XPS analysis confirms transition to

Shannon Boettcher Electrochemical Energy Storage

CV curves collected after 6 hr conditioning:

In-situ phase transformation

Rock Salt (NiO)

Ni(OH)2 electrochemistry studied

Fe increases OER activity

Shannon Boettcher Electrochemical Energy Storage

Thin-film OER catalyst quantitative

TOF = # O2 produced per metal per second

Fe:NiOOH >10x more active an IrO2 and >100x more

Shannon Boettcher Electrochemical Energy Storage

The role of Fe in NiOOH

Shannon Boettcher Electrochemical Energy Storage

Glassy C (GC) rotating disk electrode

No applied potential required

Corrigan, D.A. J. Electrochem Soc., 1987, 134, 377.

Shannon Boettcher Trotochaud,

Trotochaud, L.; Young, S.L.; Ranney, J.K.; Boettcher, S.W.

Shannon Boettcher Electrochemical Energy Storage

Is -NiOOH actually more active?

Peaks shift with crystallization

H2O OH O + H2O *OOH O2