1.

Perovskite
1.1 Introduction to Perovskites
Perovskite, named after the Russian mineralogist Lev Perovski [1], once
referred exclusively to the calcium titanate material, CaTiO3. However,
since Victor Goldschmidts studies on perovskite structures in 1926 [2],
the term now refers to, more loosely, a larger class of orthorhombic
crystal structures with an ABX3 stoichiometry.

Figure 1. ABX3 perovskite structure in its BX6 octahedral form (left) and AX12
cubo-octahedral geometry (right) [8]

While the smaller B cation takes an octahedral site shared with 6 X anions,
the larger A cation typically occupies cubo-octahedral sites shared with 12
X anions (Fig. 1). Ion geometries in perovskites are governed strictly by a
tolerance factor (t), given by t=(r A +r x )/ 2(r B + r x ) , in which r refers to the
effective ionic radii of the constituents. [1] For many years, perovskite
research has been dominated by that in oxide perovskites (where X=O),
due to their excellent ferroelectric and superconductive properties.
However, since halide perovskites were demonstrated to give power
conversion efficiencies (PCEs) as high as 3.1% for X=Br and 3.8% for X=I
in 2009 [3], the number of studies incorporating halide perovskites for
solar applications has increased vastly.
In a matter of 6 years, the PCE of halide perovskites has increased
tremendously from 3.1% in 2009 to greater than 15% in 2014 [1], making
it one of the fastest-advancing solar technologies to date. Furthermore,
perovskite PCEs have been touted to be able reach up to 50% [4]. In
addition to the stellar electrical and optical properties of halide
perovskites such as a narrow band gap and a high absorption coefficient,

the abundance of component materials and ease of manufacture has also

greatly reduced production cost, making perovskite photovoltaics (PVs) an
increasingly commercially attractive option. Start-up companies have
already promised to deliver perovskite modules by 2017 [5]; while the
cost per watt of perovskite PVs has been estimated to be only half that of
commercial Silicon PVs should they be made saleable [6]. This has, in all,
led to the dubbing of perovskite solar cell technologies as one of the
biggest scientific breakthroughs in 2013. [7]
1.2 The Evolution of Lead Halide Perovskites for Solar Cell
Applications
One of the most commonly studied halide perovskite materials for PV
applications are methylammonium lead halides (CH3NH3PbX3) where X is a
halogen ion such as I-, Br- and Cl-. In 2009, CH3NH3PbX3 nanoparticles were
first used as a dye-sensitizer to sensitize mesoporous titanium dioxide
(TiO2) charge-separating layers. Notably, for a film thickness of 3.6 m, it
was found to absorb 10 times more light than conventional rutheniumbased molecular dyes of that time. [3] From there, given the susceptibility
of ionic perovskite to dissolve in polar solvents, one immediate challenge
lay in optimizing the liquid electrolytes used then for CH 3NH3PbX3
functionality. This concern was eventually resolved through the use of
organic and later, inorganic solid hole transport materials (HTMs) to fill the
pores of TiO2, inducing a heterojunction. Hole diffusion length and the
conductivity of HTMs were important factors that had to be tailored to
meet the required TiO2 film thicknesses. During this stage of initial
research, the concept of using CH 3NH3PbX3 as a dye for dye-sensitized
solar cells remained relatively unchanged and PCEs as high at 9.7% were
obtained. [8]

Figure 2. Structural progress of perovskite-based solid-state solar cells [8]

Following that, lead-halide perovskite-based solar cell research progressed

via three significant stages, namely the meso-superstructure, pillared
structure and the planar structure outlined in Figure 2. To bring down the
synthesis temperatures of the initial sensitized cells incorporating
mesoporous TiO2, Al2O3 analogues were experimented on in mesosuperstructures to great effect. [9] Since electron injection from perovskite
to the Al2O3 scaffold was not allowed, enhanced open-circuit voltages of
over 1.1V and PCEs of up to 12% were observed largely due to the
confinement of photo-excited electrons within the perovskite phase,
thereby increasing the splitting of quasi-Fermi levels for both holes and
electrons under illumination. [7] Although poor pore filling of the HTM was
a challenge in this configuration, studies of meso-superstructures further
revealed that the mesoporous sensitization concept was not necessarily a
requirement for cell design given the finding of effective electron transfer
capabilities on top of efficient light harvesting, within perovskite itself. [8]
To make use of lead-halide perovskites new-found carrier transport
capabilities, instead of a surface coating as in sensitized and mesosuperstructures, pillared structures were prepared via the infiltration of
CH3NH3PbI3 into mesoporous TiO2 films. One-step and two-step coatings of
CH3NH3PbI3 yielded PCEs of 12% and 15% respectively in this pillared
configuration.

