1

Improving the Efficiency and Durability of Photoelectrochemical Cells

Jacob Lee

Glenelg High School

Independent Research

Mrs. Chawkat

May 25, 2020

Abstract
 2

Photoelectrochemical water splitting for hydrogen production could be an effective

method for creating renewable fuels that can be used in the future such as hydrogen or

hydrocarbon fuels. However, this method currently has low efficiency and durability, making it

impractical for large scale use. This paper details some properties of photoelectrochemical cells

that lead to low durability and efficiency and mentions some strategies that can be used to

improve PEC. This paper combines secondary research compiled from experts, as well as

primary research in the forms of interviews and meta-analysis. This paper mentions bandgap as

the main property regarding efficiency, and also mentions the strategies of hydrogen treatment,

oxygen deficiency, and protective layers to improve durability of PEC cells.

Introduction

Currently, global warming caused by fossil fuel emissions is looking to pose an issue in

the future. One way of reducing this is by using renewable energy sources such as photovoltaic

solar panels. Current solar panels are generally made from two types of silicon, N-silicon and P-

silicon. When light hits the solar panel, it can dislodge electrons from their bonds, creating

electron-hole pairs. When this occurs, the electrons flow toward the N-silicon, and the holes flow

toward the P-silicon. When a circuit connects the two types of silicon, electrons flow from the N-

silicon to the P-silicon to fill the holes (Komp, 2016). One problem with solar panels is that they

only provide electrical current that is difficult to store for a long time. Batteries that could store

the energy are expensive and hard to make. Additionally, this would not allow the energy to be

used for transportation, which accounts for 19% of fossil fuel usage (Tuller, 2017). An

alternative solution to this problem is the creation of solar fuels. Photoelectrochemical(PEC)

water splitting can be used to create these solar fuels in the form of hydrogen or hydrocarbon

fuels by combining photovoltaics with electrolysis(water splitting). Harry Tuller, a professor of

 3

electronic materials at Massachusetts Institute of Technology, writes, “light (photons) absorbed

in a photoelectrode create electron–hole pairs that are separated by internal electric fields, as in

PV cells. After separation, the holes drive the respective water oxidation reaction (forming O2)

at the photoanode and electrons drive the water reduction reaction (forming H2) at the

photocathode”. This H2 can also be used to synthesize hydrocarbon fuels, as mentioned by

Prashant Jain and Sungju Yu. These fuels are more energy dense, and although they release

carbon, it is a carbon neutral process if PEC water splitting is combined with carbon capture.

However, PEC is not without its own drawbacks. It is less efficient than photovoltaics,

which currently have an efficiency of over 45% in laboratories (NREL, 2019), while PEC cells

currently have peak efficiencies of around 10% (Verlage, 2015). Also, PEC cells are not very

durable, with current devices only lasting for around 100 hours, according to Micha Ben-Naim.

Unfortunately, efficiency and durability come as trade offs, however strategies have emerged to

mitigate drops in efficiency as a result of increased durability. In order to improve the feasibility

of Solar Hydrogen Production, photocatalysts, which are the main components of

Photoelectrochemical cells that split water need to be improved in terms of durability, while

maintaining efficiency by maintaining an optimized band gap, using protective layers, decreasing

electron-hole recombination through hydrogen treatment, using oxygen deficient oxide

photocatalysts, and reducing corrosion reactions.

Literature Review

One important step in improving PEC cells is finding a photocatalyst with an optimal

band gap. According to Dr. James Young, a postdoctoral researcher at the National Renewable

Energy Laboratory (NREL), an band gap can not be too high or too low, as a bandgap that is too

high results in less light being absorbed, and a bandgap that is too low results in more light being
 4

absorbed, but not enough energy is produced to meet the 1.6V requirement for water splitting.

One common material used for PEC, TiO2, has a high bandgap of 3.2eV and only absorbs

ultraviolet light, resulting in a low efficiency. An ideal multi-layer cell has one layer with 1.70eV

bandgap and another layer with 1.05eV bandgap (Young, 2017). However, materials with the

ideal band gaps are often very unstable and degrade quickly from electrolyte contact. Because of

this, other more stable materials with slightly different band gaps are used more frequently.

Currently, PEC durability is a larger problem than efficiency, however any materials used for

PEC cells need to have a reasonable band gap in order to be useful.

