ll
Future Energy
Toward Controlled
Thermal Energy
Storage and
Release in Organic
Phase Change
Materials
Mihael A. Gerkman1
and Grace G.D. Han1,*
Grace Han was born in South Korea and
graduated from POSTECH with a BS in
Chemistry. She obtained her PhD in
Chemistry at MIT in 2015 and joined the
Department of Materials Science and En-
gineering at MIT as a postdoctoral asso-
ciate. Grace started her independent
career as an assistant professor at the
Department of Chemistry at Brandeis Uni-
versity in 2018. Her research interests
span energy conversion and storage, mo-
lecular switch chemistry, phase transition
of materials, and atomic-resolution mo-
lecular imaging.
Mihael Gerkman received his BS in
Chemistry from SUNY Potsdam in
2016. Currently, he is pursuing his
PhD at Brandies University in the Han
group. His research is focused on the
synthesis of novel molecular switches
and the study of their reversible isomer-
ization dynamics in condensed phases
for thermal energy storage applica-
tions.
Introduction
A significant portion of energy input in in-
dustrial processes, about 20%–50%, is
lost as waste heat, and about 63% of
that wasted energy is released at temper-
atures below 100 C.1 This massive
amount of low-grade waste heat is not
currently recovered by economically
viable means, as opposed to medium-
or high-grade waste heat being effec-
tively harnessed to generate power.
Thermoelectric generators can be a solu-
tion for low- and medium-grade heat re-
covery, but their low efficiencies, gener-
ally less than 2%, have precluded their
implementation at an industrial scale.
An alternative way of harvesting low-
grade waste heat is to store it in a chem-
ical form, using either reversible reac-
tions (i.e., thermochemical energy stor-
age) or physical state changes (i.e.,
thermophysical energy storage).2 Fig-
Joule 4, 1621–1625, August 19, 2020 ª 2020 Elsevier Inc. 1621
ure 1A summarizes state-of-the-art
thermal energy storage processes and
representative chemicals. These stor-
age methods span a wide range of
operating temperatures and energy
storage densities, presenting variable
efficacy of each type of process. For
example, ammonia-based thermo-
chemical conversion is shown as a ther-
mochemical reaction, indicating that
gas-phase reactions require large-vol-
ume vessels and yield low-volumetric
energy densities. Thermochemical re-
actions are typically operated at high
temperatures, which make them less
suitable for low-grade waste heat re-
covery. Sorption-based thermochem-
ical reactions can be alternatives for
harvesting low-to-medium-grade waste
heat. However, the requirements of
condensers and evaporators for liquid
storage as well as large gas storage
tanks are less desirable for realizing
portable applications. Thermophysical
energy storage can be classified into
sensible heat and latent heat storages.
The curved lines in Figure 1A show the
sensible heat storage in various solids
and fluids with high heat capacities.
Molten salts and organics are also
used for sensible heat storage, despite
being omitted from the plot to reduce
visual complexity. These solids and
fluids can gradually store and release
heat, and the total energy storage relies
on the large gap between the low and
high end of operating temperatures.
On the other hand, phase change mate-
rials (PCMs) are able to store relatively
large quantities of latent heat within a
very small window of temperature
change because of phase transitions
occurring at a constant temperature,
for example, at a melting point. Inor-
ganic salts (e.g., metal chlorides, hy-
droxides, hydrides, etc.), salt hydrates,
and aliphatic organics are the most
common PCMs, and the latter two
types are the most suitable for low-
grade waste heat recovery. Detailed
 ll
Figure 1. Current State-of-the-Art Thermal Energy Storage Materials
(A) Thermochemical and thermophysical energy storage materials plotted in a wide range of
operation temperatures and energy densities.
(B) Area of organic PCMs magnified from (A). Conventional passive PCMs are marked as circles and
diamonds, and the light-controlled PCMs and composites are shown as their windows of controlled
heat absorption and release temperatures.
ranges of temperatures and energy
densities are described in Figure 1B
for organic PCMs, highlighting the ali-
phatics and polyethylene glycol (PEG)
with phase transitions under 100 C.