Moving on, planar lead-halide perovskite structures were

subsequently developed via vapour deposition to take full advantage of

CH3NH3PbI3-xClxs charge transport properties. PCEs over 15% were
derived, demonstrating that much simpler planar architectures could

possibly give better solar cell performance. [1] From the versatility of leadhalide perovskites demonstrated through these studies, it may be further
concluded that such perovskites are likely to be highly compatible with
first and second generation solar technologies, giving added reason for
rapid adoption to utility-scale power generation. [7]
1.3 Advantages of Lead-Halide Perovskite Solar Cells
1.3.1 Optical and Electrical Properties
Lead-Halide Perovskites generally have narrow bandgaps in the range of
2.3-1.6eV, which suggests the propensity for high efficiencies given its
closeness to the optimal gap of 1.4eV for a single-junction solar cells at
AM 1.5. [10]

Figure 3. Absorption coefficient () as a function of wavelength for perovskite

CH3NH3PbI3 nanodot coated with 1.4 mm TiO2 film [1]

This notion is further backed by the excellent light absorption capabilities

of lead-halide perovskites. Having absorption coefficients on the order of
104cm-1 (Fig. 3), perovskite materials can absorb solar energy more
efficiently and over a broader spectrum than most conventional PV
materials. [1] Accordingly, the absorption depth of lead-halide perovskites
was determined to be approximately 600 nm, suggesting very little
material is required for good light absorption. What remains, is a matter of
optimizing cell structure (i.e. meso-super versus planar structures) to suit
the diffusion lengths of the charge carriers which is in fact highly
dependent on the type of halide utilized. [8] It is therefore these
inherently

good,

cost-effective

properties

that

make

perovskites such a promising material for solar applications.

1.3.2 Material and Processing Considerations

lead-halide

One other advantage of lead-halide perovskites is that its components are

common and easily obtainable unlike rare PV metals such as tellurium,
which are limited in supply on earth. Lead-hallide perovskite-based PV
cells are also generally easy to manufacture and process. Common
methods of doing so may be split essentially into solvent-based and
vapour deposition techniques. Solvent-based techniques typically include
spin and immersive-dip coating. While films produced by these methods
typically suffer from defects, a more recent room temperature solventsolvent extraction method has been found to produce high-quality
crystalline films with tailored thicknesses down to 20 nm across several
square

centimetres.

Vapour-based

techniques

on

the

other

hand,

generally require annealing at temperatures above 100C. Their benefits

though, comprise of yielding multi-stacked thin films over larger areas and
conferring more homogeneity to film thickness. [11] Commonalities across
both techniques are that they can be carried out in traditional lab
environments with simple wet chemistry. [12] Compared to commercial
silicon-based solar cells which require special clean room facilities and
high temperatures of up to 1000C for processing, lead-halide perovskites
may hence be concluded to be more cost-effective in terms of raw
material and processing costs.
1.4 Disadvantages of Lead-Halide Perovskite Solar Cells
1.4.1 Issues of Cell Stability
Lead-halide perovskites are extremely sensitive to water and moisture due
to the hygroscopic nature of the organic component. Prolonged contact
will moisture will result in the rapid degradation of the cell. [13] To
circumvent this, carbon nanotubes and inert polymer matrices have been
used to encapsulate the perovskite, preventing immediate degradation. A
recent introduction of a micrometre thick carbon back contact to act as a
water-retaining layer has also been found to extend stable cell life to more
than a 1000 hours. [14] UV light-induced instability is another problem
that perovskite solar cells incorporating mesoporous oxides face. UVinduced photo-generated holes and oxygen radicals in TiO 2 have been