One class of materials that often have favorable band gaps are 3-5 semiconductors. These

materials are combinations of elements from groups 3 and 5 of the periodic table. According to

Todd Deutch, “The current 43.5% PV efficiency and 12.4% PEC water splitting efficiency

records were set with III-V semiconductor materials. These high efficiencies are a result of direct

transition optical band gaps” (Deutsch et al., 2013). 3-5 semiconductors are the most efficient

materials for both PV and PEC applications. However, compared to other materials like TiO2,

these materials are not stable, and maintain their efficiency for only 3-4 days of electrolyte

contact. In order for these types of materials to be viable for use, other strategies need to be used

in order to increase their durabilities.

Another important step for improving PEC durability is using protective layers.

Protective layers are layers of material that coat the photocatalyst so it is not degraded from

electrolyte contact, which is the main cause of PEC degradation. Although protective layers

lower efficiency, they are the most important tool for improving durability of photocatalysts that

are not normally stable in an electrolyte. One promising material for a protective layer is TiO2.

Although TiO2 has an unideal bandgap for use as a photocatalyst, when combined with a 3-5 and
 5

used as a protective layer, TiO2 can be used to improve the durability of PEC cells while still

maintaining over 10% efficiency. According to Erik Verlage, “exploiting the stability of the

amorphous TiO2 protection layer, we describe herein a photovoltaic-biased electrosynthetic cell

consisting of a GaAs/GaInP2/TiO2/Ni photoanode connected to a Ni–Mo coated

counterelectrode that effects unassisted solar-driven watersplitting for 80 h of continuous

operation at 1 sun illumination in 1.0 M KOH(aq), with ZSTH = 10.5%” (Verlage et al, 2015).

Here, a photocatalyst is presented that uses a protective layer and still has over 10% efficiency,

which is required for viability in commercial use. The usage of TiO2 as a protective layer is also

corroborated by Jianyun Zheng, who writes “the conformal crystalline TiO2 layer substantially

enhances the lifetime of the photocathodes in both strong acid and alkaline electrolyte solutions”

(Zheng et al, 2018). TiO2 is an effective protective layer because it is resistant to multiple types

of electrolyte solutions. According to an interview with James Young, this is because TiO2 is

both thermodynamically and kinetically stable compared to 3-5 semiconductors. Ideally, a more

durable 3-5 semiconductor could be found, however a TiO2 protective layer is an effective way

to increase durability without significant efficiency drops.

Another important step for creating an ideal PEC cell is

reducing electron hole recombination. This is when the electron and

hole move back together rather than flowing away from each other

and recombining after the electron has been used for current. One

method for doing this is hydrogen treatment, which involves putting

the photocatalyst into high temperature hydrogen gas. According to

Frederico Pesci, “Hydrogen treatments of TiO2 nanoparticles at a

moderate pressure (20 bar, 200 °C for 5 days) led to the formation of
 6

TiO2 with highly disordered surfaces and crystalline cores. The

surface disorder leads to band gap narrowing down to 1.0 eV, with a

large shift in the valence band edge taking place.(14) The black TiO2

was found to exhibit remarkable photocatalytic activity for H2

evolution” (2013). The usage of hydrogen treatment to create defects

in a photocatalyst increases the efficiency of the photocatalyst.

Pesci also writes, “near complete suppression of electron–hole

recombination can be achieved at only −0.6 V vs Ag/AgCl on H:TiO2

following UV excitation” (2013). The increase in hydrogen production

can be explained by the reduction in electron-hole recombination,

which lowers PEC efficiency.

Another method for improving PEC cells is oxygen deficiency, which is when some

oxygens are removed from an oxide photocatalyst such as TiO2. This creates defects in the

material that are actually beneficial for light absorption. According to Federico Pesci, “an

increase in the concentration of oxygen vacancies (Vo) lying 0.75 and 1.18 eV below the

conduction band edge occurs (scheme 1), which is in line with previous studies on single crystal

rutile TiO2 in which hydrogen treatment-induced Vo are known to lead to improved visible light

absorption”(2013). This method could be used to improve the efficiency of lower efficiency,

higher durability materials such as TiO2, which would make them more viable for PEC use.