The strong van der Waals interactions
between long aliphatic chains serve as
a major driving force for energy stor-
age, while H-bonds govern the energy
storage for more polar organic PCMs
such as sugar alcohols and polyols.
All of the listed conventional PCMs
have an intrinsic limitation, i.e., lack of
control over heat absorption and
release temperatures and heat storage
time. Reversible phase transitions
commonly occur at fixed melting and
crystallization points that are very close
to each other. Therefore, upon initial
melting, the liquefied PCMs can be
immediately crystallized and lose the
latent heat—if the temperature of envi-
ronment drops below the melting or
crystallization points. In this case, the
latent heat storage is very short-lived,
particularly after the removal of the
waste heat source. Highly polar PCMs
such as salt hydrates and sugar alcohols
have another type of latent heat stor-
age problem. Because of the high-den-
sity H-bonds cross-linking the network,
the liquefied PCMs exhibit a large de-
gree of uncontrolled supercooling.
Typically, these molten PCMs exhibit
batch-to-batch variable crystallization
1622 Joule 4, 1621–1625, August 19, 2020
behavior, as they are highly susceptible
to accidental crystallization by impu-
rities at the surface. These uncontrolla-
ble heat release processes remain a
challenge for long-term latent heat
storage in conventional PCMs without
substantial insulation and extreme puri-
fication, thus urging the development
of methods that enable more control
over the latent heat storage and
release.
In this Future Energy perspective
article, we introduce recently devel-
oped optical methods that demon-
strate the active control over the latent
heat storage in organic PCMs—see
the bars in Figure 1B that mark the win-
dows of light-controlled heat release
from novel PCMs. Mechanisms of im-
plementing other triggering stimuli
are showcased as future directions,
opening up opportunities for latent
heat storage that is controlled indepen-
dently from temperature change. These
control methods are introduced within
the scope of organic PCMs, but they
are generally applicable to other types
of PCMs, provided that molecules are
designed to function at the respective
operating conditions.
Recent Advances
A novel strategy of controlling melting
or glass transition temperatures of
small molecules and polymers has
Future Energy
been developed by chemists in the mo-
lecular switch field by incorporating
photo-switching units to pre-existing
scaffolds.3 Photo-switches such as azo-
benzenes have been independently
investigated for exploiting their isomer-
ization energy for solar energy conver-
sion and storage.4 It is only recent, how-
ever, to consider these strategies for
triggering heat release from organic
PCMs that are easy to modify with
photo-switching moieties. A general
operation scheme is shown in Figure 2A,
where the gray rods represent aliphatic
chains of conventional organic PCMs
with blue and red indicating the two
states of photo-switch (OFF and ON)
attached to the PCMs. The photo-
switches undergo reversible structural
changes upon UV and visible light ab-
sorption, and such drastic change
enable the control over the phase of
PCMs.
Initially, the switch-decorated PCMs
form crystalline solid, similar to the
typical solid-state paraffin or fatty acids.
The blue switches at their OFF state are
planar as a ground-state structure. The
waste heat absorption by the PCMs
above their melting point produces
liquid PCMs (step 1) that would gener-
ally solidify back to the initial crystalline
form once the waste heat source is
removed. Step 2 activates the switch
by UV irradiation, and the resulting
liquid PCMs with ON-state switches
can be preserved even at temperatures
much lower than the initial melting/
crystallization points, as low as 45 C
(step 3).5 The switches with bent struc-
tures prevent the crystallization of
aliphatic chains, effectively lowering
the crystallization point. The reverse
switching is triggered by visible light
irradiation (step 4), which controllably
crystallizes the PCMs and releases the
latent heat at chosen temperatures.
The energy diagram in Figure 2B shows
that upon melting (step 1), the UV irra-
diation raises the energy level of
switches by DHiso (isomerization energy
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Future Energy

release. A third challenge associated

with the optical triggering is the incom-
plete crystallization of bulk liquid
PCMs. Once the surface of bulk PCMs
absorbs light and crystallizes, the solid
layer formed on top scatters incident
light and limits the penetration of
trigger light into the deeper part.