found to cause declines in device performance and further research with

the exception of substituting TiO2 for Al2O3, is required to resolve this. [15]
1.4.2 Issues of Toxicity
Lead-halide perovskite-based solar cell disposal poses a problem because
of the toxic lead contained that can easily contaminate the environment.
Researchers are currently experimenting with substituting lead for tin.
However, some immediate drawbacks observed were the poor moisture
and oxygen resistance of tin-based perovskites.
2. Photovoltaic Energy Storage
2.1 Introduction to Photovoltaic Energy Storage
In the next section, emerging technologies in solar energy storage will be
reviewed. Solar energy, being diurnal in nature and subject to varying
weather conditions, can only be effectively utilized 24/7 should an
inexpensive large-scale energy storage mechanism be developed. While
batteries may a seem a natural approach with respect to storing solar
energy, enormous quantities of batteries would be required to be costeffective over the averaged 30-year amortized lifetime of a photovoltaic
system. Moreover, they would have to cost as little as that of lead-acid
batteries while having the cyclability of a typical lithium-ion battery. Some
potential next-generation energy storage devices that could solve the
problems of current batteries include superconducting transmission grids,
supercapacitors as well as flywheels. However, the most cost-effective
methods of large-scale solar energy storage may be put down to flow
batteries, hydrogen fuel and hybrid PV-thermal collector systems. [16]
2.2 Flow Batteries
Flow batteries are electrochemical devices that convert the chemical
energy stored in electro-active materials directly into electrical energy,
similar to conventional batteries and fuel cells.

Figure 4. Schematic diagram of a redox flow battery [17]

What sets flow batteries apart however, is the mechanism of storing

energy in their electrolytes as opposed to their electrodes. During
discharging in a flow battery, two liquids are pumped from separate
reservoirs into a common tank in which they undergo chemical reactions
and exchange ions across a membrane, generating electricity. (Fig. 4)
During charging however, the chemical reactions are reversed. One
significant advantage of flow batteries is the relatively flexibility in which
their components may be arranged given that the chemical storage
components

maybe

stored

separately

from

the power

conversion

components. However, energy storage is largely limited by electrolyte

quantity and electrode surface area. Some of the most significant types of
flow batteries are the redox, membraneless, organic and nano-network
types. [17]
2.2.1 Redox Flow Batteries
Redox flow batteries typically employ redox charge and discharge
mechanisms to store energy within the electrolyte; which may be given by
the general equations,

For the anode (1) and cathode (2) respectively. [17] Some of the most
common redox flow batteries are those that employ Vanadium, Bromine,
Cerium and Zinc as redox species. Advantages of redox flow cells include
that

of

having

quick

response

times,

high

electricity-to-electricity

conversion, no cell-to-cell equalization requirement and the relative safety

of storing active materials away from their reactive point source.
Disadvantages however, comprise the corrosiveness of the electrolytes
due to their high ionic concentrations. This makes it particularly hard
when it comes to selecting materials for the construction of other
components such as the pumps, flow fields and pipes and that come into
direct contact with the electrolyte. Furthermore, besides the inherent
complexity of flow battery systems that make them more suited for largescale applications, materials such as vanadium are very expensive. Cost
analysis suggests that vanadium could contribute up to $110/ kWh at
current vanadium prices; which is approximately 50% of the target cost of
$200/ kWh. [18]
2.2.2 Membraneless Flow Batteries
Membraneless flow batteries are very similar to redox flow batteries with
the exception of not having a separating membrane. The functionality of
these kinds of batteries may be attributed to the concept of laminar flow,
in which the solutions stream past the electrodes in parallel with little
mixing. This allows for combinations of electro-active materials such as
liquid bromine and hydrogen, given that in typical redox flow batteries,
contact between bromine and hydrogen would lead to the formation of
membrane-destructive hydrobromic acid. Membraneless flow batteries are
a significant innovation, producing as much as three times the power of
other membraneless systems and yielding a power density of up to 7950
W m-2, which is an order of magnitude greater than lithium-ion batteries.
[19]
2.2.3 Organic Flow Batteries

One other problem of using metal ions in redox flow batteries is that of
low energy densities, given the poor solubility of metal salts in solvents,
especially water. To overcome these solubility issues, organic redox-active
materials known as quinones have been introduced. The advantage of
quinones is their propensity for kinetically efficient redox reactions (a
1000 times faster than vanadium) and a variety of modifications by
tailoring the functional groups attached.