Also, oxygen deficiency is not just limited to TiO2, Pesci states that it can be used on other

photocatalysts such as α-Fe2O3 and WO3. This can also be used on protective layers for

photocatalysts in order to lessen the reduction in efficiency of the protective layers. One study

mentions the usage of this idea in TiO2 protective layers,“A facile method for resolving the
 7

trade-off between efficiency and stability of the Si-based photocathodes is expounded by

constructing crystalline TiO2 protective layer with graded oxygen defects. In these cases, graded

oxygen defects are the most important factor for activating and enhancing PEC behaviors of Si-

based photocathodes with crystalline TiO2 protective layer” (Zheng et al, 2018). If other oxide

materials could be used as more efficient protective layers, oxygen deficiency could be an

effective way to improve them in order to lessen the negative aspects of protective layers. Also,

because TiO2 is a promising protective layer, the fact that oxygen treatment improves the

efficiency of it is very important for its use.

Another important strategy for improving PEC durability is minimizing corrosion

reactions. These are the reactions that cause the degradation of the PEC cell, and must be

minimized by improving kinetic and thermodynamic stability. Because of the effective 1.7V-

1.8V activation energy of water splitting, certain other reactions also become possible as well,

and some of these are corrosion reactions. Photocatalysts and protective layers must be made out

of materials that are not prone to spontaneous corrosion reactions when immersed in an

electrolyte at higher energy levels. According to Yuyu Bu and Jin-Ping Ao, the usage of TiO2 as

a protective layer minimizes these corrosion reactions. James Young also states that choosing

stable states of a photocatalyst from a Pourbaix diagram that compares electrochemical potential

to pH of the electrolyte reduces corrosion as well. However, a TiO2 protective layer seems like

the most effective method for reducing corrosion because it has low impacts on efficiency.

Data Collection

Part 1:

Interview Questions

Question 1: Why did you decide to research photoelectrochemical cells?

 8

Question 2: What are some of your current research interests?

Question 3: What are some of the most promising photocatalysts at the moment, and why are

these photocatalysts effective?

Question 4: I read a source about using oxygen deficient materials to decrease electron-hole

recombination in PEC cells. Is this an effective method of fixing this problem, and why? If not,

what are other methods?

Question 5: According to Efficient Suppression of Electron–Hole Recombination in Oxygen-

Deficient Hydrogen-Treated TiO2 Nanowires for Photoelectrochemical Water Splitting by

Federico Pesci, Hydrogen treatment enhances the properties of TiO2. Does this work for all

photocatalysts to increase efficiency, and does it have any impact on durability? If so, what

exactly are these effects?

Question 6: What properties of a material lead to a high Incident Photon to Current Efficiency?

Question 7: What exactly is photocurrent stability, and how is this an important factor in

durability or efficiency?

Question 8: In an interview with Dr. Young, he mentioned kinetic stability (minimizing a

corrosion reaction), and thermodynamic stability. How can these two types of stability be

increased; what properties of a material govern these stabilities?

Question 9: What are other key properties of durable photocatalysts other than good kinetic and

thermodynamic stabilities, and which of these properties has the most significant impact on

durability?

Question 10: How durable, in terms of hours, are current PEC cells, and how durable do they

need to be to be viable?

Micha Ben- Ryan Pekarek Notes

 9

Naim NREL
postdoctoral
Graduate researcher
student at
Stanford

Questio - Oxygen Couldn’t find the - 3-5 semiconductors are the

n deficiency recording but he most promising
asked: is a "viable said similar photocatalysts
and things - TiO2 is a promising
Question 4 interesting protective layer
strategy". - Need to research using
- Protective hydrogen treated or oxygen
layers also deficient TiO2 for protective
used for layer
this - Protective layers are good for
- Band increasing durability
alignment - However these layers
changes sacrifice efficiency
used as - Current devices are not even
well close to being stable enough
for use
- Need to look for effective
catalysts to minimize
corrosion reaction
- Need light and dark stability
- Light - Able to be
durable when
absorbing energy by
minimizing corrosion
reaction
- Dark - Able to be
durable from
electrolyte contact by
using protective layer
to insulate
photocatalyst

Questio - Use
n catalysts to
 10

asked: accelerate
water
Questio splitting to
n8 reduce
corrosion
- Choose
photocataly
st that is
more
resistant to
corrosion
- Corrosion
results
from
electrolyte
contact
- Protective
Layer
reduces
corrosion at
cost of
efficiency

Conclu Same as notes

sions because I could
only find one of
the interviews

Li, Zhaosheng & Luo, Wenjun & Zhang, Minglong & Feng, Jianyong & Zou, Zhigang.

