The role of electrochemical science and engineering in our

transition to a more sustainable energy infrastructure

Derek M. Hall
Assistant Professor and Program Lead of Energy Engineering
Department of Energy And Mineral Engineering
Morgan Lecture Series, May 2021

Credit: https://medium.com/@aleemuddinm

THE ENERGY UNIVERSITY

Decarbonization of the Grid and Transportation
Where are we now?
• Global CO2 production is continuing to grow
despite international efforts to curb emissions.

• Though we have reduced its growth, more

changes are still needed.

• The international community needs to cut total

emissions in half by 2030 or sooner to avoid
ecological disasters.

Source: J. Falk, O. Gaffney, A. K. Bhowmik, P. Bergmark,V. Galaz, N. Gaskell, S. Henningsson, M. Höjer,L. Jacobson, K.
Jónás, T. Kåberger, D. Klingenfeld, J. Lenhart, B. Loken, D. Lundén, J. Malmodin,T. Malmqvist, V. Olausson, I. Otto, A.
Pearce, E. Pihl, T. Shalit, Exponential Roadmap 1.5.1. FutureCredit:
Earth.https://medium.com/@aleemuddinm
Sweden. (January 2020.)

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 Sustainable energy is starting to
make economic sense.
• Renewables are now cost-competitive without
accounting for health and environmental impacts.

• Globally, 90% of all new power generation installations

were renewable in 2020.

• Multiple transportation companies have announced

plans to transition to all-electric vehicles. The U.S.
president was just testing an all-electric F-150, one of
the most popular vehicle models in the U.S.

Sources: [1] J. Falk, O. Gaffney, A. K. Bhowmik, P. Bergmark,V. Galaz, N. Gaskell, S. Henningsson, M. Höjer,L.
Jacobson, K. Jónás, T. Kåberger, D. Klingenfeld, J. Lenhart, B. Loken, D. Lundén, J. Malmodin,T. Malmqvist, V.
Olausson, I. Otto, A. Pearce, E. Pihl, T. Shalit, Exponential Roadmap 1.5.1. Future Earth. Sweden. (January 2020.)
[2] 2019-2021 IEA (www.iea.org)
Credit: https://medium.com/@aleemuddinm

THE ENERGY UNIVERSITY

 How can we make deep cuts to our emissions?

Source: J. Falk, O. Gaffney, A. K. Bhowmik, P. Bergmark,V. Galaz, N. Gaskell, S. Henningsson, M. Höjer,L. Jacobson, K. Jónás, T. Kåberger, D. Klingenfeld, J. Lenhart, B. Loken, D. Lundén, J. Malmodin,T. Malmqvist, V.
Olausson, I. Otto, A. Pearce, E. Pihl, T. Shalit, Exponential Roadmap 1.5.1. Future Earth. Sweden. (January 2020.)
Credit: https://medium.com/@aleemuddinm

THE ENERGY UNIVERSITY

New electrochemical devices can help us reduce
our carbon emissions.

Decarbonizing our Electrical Grid

(Grid-Scale Electric Energy Storage)

Decarbonizing our Transportation

(Battery & Hydrogen-Powered Vehicles)

Improving our Energy Efficiency

(Thermally Rechargeable Batteries to Capture Waste Heat)

Credit: https://medium.com/@aleemuddinm

THE ENERGY UNIVERSITY

Decarbonizing The Electrical Grid
(Grid-Scale Electric Energy Storage)
 How much energy storage do we really need?

• A recent study estimates the State of

California (~6th largest economy in the world)
needs between 6 - 12 GWs of new storage.

• This means we need about 100 of the

world’s largest batteries or ~6 billion cell
phone batteries for just California alone.

Credit: https://medium.com/@aleemuddinm
Hall, D. M., Grenier, J., Duffy, T. S., & Lvov, S. N. (2020). The Energy Storage Density of Redox Flow Battery Chemistries: A Thermodynamic Analysis.
Journal of the Electrochemical Society, 167(11).
Williams, J. H., Debenedictis, A., Ghanadan, R., Mahone, A., Moore, J., Iii, W. R. M., Price, S., & Torn, M. S. (2012). The Technology Path to Deep
Greenhouse Gas
Battery storage capacity is growing quickly.