All of the stated challenges signify the

necessity for an alternative switching
tool to the optical method, particularly
for a rapid and complete triggered
Figure 2. Optically Controlled Thermal Energy Storage in Organic PCMs heat release process. Thermal activa-
(A) Schematic of (1) thermal energy absorption by switch-decorated PCMs, (2) UV activation of the tion for the reverse switching is
liquefied PCMs, (3) cooling of liquefied PCMs, and (4) visible-light-triggered reverse switching and excluded from viable methods, as the
heat release. The straight and curved gray rods represent crystalline and liquid phases,
necessary external thermal energy
respectively.
(B) Schematic energy diagram of enthalpy and temperature changes of PCMs along (1–4) stepwise input is considered unavailable at
process. target places for heat release (cooler
than waste heat source). We introduce
several alternative triggering methods
between OFF and ON structures). The composites release heat between that were identified from fundamental
liquid PCMs with ON switches establish room temperature and 60 C, showing research on molecular switches, mostly
a lowered crystallization point (Tc) as a great potential for mild heating appli- conducted in solutions or on monolayer
low as 45 C, then the visible light trig- cations such as wearable gadgets and films. These ideas demonstrated at the
gering crystallizes the liquid phase at food and water heating. molecular level pave the way for con-
any temperature between the initial trolling transitions of organic PCMs at
Tm and new Tc. The total heat released Challenges bulk scale, provided that such chemical
from this process is the crystallization The optical control method incorpo- methods are successfully translated in
energy (DHc) of PCMs combined with rates common photo-switches, such as condensed phases.
the isomerization energy (DHiso) of azobenzene derivatives, that possess
switches. intrinsic challenges for large-scale ap- Future Directions
plications. First, the quantum yields of Mechanical Triggering
Selecting molecular switches that conventional switches are low (10%– Figure 3A illustrates various strategies
respond to orthogonal wavelengths of 40% for forward and reverse transi- that can be applied to liquefied PCMs
light for reversible structural change is tions), which decreases the overall effi- to trigger the heat release. First, the
a key to accomplishing this cycle. The ciency of the storage system. However, ON switches in stage 2 can be mechan-
optical control of phase transition was this issue is being actively tackled by ically triggered to revert to the OFF-
also successfully manifested in the the molecular switch field via judicious state structure in stage 1. A recent
organic composite systems, i.e., the modifications of switch structures, report on the reverse switching of azo-
non-covalent mixture of photo- yielding vastly improved quantum benzene monolayer by mechanical
switches and conventional PCMs such yields (e.g., 90%).7 A second major sweeping with AFM tips highlights the
as fatty acids (marked as light- challenge is achieving a fine balance viability of this process,8 also supported
controlled composite in Figure 1B).6 In pursuing between a long storage time by a variety of mechanochemical isom-
such composites, the switches act as (i.e., long half-life of ON switch) and a erization reactions discovered to date.
dopants in aliphatic PCM medium and rapid triggering of crystallization. Half- The activation energy barrier for the
alter the phase transition temperatures lives of switches have been greatly mechanical switching of azobenzene
of the passive PCMs through intermo- improved up to 46 years as opposed was estimated to be 1.5 eV, which is
lecular interactions. The composites to weeks for conventional counter- less than the photon energy at 450 nm
also exhibit the identical heat storage parts.5 However, these stabilized (2.7 eV) required for reversion. Chal-
cycle in Figure 2B, despite the window switches often display suboptimal lenges remain in applying mechanical
of light-controlled heat release being reverse switching kinetics, hindering forces to affect the majority of randomly
limited to 15 C. The light-controlled instantaneous light-triggered heat distributed switches, which can be

Joule 4, 1621–1625, August 19, 2020 1623

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Figure 3. New Strategies for Triggering Heat Release
(A) Schematic of solid-state PCMs being thermally charged and UV-activated, then triggered to be
crystallized by various alternative methods.
(B) Energy diagram illustrating the activation energy reduction for the reverse isomerization via
redox or ion binding.
potentially addressed by incorporating
an oligomeric or polymeric PCM
network for effective transduction of
mechanical energy to switching units.