(2013). Photoelectrochemical cells for solar hydrogen production: Current

state of promising photoelectrodes, methods to improve their properties,

and outlook. Energy Environ. Sci.. 6. 347-370. 10.1039/C2EE22618A.

 11

Yang, W., Prabhakar, R. R., Tan, J., Tilley, D., & Moon, J. (2019). Strategies

for enhancing the photocurrent, photovoltage, and stability of

photoelectrodes for photoelectrochemical water splitting. Royal Society of

Chemistry, (48). https://doi.org/10.1039/c8cs00997j

Source 1 Source 2 Synthesis

Objecti - Analyze - Compare - Important

ve specific PEC cells methods for
promising to other improving
photocatalysts similar durability are
- Analyze technologie protective layer
methods for s and surface
improving - Analyzing treatment
PEC the factors - Band alignment
performance that impact changes are
- Discussing PEC cells important for
ways to durability efficiency
improve PEC and - Doping can be
durability efficiency used for both
efficiency or
durability
depending on
what type of
doping is used
and what it is
used on

Method - Doping - Doping - Doping can be

s - Surface - Protective used on
treatment layer protective layer
 12

- Electrocatalyst - Protective
s layer to and
- Band structure catalyst photocatalyst
modificiation interface
- Protective - Improving
layer band
alignment

Part 2:

Rationale:

A mixed-method approach between qualitative and quantitative data collection, in the

form of interviews and meta-analysis, was used. Using a combination of interviews and meta-

analysis is the most effective for this research because initially, an experiment would have been

ideal, however, due to the lack of resources, such as the semiconductors that would be used as

photocatalysts and a way to measure hydrogen production, meta-analysis is used instead to take

this type of data from other studies. However, these studies are more difficult to locate than

expected, so a combined method of using some meta-analysis of other studies in addition to

some interviews with experts in the field is used.

Analysis:

Some results from the data collection include that protective layers are effective to

improve durability of PEC cells, and generally these protective layers are made out of oxide

materials. The data also includes Titanium(IV) Oxide as a good candidate to use as a protective

layer, which confirms information from the literary review. In addition, multiple interviews (I

ran out of time to transcribe all of them) mention thermodynamic and kinetic stability as
 13

important factors to consider with PEC, as well as electrochemical potential and pH. Pourbaix

diagrams can be used to determine stable states at certain potential pH ranges to determine what

materials will be the most effective. Also, more than 1.23V is required for water splitting, as

1.23V is the thermodynamic minimum, while kinetic losses result in a approximately 1.8V

requirement, which is also found in the literature review. Also, Micha Ben-Naim states that the

purpose of the protective layer is that it should prevent the photocatalyst from touching the

electrolyte, as this leads to the most corrosion. This stability, dark stability, is required for the

system to remain functional at all. He also states that as photons are absorbed and electrons are

excited, the electric current can lead to corrosion reactions that would normally not be possible.

This light stability is required in addition to dark stability for a system to maintain efficiency.

The results were generally not surprising and maintained constant with the literature review. One

surprising result was that the best current devices are functional for only 100 hours, and lose

efficiency before this as well. The results of the data collection allow for a better idea of specific

properties that could be important for photocatalysts and protective layers. The results also

highlight the current issues with durability in particular, as efficiency is not as much of a

problem. In addition, the meta-analysis sources also provide specific materials that could be

effective as photocatalysts, such as Si, CIGS, Fe2O3, BiVO4, and Cu2O. Some limitations of the

methods that were used include the inability to actually test specific materials, and the fact that

two types of data were collected leads to variances in the data, for example, one meta-analysis

talked about specific materials that could be used as protective layers, however the other meta-

analysis source and did not, and the interviews only mentioned TiO2.

Conclusion:
 14

The results of this data collection highlight the major flaws with current PEC devices,

specifically in the area of durability. The data mentions various properties that need to be

improved for durability, and others that need to be maintained to keep a higher efficiency. By

improving these properties of materials, researchers can create more durable PEC cells that can

actually be used to generate hydrogen that can be used as an alternative fuel to fossil fuels. The

main new ideas from the data collection were the ideas of the protective layer, and minimizing

corrosion reactions.