• The U.S. is quickly

approaching its first
GW of battery storage.

• Unless other solutions

become available, this
trend is expected to
continue.

Energy Information Administration, U. (2020). U.S. Battery Storage Market Trends. www.eia.gov
Redox flow batteries are a promising alternative to
Li-ion batteries for stationary energy storage.

Li-ion Flow Batteries

2,000 cycles 13,000 cycles
400 Wh L-1 40 Wh L-1
1000 W L-1 1.5 W L-1
200 USD kWh-1 100 USD kWh-1

Kim, K. J., Park, M. S., Kim, Y. J., Kim, J. H., Dou, S. X., & Skyllas-Kazacos, M. (2015). A technology review of electrodes and reaction mechanisms
in vanadium redox flow batteries. Journal of Materials Chemistry A, 3(33), 16913–16933.
IRENA. (2017). Electricity storage and renewables: Costs and markets to 2030. In International Renewable Energy Agency (Issue October).
Flow batteries use a lot of carbon materials.
• The flow cell which
determines the power
capacity of the system is
made mostly of carbon-
based materials.

• The flow fields used to

transport battery solutions
are made from graphite
plates.

• The electrode materials are

carbon-based materials.

https://www.sandia.gov/ess-
ssl/docs/pr_conferences/2012/papers/Friday/Session2/04_Sprenkle_PeerReview.pdf
Flow battery performance depends strongly their carbon-
based components.

I. Catalytic Activity

II. Electric Conductivity

III. Fluid Permeability

Carbon Cloth Carbon Paper Carbon Felt

Kim, K. J., Park, M. S., Kim, Y. J., Kim, J. H., Dou, S. X., & Skyllas-Kazacos, M. (2015). A technology review of electrodes and reaction
mechanisms in vanadium redox flow batteries. Journal of Materials Chemistry A, 3(33), 16913–16933.
Mench, M. M. (2008). Performance Characterization of Fuel Cell Systems. In Fuel Cell Engines (pp. 121–189). John Wiley and Sons Inc.
Smarter electrode materials provide more power density and
energy storage capacity.

13

Hall, D. M., Grenier, J., Duffy, T. S., & Lvov, S. N. (2020). The Energy Storage Density of Redox Flow Battery Chemistries: A Thermodynamic Analysis.
Journal of The Electrochemical Society, 167(11), 110536.
Mench, M. M. (2008). Performance Characterization of Fuel Cell Systems. In Fuel Cell Engines (pp. 121–189). John Wiley and Sons Inc.
Rotating disc electrodes can classify redox battery
chemistries by their preferences to electrode materials.

• Different electrode materials

were selected as baseline
materials: pyrolytic graphite
oriented as (1) edge-plane
(PGE) and (2) basal-plane
(PGB), and glassy carbon
(GC).

• These electrode materials will

be compared to classic metal-
based electrodes.

• Raman spectroscopy and

XPS were used to classify
differences in the electrode
materials.
McCreery, R. L. (2008). Advanced carbon electrode materials for molecular electrochemistry. Chemical
Reviews, 108(7), 2646–2687. https://doi.org/10.1021/cr068076m
 Other redox couples are more sensitive to the electrode material (courtesy
of electrochemical impedance spectroscopy).
10
• The ferri to ferrocyanide
8 2000 RPM GC
reaction is more responsive to
2000 RPM PGB
-Zimag / (Ω)

6 2000 RPM PGE changes in the electrode

2000 RPM Pt surface.
4

2 • Clear differences between Pt

0
and carbon-based materials
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 are readily observed.
Zreal / (Ω)
Material j0 / mA cm-2
• Differences between carbon-
based electrodes, are less
PGE 60 ± 17
apparent.
PGB 52 ± 8
GC 30 ± 4
Pt 156 ± 20
McCreery, R. L. (2008). Advanced carbon electrode materials for molecular electrochemistry. Chemical
Reviews, 108(7), 2646–2687. https://doi.org/10.1021/cr068076m
 Some reactions show minimal preferences between
electrocatalytic materials.
• The V(IV) to V(V) redox reaction is
essential to the all-vanadium redox flow
battery.