Mechanical triggering in the form of
shearing, compression, shock wave,
and so on can also be applied to other
bulk functional molecular liquids that
exhibit supercooling in the absence of
switch units. Instead of inducing isomer-
ization, mechanical energy can alter the
arrangement of the supercooled mole-
cules and harness the energy difference
associated with intermolecular interac-
tion changes. The mechanical energy
applied to supercooled liquids can
generate initial nucleation seeds that
induce the propagation of crystalliza-
tion. Shear-triggered crystallization has
been reported in small molecular sys-
tems for aggregation-induced emission
at the activation pressure of 0.9 kPa.9
Designing molecules that possess large
energy gap between the stabilized
liquid phase and crystalline phase will
be a key aspect for accomplishing ther-
mal applications.
Electrical Triggering
Other suggested methods fundamen-
tally reduce the activation barrier of
the reverse isomerization by applying
redox or ion binding to ON switches.
Electrical switching of various photo-
isomers such as azobenzene, spiro-
pyran, and diarylethene have been re-
1624 Joule 4, 1621–1625, August 19, 2020
ported in solution. Oxidation or reduc-
tion of ON switches generates cationic
or anionic radical species that readily
revert to the OFF structures because
of the significantly reduced activation
barriers (Figure 3B). Fundamental
work by Hecht and co-workers reports
(photo)redox catalysis of azobenzene
reverse switching and the significantly
increased reversion kinetics, i.e., 1017
times faster than the reversion of
neutral counterpart.10 The activation
energy for the reversion is calculated
to drop down to 0.1–0.3 eV for radical
anions and cations, as compared with
1–1.2 eV for neutral species. The
radical species are illustrated as the
activated ON switches (stage 3) in Fig-
ure 3A, which can rapidly revert to
OFF switch radicals (stage 4) before
crystallizing to release heat (stage 1).
The electrochemical activation of
azobenzene has been performed on
Langmuir-Blodgett films and liquid
crystals, while its application to bulk
materials for thermal energy release
remains unexplored, to the best of
our knowledge. Large-area electrodes
such as transparent conducting oxide
on glass can be used to electrically
trigger the isomerization of bulk mate-
rials. This catalytic activation process
is expected to open up a new avenue
for electrically controlled heat storage
in organic PCMs with more complete
and rapid heat release.
Future Energy
Coordination-based Triggering
The coordination of proton11 and other
cations12 to azo group has been also
shown to facilitate the reverse switching
in solution. Fuchter and co-workers
report arylazopyrazole systems with
intrinsically long half-lives and their
effective reduction by acid treatment.11
This strategy can be implemented to
condensed-phase materials such that
fine-tuning pH or ion concentration
can rapidly induce heat release from
liquid PCMs. The loss of protons and
ions from stage 4 prior to the crystalliza-
tion (stage 1) requires further investiga-
tion. An over-arching technical chal-
lenge to address for alternative
triggering methods is to form a closed
system which reversibly and selectively
respond to the external stimuli.
Conclusions
This emerging area of controlled heat
storage in organic PCMs would attract
the interdisciplinary efforts from chemis-
try, materials science, and mechanical en-
gineering. The success of achieving large-
scale functional devices relies on molecu-
lar design, materials optimization, and
fabrication of effective heat-transfer de-
vices. Elucidating fundamental control
mechanisms and diversifying the trigger
methods will be the first step for the even-
tual device-level success. Organic PCMs
such as paraffins and fatty acids are well-
known affordable materials at the cost
level of less than $1,000 per ton. Through
simple and high-yielding syntheses, the
photoactive PCMs can be achieved at an
industrial scale. The cost of operation is
also estimated to be reasonable; the us-
age of 0.1 kWh of electricity ($13) is ex-
pected for charging a kilogram-scale ther-
mal battery during the initial photo-
activation, which is the most energy-
consuming step throughout the whole
waste heat storage-and-release cycle.