While energy density can

become an issue should the molecular weight of the quinones utilized

become too large, current quinone-based flow batteries have shown
excellent stability at 5000 cycles and have discharged energy densities of
over 50 Wh kg-1. Quinone-based flow batteries also represent an edge
over vanadium-based ones by being 8 times less costly. [20]
2.2.4 Nano-network Flow Batteries
Nano-network based flow batteries are an even more recent invention
than organic-based ones. The principle behind these batteries involves
forming networks of nanoparticles that maintain electrical connections
even as liquid flows. In this way, unlike conventional flow batteries
whereby electricity is extracted only from the ions that come into direct
contact with the electrodes, the nanoparticle network makes it possible to
generate up to 6 times more energy given that the entire network of
particles may be charged simultaneously. While indeed an exciting
concept, further research is required especially in the areas of lowering
cost and extending device life. [21]
2.3 Hydrogen Fuel Storage
Another method of storing electrical energy is that modelled after the
natural enzyme reactions of hydrogenase by inducing water electrolysis
via solar-generated currents, producing hydrogen fuel for storage and
oxygen. Methods of doing so that have been investigated generally
involve the use of platinum or nickle-based electrodes in separate fuelforming systems. Platinum electrodes pose a very high cost barrier for
large scale commercialization. On the other hand, nickle-based electrode,

while far cheaper, require scrubbing the input stream to remove

contaminating carbon dioxide. Energy conversion efficiencies also remain
low, hitting a maximum of 30%. [22] Recently however, an integrated
photovoltaic fuel-generating system has been designed. Made of earthabundant, inexpensive materials, the device boasts a photovoltaic silicon
sheet sandwiched by a cobalt-based catalyst and nickel-molybdenum-zinc
alloy to produce oxygen and hydrogen from water respectively. (Fig. 5
below)

[22]

This

device

poses

great

potential

for

free-standing

applications given that the only pre-requisites for device functioning are
light and water wires and external circuits are unneeded. The efficiencies
and cyclability of this device however, can still be greatly improved.

Figure 5. Integrated photovoltaic fuel-generating system [22]

2.4 Hybrid Photovoltaic-Thermal Energy Storage

Besides

developing storage mechanisms

for the

electrical energy

produced directly via PV reactions, hybrid PV-thermal (PVT) collector

systems have also been developed to harness the large amounts of waste
heat generated by the low-efficiency PV reactions. Hybrid PVTs function to

simultaneously convert solar energy into electricity and heat in order to

increase the overall power conversion efficiency of solar modules. The
process of harnessing waste heat energy for subsequent consumption
such as domestic hot water production, is largely reliant on the media
used for heat collection. Developing heat collecting materials may be
essentially split into two types sensible and latent heat storage
materials. Sensible heat storage relies on the rise and fall of the storage
materials own temperature. Although solid sensible heat materials such
as concrete have high heat conductivities, they generally suffer from low
heat capacities. One the other hand, amongst liquid sensible heat
materials, molten salts are generally regarded as most ideal due to their
thermal stability, low vapour pressure, high thermal conductivities, low
viscosity and lack of safety issues. Moreover, in recent years, tenary salt
mixtures with melting points as low as 76C have been discovered. In all,
the main advantage of sensible heat materials is their low cost, relative to
other heat harnessing materials.
Latent heat storage materials on the other hand, are capable of storing
and releasing large amounts of heat by means of phase change
mechanisms such as melting and solidification. Since phase transition
enthalpies are generally high, latent heat storages typically have much
higher heat storage densities than sensible heat storages. Furthermore,
since latent heat storage materials tend to work in an isothermal way
because of phase change, they are especially suited to applications that
require strict working temperatures. The disadvantage of latent heat
storage materials however, their low thermal conductivities. As a result,
these materials usually call for the implementation of additional heat
transfer enhancement technologies such as metal foams and carbon
fibres. [23]
References
[1] Park N. G. (2015). Perovskite Solar Cells: An Emerging Photovoltaic
Technology. Materials Today, 18(2), 65-72.