Conclusion

Overall, in order for PEC to be a viable option for energy production in the future, both

the durability and efficiency of PEC devices need to be improved. This can be done in a variety

of ways, and currently protective layers stand out as the most important method for improving

durability in all ways. However, if an oxide protective layer is used on a 3-5 photocatalyst,

hydrogen treatment and oxygen deficiency can be used to lessen the negative impacts on

efficiency caused by the use of a protective layer. Also, 3-5 photocatalysts are ideal for use

because of their ideal band gaps that allow them to absorb more light and generate more energy.

TiO2 appears to be a promising candidate for use as a protective layer.

 15

References

Bu, Y., & Ao, J.-P. (2017). A review on photoelectrochemical cathodic protection semiconductor

thin films for metals. Green Energy and Environment, 2(4).

https://doi.org/10.1016/j.gee.2017.02.003

Deutsch, T., Wang, H., Chen, Z., Ardo, S., Hu, S., Sunkara, M., . . . Boettcher, S. (2013,

October). III-V semiconductor systems for high-efficiency solar water splitting

applications. Retrieved May 25, 2020, from

https://www.energy.gov/sites/prod/files/2014/03/f12/pec_white_papers.pdf

Li, Zhaosheng & Luo, Wenjun & Zhang, Minglong & Feng, Jianyong & Zou, Zhigang. (2013).

Photoelectrochemical cells for solar hydrogen production: Current state of promising

photoelectrodes, methods to improve their properties, and outlook. Energy Environ. Sci..

6. 347-370. 10.1039/C2EE22618A.

National Renewable Energy Laboratory. (2019). Best research cell efficiency. Retrieved May 25,

2020, from https://www.nrel.gov/pv/cell-efficiency.html

Pesci, F. M., Wang, G., Clug, D. R., Li, Y., & Cowan, A. J. (2013). Efficient Suppression of

Electron–Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO2 Nanowires

for Photoelectrochemical Water Splitting. The Journal of Physical Chemistry C.

https://doi.org/10.1021/jp4099914

TED-Ed. (2016, January 5). How do solar panels work? - Richard Komp [Video file]. Retrieved

from https://www.youtube.com/watch?v=xKxrkht7CpY
 16

Tuller, H. L. (2017, January 30). Solar to fuels conversion technologies: a perspective. Retrieved

January 20, 2020, from Materials for Renewable and Sustainable Energy website:

https://www.ncbi.nlm.nih.gov/pmc/articles/PMC5283507/

Verlage, E., Liu, S., Liu, R., Jones, R., Sun, K., Xiang, C., . . . Atwater, H. (2015, August 17). A

monolithically integrated, intrinsically safe, 10% efficient, solar-driven water-splitting

system based on active, stable earth-abundant electrocatalysts in conjunction with

tandem III–V light absorbers protected by amorphous TiO2 films. Retrieved May 26,

2020, from https://daedalus.caltech.edu/files/2015/08/A-monolithically-integrated-

intrinsically-safe.pdf

Yang, W., Prabhakar, R. R., Tan, J., Tilley, D., & Moon, J. (2019). Strategies for enhancing the

photocurrent, photovoltage, and stability of photoelectrodes for photoelectrochemical

water splitting. Royal Society of Chemistry, (48). https://doi.org/10.1039/c8cs00997j

Young, J., Steiner, M., Döscher, H. et al. Direct solar-to-hydrogen conversion via inverted

metamorphic multi-junction semiconductor architectures. Nat Energy 2, 17028 (2017).

https://doi.org/10.1038/nenergy.2017.28

Yu, S., Jain, P.K. Plasmonic photosynthesis of C1–C3 hydrocarbons from carbon dioxide

assisted by an ionic liquid. Nat Commun 10, 2022 (2019) doi:10.1038/s41467-019-

10084-5

Zheng, J., Lyu, Y., Wang, R., Xie, C., Zhou, H., Jiang, S. P., & Wang, S. (2018, September 3).

Crystalline TiO2 protective layer with graded oxygen defects for efficient and stable

silicon-based photocathode. Retrieved May 25, 2020, from

https://www.nature.com/articles/s41467-018-05580-z