• The dependence of this reaction on the

electrocatalytic material is still being
debated.

20000
• Classic rotating disc electrode studies
Material j0 / μA cm-2
show that it is quite insensitive and slow.
PGE 4.6 ± 0.5
PGB 1.6 ± 0.02
GC 4.8 ± 0.2
Pt 3.5 ± 0.7

McCreery, R. L. (2008). Advanced carbon electrode materials for molecular electrochemistry. Chemical
Reviews, 108(7), 2646–2687. https://doi.org/10.1021/cr068076m
Here is a “fun” figure that shows the extent of this debate for
two reactions as of 2020.

Roznyatovskaya, N., Noack, J., Pinkwart, K., & Tübke, J. (2020). Aspects of electron transfer processes in vanadium redox-flow batteries. Current
Opinion in Electrochemistry, 19(Ii), 42–48. https://doi.org/10.1016/j.coelec.2019.10.003
Decarbonizing Transportation
(Battery & Hydrogen-Powered Vehicles)
Hydrogen is a key feedstock for multiple industries.

IEA. (2019). The Future of Hydrogen: Seizing today’s opportunities. June. https://doi.org/10.1787/1e0514c4-en
Most hydrogen is produced from fossil fuels (not good!).

IEA. (2019). The Future of Hydrogen: Seizing today’s opportunities. June. https://doi.org/10.1787/1e0514c4-en
Hydrogen is being pushed as an alternative to power HDVs,
aircrafts and trains.

• Li-ion batteries currently

lack the gravimetric
power densities needed
to power larger vehicles.

• Hydrogen power remains

one of the few options
capable of
decarbonizing these
systems.

Cullen, D. A., Neyerlin, K. C., Ahluwalia, R. K., Mukundan, R., More, K. L., Borup, R. L., Weber, A. Z., Myers, D. J., & Kusoglu, A. (2021). New roads
and challenges for fuel cells in heavy-duty transportation. Nature Energy. https://doi.org/10.1038/s41560-021-00775-z
To decarbonize hydrogen production, seawater electrolysis
and hybrid-thermochemical cycles are promising options.

Naterer, G., Suppiah, S., Lewis, M et al (2009). Recent Canadian advances in nuclear-based hydrogen production and the thermochemical Cu–
Cl cycle. International Journal of Hydrogen Energy, 34, 2901–2917.
Shi, L., Rossi, R., Son, M., Hall, D. M., Hickner, M. A., Gorski, C. A., & Logan, B. E. (2020). Using reverse osmosis membranes to control ion
transport during water electrolysis. Energy and Environmental Science, 13(9), 3138–3148.
PEM water electrolysis systems use carbon substrates at the
negative electrode but avoid it them at the positive
electrodes.
• The highly oxidative environment present
at the positive electrode result in CO2
production from any carbon materials
present.

• Carbon materials are still used at the

negative electrode as the substrate/gas
diffusion layer and the flow field.

• Considerable focus is currently on how

best to apply catalysts to these substrates.

Chisholm, G., Kitson, P. J., Kirkaldy, N. D., Bloor, L. G., & Cronin, L. (2014). 3D printed flow plates for the electrolysis of water: An economic and
adaptable approach to device manufacture. Energy and Environmental Science, 7(9), 3026–3032. https://doi.org/10.1039/c4ee01426j
Current challenges in PEM electrolysis are focused on
reducing system costs and water quality sensitivity.

• New strategies are needed

to reduce the cost of PEM
membrane and catalyst
materials.

• Recent studies have shown

that reverse osmosis
membranes are an attractive
low-cost alternative.

Shi, L., Rossi, R., Son, M., Hall, D. M., Hickner, M. A., Gorski, C. A., & Logan, B. E. (2020). Using reverse osmosis membranes to control ion
transport during water electrolysis. Energy and Environmental Science, 13(9), 3138–3148.
Thermochemical cycles reduce the electric potential needed
to split water by including thermochemical reactions.

• These systems use the

classic flow cell design,
with carbon-based
materials on both sides
of the membrane.

• The use of heat, to

offset electric power
resulted in favorable
efficiencies and
competitive costs.