[2] Goldschmidt V. M. (1926). Die Gesetze der Krystallochemie. Die

Naturwissenschaften, 14(21), 477-485.
[3] Kojima A. et al. (2009). Organometal Halide Perovskites as VisibleLight Sensitizers for Photovoltaic Cells. JACS, 131, 6050-6051.
[4] Bulkin B. (2014). Perovskites: The Future of Solar Power? Retrieved
from http://www.theguardian.com/sustainable-business/perovskites-futuresolar-power.
[5] Wang U. (2014, 18 September). Perovskite Offers Shot at Cheaper
Solar Energy. Retrieved from http://www.wsj.com/articles/perovskiteoffers-shot-at-cheaper-solar-energy-1411937799.
[6] Economist.com. (2013, 28 October). Cell a Million? Retrieved from
http://www.economist.com/node/21588588.
[7] Liu M. et al. (2013). Efficient Planar Heterojunction Perovskite Solar
Cells by Vapour Deposition. Nature, 501, 395-398.
[8] Kim H. et al. (2014). Organolead Halide Perovskite: New Horizons in
Solar Cell Research. The Journal of Physical Chemistry C, 118, 5615-5625.
[9] Liu D. et al. (2013). Perovskite Solar Cells with a Planar Heterojunction
Structure Prepared Using Room-temperature Solution Processing
Techniques. Nature Photonics, 8, 133-138.
[10] Eperon G. E. et al. (2014). Formamidinium Lead Trihalide: A Broadly
Tunable Perovskite for Efficient Planar Heterojunction Solar Cells. Energy &
Environmental Science, 3, 982-988.
[11] Zhou Y. et al. (2015). Room-temperature Crystallization of Hybridperovskite Thin Films via Solvent-Solvent Extraction for High-Performance
Solar Cells. Journal of Materials Chemistry A, 3, 8178-8184.
[12] Snaith H. J. (2013). Perovskites: The Emergence of a New Era for LowCost, High-Efficiency Solar Cells. Journal of Physical Chemistry Letters,
4(21), 3623-3630.
[13] Severin N. et al. (2014). Carbon Nanotube/ Polymer Composites as a
Highly Stable Hole Collection Layer in Pervoskite Solar Cells. Nano Letters,
14(10), 5561-5568.
[14] Mei A. et al. (2014). A Hole-conductor-free, Fully Printable Mesoscopic
Perovskite Solar Cell with High Stability. Science, 345, 295-298.

[15] Leijtens T. et al. (2013). Overcoming Ultraviolet Light Instability of

Sensitized

TiO2

with

Meso-superstructured

Organometal

Tri-halide

Perovskite Solar Cells. Nature Communications, 4, 2885.

[16] Lewis S. N. (2007). Toward Cost-Effective Solar Energy Use. Science,
315, 798-801.
[17] Weber A. Z. et al. (2011). Redox Flow Batteries: A Review. Journal of
Applied Electrochemistry, 41, 1137-1164.
[18] Nguyen T. et al. (2010). Flow Batteries. The Electrochemical Society
Interface, 54-56.
[19] Braff W. A. et al. (2013). Membrane-less Hydrogen Bromine Flow
Battery. Nature Communications, 4, 2346.
[20] Soloveichik G. L. (2014). Metal-free Energy Storage. Nature, 505, 163165.
[21] Bullis K. (2014). Promise Cheaper Batteries for Storing Renewable
Energy.

Retrieved

from

http://www.technologyreview.com/news/526811/nanoparticle-networkspromise-cheaper-batteries-for-storing-renewable-energy/.
[22] Reece S Y. et al. (2011). Wireless Solar Water Splitting Using SiliconBased Semiconductors and Earth-Abundant Catalysts. Science, 334, 645648.
[23] Tian Y. et al. (2012). A Review of Solar Collectors and Thermal Energy
Storage in Solar Thermal Applications. Applied Energy, 104, 538-553.