Instead of employing LEDs or arc lamps,
optical filters can be applied to harness
desirable ranges of solar spectrum and
further reduce the cost of operation. We
believe that the controllability of heat
storage will further expand the utility of

Future Energy
PCMs for low-grade waste heat recovery,
and various mobile applications such as
automobile and personal heating in
particular will significantly benefit from
the lightweight, affordable, highly pro-
cessable, and most importantly switch-
able organic PCMs.
ACKNOWLEDGMENTS
We acknowledge the SPROUT award
(2019-042) from Brandeis Office of Tech-
nology Licensing and Provost Research
Award from Brandeis University.
DECLARATION OF INTERESTS
M.A.G. and G.G.D.H. hold the following
patents in relation to heat storage in
phase change materials: PCT/US2020/
031344 and U.S. Provisional 62/969,634
(2020).
1. Wang, X., Huang, Y.T., Liu, C., Mu, K., Li,
K.H., Wang, S., Yang, Y., Wang, L., Su, C.H.,
and Feng, S.P. (2019). Direct thermal
charging cell for converting low-grade heat
to electricity. Nat. Commun. 10, 4151.
2. Weinstein, L.A., Loomis, J., Bhatia, B.,
Bierman, D.M., Wang, E.N., and Chen, G.
(2015). Concentrating solar power. Chem.
Rev. 115, 12797–12838.
3. Xu, W.C., Sun, S., and Wu, S. (2019).
Photoinduced reversible solid-to-liquid
transitions for photoswitchable materials.
Angew. Chem. Int. Ed. Engl. 58, 9712–
9740.
4. Dong, L., Feng, Y., Wang, L., and Feng, W.
(2018). Azobenzene-based solar thermal
fuels: design, properties, and applications.
Chem. Soc. Rev. 47, 7339–7368.
5. Gerkman, M.A., Gibson, R.S.L., Calbo, J.,
Shi, Y., Fuchter, M.J., and Han, G.G.D. (2020).
Arylazopyrazoles for long-term thermal
energy storage and optically triggered heat
release below 0  C. J. Am. Chem. Soc. 142,
8688–8695.
6. Han, G.G.D., Li, H., and Grossman, J.C.
(2017). Optically-controlled long-term
storage and release of thermal energy in
phase-change materials. Nat. Commun. 8,
1446.
7. Moormann, W., Tellkamp, T., Stadler, E.,
Röhricht, F., Näther, C., Puttreddy, R.,
Rissanen, K., Gescheidt, G., and Herges, R.
(2020). Efficient conversion of light to
chemical energy: Directional, chiral
photoswitches with very high quantum
yields. Angew. Chem. Int. Ed. Engl.
Published online April 29, 2020. https://doi.
org/10.1002/anie.202005361.
ll
8. Berson, J., Moosmann, M., Walheim, S., and
Schimmel, T. (2019). Mechanically induced
switching of molecular layers. Nano Lett. 19,
816–822.
9. Chung, K., Kwon, M.S., Leung, B.M., Wong-
Foy, A.G., Kim, M.S., Kim, J., Takayama, S.,
Gierschner, J., Matzger, A.J., and Kim, J.
(2015). Shear-triggered crystallization and
light emission of a thermally stable
organic supercooled liquid. ACS Cent. Sci. 1,
94–102.
10. Goulet-Hanssens, A., Rietze, C., Titov, E.,
Abdullahu, L., Grubert, L., Saalfrank, P.,
and Hecht, S. (2018). Hole catalysis as a
general mechanism for efficient and
wavelength-independent Z / E
azobenzene isomerization. Chem 4, 1740–
1755.
11. Gibson, R.S.L., Calbo, J., and Fuchter, M.J.
(2019). Chemical Z- E isomer switching of
arylazopyrazoles using acid.
ChemPhotoChem. 3, 372–377.
12. Hanopolskyi, A.I., De, S., Białek, M.J.,
Diskin-Posner, Y., Avram, L., Feller, M.,
and Klajn, R. (2019). Reversible switching
of arylazopyrazole within a metal-organic
cage. Beilstein J. Org. Chem. 15, 2398–
2407.
1Department of Chemistry, Brandeis University,
415 South Street, Waltham, MA 02453, USA
*Correspondence: gracehan@brandeis.edu
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