Naterer, G., Suppiah, S., Lewis, M et al (2009). Recent Canadian advances in nuclear-based hydrogen production and the thermochemical Cu–
Cl cycle. International Journal of Hydrogen Energy, 34, 2901–2917.
Hall, D. M., Akinfiev, N. N., LaRow, E. G., Schatz, R. S., & Lvov, S. N. (2014). Thermodynamics and Efficiency of a CuCl(aq)/HCl(aq) Electrolyzer.
Electrochimica Acta, 143, 70–82. https://doi.org/10.1016/j.electacta.2014.08.018
The fast nature of the anodic reaction, indicated that mass
transport issues dominated losses.

Use of carbon-based materials at the

anode with improved catalyst application
methods for the cathode dramatically
improved performance and reduced Pt
catalyst loadings by 75% percent.

Hall, D. M., LaRow, E. G., Schatz, R. S., Beck, J. R., & Lvov, S. N. (2015). Electrochemical Kinetics of CuCl(aq)/HCl(aq) Electrolyzer for
Hydrogen Production via a Cu-Cl Thermochemical Cycle. Journal of The Electrochemical Society, 162(1), F108–F114.
https://doi.org/10.1149/2.0661501jes
Improving Energy Efficiency
(Thermally Rechargeable Batteries)
Massive amounts of low-grade waste heat is produced in the
U.S every year.
• A large portion of the energy we
consume is lost as waste heat.

• The bulk of this energy stream is at

a low temperature (low-grade).
2%3% 6%
>500 ⁰C
23% 400-500 ⁰C
300-400 ⁰C
66%
200-300 ⁰C
100-200 ⁰C

M. Rahimi, A.P. Straub, F. Zhang, X. Zhu, M. Elimelech, C.A. Gorski, B.E. Logan, Emerging electrochemical and membrane-based systems to
convert low-grade heat to electricity, Energy Environ. Sci. 11 (2018) 276–285.
C. Haddad, C. Perilhon, A. Danlos, M-X. Francois, G. Descombes, Some efficient solutions to recover low and medium waste heat:
competitiveness of the thermoacoustic technology, Energy Procedia 50 (2014) 1056-1069.
Most methods lack the power density and cost effectiveness
to be viable solutions.

• TRBs have the highest power

Thermally Regenerative
Thermo-Osmotic
Energy Conversion Electrochemical Cycles density among heat-electric
Salinity Gradient Energy
Thermally
energy conversion technologies.
Regenerative
Batteries
• TRB energy efficiencies are
comparable to alternative
approaches employing other
Thermoelectrochemical Cells
electrochemical energy
conversion systems.

M. Rahimi, A.P. Straub, F. Zhang, X. Zhu, M. Elimelech, C.A. Gorski, B.E. Logan, Emerging electrochemical and membrane-based systems
to convert low-grade heat to electricity, Energy Environ. Sci. 11 (2018) 276–285.
Thermally regenerative batteries (TRBS) are a promising new
technology to support thermal power generation units.
Electrochemical Series / V

Ag+(aq) + e- = Ag(s)
Catholyte
Addition of ammonia

Ag(NH3)2+(aq) + e- = Ag(s) + 2NH3(aq)

Anolyte
 Finite element analysis modeling provides insights into how
fiber arrangement and flow regimes impact performance.

a) Finalized mesh around three in-line fibers in the computational

Schematic of (a) in-line and (b) staggered fiber arrangements. Domains are: N –
negative channel (blue) and P – positive channel (green). Boundaries are: 1 – domain. b) Comparison of the Butler-Volmer equation (with IR
positive electrolyte inlet, 2 – positive electrode surface, 3 – ion exchange correction) to COMSOL results for a channel geometry using the same
membrane, 4 – negative electrode, and 5 – positive electrolyte outlet. simulation parameters as the rest of the study.
Cross, N., Hall, D. M., Lvov, S., Logan, B., & Rau, M. (2021). The Impact of Fiber Arrangement and Advective
Transport in Porous Electrodes for Silver-Based Thermally Regenerated Batteries. Electrochimica Acta.
https://doi.org/10.1016/j.electacta.2021.138527
Staggered fiber arrangements lead to smaller concentration
gradients and higher power densities.

Cross, N., Hall, D. M., Lvov, S., Logan, B., & Rau, M. (2021). The Impact of Fiber Arrangement and Advective
Transport in Porous Electrodes for Silver-Based Thermally Regenerated Batteries. Electrochimica Acta.
https://doi.org/10.1016/j.electacta.2021.138527
If we have minimal control over fiber placement, variable
void fraction is a comprise between plugging time and
power density.

Variable void (VV) fraction layout

Cross, N., Hall, D. M., Lvov, S., Logan, B., & Rau, M. (2021). The Impact of Fiber Arrangement and Advective
Transport in Porous Electrodes for Silver-Based Thermally Regenerated Batteries. Electrochimica Acta.
https://doi.org/10.1016/j.electacta.2021.138527
 The all-aqueous TRB shows promising signs of out-
performing previous TRBs for key metrics.

CuBr20(aq) + e- = CuBr2-(aq)
Electrochemical Series

Weak ligand, Br-(aq)

Cu2+(aq) + e- = Cu+(aq)

Strong ligand, NH3(aq)

Cu(NH3)22+(aq) + e- = Cu(NH3)2+ (aq)

Springer, R., Cross, N., Lvov, S. N., Logan, B. E., Gorski, C. A., & Hall, D. M. (2021). An all-aqueous thermally regenerative ammonia
battery chemistry using Cu(I,II) redox reactions. JECS. 1–12.
 These new TRB chemistries are limited by the conductivity of
the system and electrode permeability.

400 -120
350 W m-2
350
Power Density / (W m-2)

300 N115 -90

240 W m-2

Zi / (Ω cm2)
250
200 -60
150 123 W m-2 Anode
100 N117 -30 Cathode
50
AEM
0
0
0 30 60 90 120
0 300 600 900 1200
jcell / (A m )
-2
Zr / (Ω cm2)

Springer, R., Cross, N., Lvov, S. N., Logan, B. E., Gorski, C. A., & Hall, D. M. (2021). An all-aqueous thermally regenerative ammonia
battery chemistry using Cu(I,II) redox reactions. JECS. 1–12.
 The all-aqueous TRB out-performs previous TRBs in key
metrics.
400
350
Peak Power Density / (W m-2)

Avoids Increases
300 All-aq Cu-TRAB dendrite power
250 Cu nanoslurry formation density
200 Ag-TRAB
Cu/Ni-TRAB Increases High
150 energy coulombic
Cu-TRAB density efficiency
100
Cu/Zn-TRAB
50
Cu-TREnB
0
75 85 95
Cell Coulombic Efficiency / (%)

Springer, R., Cross, N., Lvov, S. N., Logan, B. E., Gorski, C. A., & Hall, D. M. (2021). An all-aqueous thermally regenerative ammonia
battery chemistry using Cu(I,II) redox reactions. JECS. 1–12.
These new TRB chemistries offers pathways to further reduce
electricity prices.

• The performance of TRBs are in-line

with developed technologies.

• Our new chemistries rely on less

expensive materials and provide better
performance.
Cost of metals
Copper: $0.66 / 100 g
Vanadium: $2.7 / 100 g
Lithium: $9.5 / 100 g

X. Wei, W. Pan, W. Duan, A. Hollas, Z. Yang, B. Li, Z. Nie, Materials and Systems for Organic Redox Flow Batteries: Status and Challenges, ACS Energy Lett. 2 (2017) 2187–2204.
M. Rahimi, T. Kim, C.A. Gorski, B.E. Logan, A thermally regenerative ammonia battery with carbon-silver electrodes for converting low-grade waste heat to electricity, J. Power
Sources. 373 (2018) 95–102.
 Acknowledgements

PSU Collaborators
Serguei Lvov, Bruce Logan, Matthew Rau, Christopher Gorski, Ljubisa Radovic

MRI Staff
Maxwell Wetherington, Tawanda Zimudzi

Students
Renaldo Springer, Nicholas Cross, Ridge Bachmann, Marah McCauley
Questions

Decarbonizing our Electrical Grid

(Grid-Scale Electric Energy Storage)

Decarbonizing our Transportation

(Battery & Hydrogen-Powered Vehicles)

Improving our Energy Efficiency

(Thermally Rechargeable Batteries to Capture Waste Heat)