Articles

https://doi.org/10.1038/s41560-021-00778-w

Rate capability and Ragone plots for phase change

thermal energy storage
Jason Woods    ✉, Allison Mahvi   , Anurag Goyal   , Eric Kozubal   , Adewale Odukomaiya    and
Roderick Jackson

Phase change materials can improve the efficiency of energy systems by time shifting or reducing peak thermal loads. The value
of a phase change material is defined by its energy and power density—the total available storage capacity and the speed at
which it can be accessed. These are influenced by material properties but cannot be defined with these properties alone. Here
we show the close link between energy and power density by developing thermal rate capability and Ragone plots, a frame-
work widely used to describe the trade-off between energy and power in electrochemical storage systems (that is, batteries).
Our results elucidate how material properties, geometry and operating conditions influence the performance of phase change
thermal storage. This research sets a clear framework for comparing thermal storage materials and devices and can be used by
researchers and designers to increase clean energy use with storage.

T
hermal energy storage can shift electric load for building
space conditioning1–4, extend the capacity of solar-thermal
power plants5,6, enable pumped-heat grid electrical storage7–10
and manage thermal loads from electronic equipment11–13. Phase
change materials (PCMs) are a promising thermal storage medium
because they can absorb and release their latent heat as they tran-
sition phases, usually between solid and liquid. Because phase
change occurs at a nearly constant temperature, useful energy can
be provided or stored for a longer period at a steady temperature.
Researchers have explored many PCMs for thermal storage, such as
paraffin waxes and salt hydrates for space cooling14,15 and inorganic
salts, metal alloys and silicon for power generation9,16–18.
The key attributes of any storage device are its energy and power
characteristics19. These attributes are often compared on Ragone
plots in electrochemical storage research20–24, which plot the specific
power (W kg−1) against the accessible specific energy (W h kg−1).
Researchers have developed figures of merit12,25,26 to try to quantify
the trade-off between the energy and power capabilities for ther-
mal storage materials, and these figures of merit have been used to
construct approximations of thermal Ragone plots27. In addition to
the work by Yazawa et al., Christen developed what he referred to as
‘Ragone plots’ for thermal storage, but approached it from a simpli-
fied thermodynamic perspective that cannot evaluate specific mate-
rials or designs of thermal storage devices28.
The thermal storage figures of merit point towards the need for
improved material properties for PCMs. For example, PCMs often
suffer from low power density (how quickly energy can be trans-
ferred to and from the thermal storage device) because of their low
thermal conductivity. Materials research has focused on increasing
this conductivity12,29–34, which is often accomplished by adding ther-
mally conductive fillers to the PCM or using matrices to contain it.
Although these composites have higher power densities, they have
lower storage capacities because the filler or matrix displaces some
of the PCM.
Using these figures of merit to quantify the energy and power
capabilities of a thermal storage material leads to three key limita-
tions. First, the true power and energy density of a device are also
affected by the application, device design and operating conditions,
which is lost when focused solely on material properties. Second,
these figures of merit cannot be determined experimentally on the
device level because they are simply a combination of indepen-
dently measured material properties. Finally, the previously pro-
posed figures of merit cannot distinguish between two materials
where one has a higher power figure of merit and the other a higher
energy figure of merit. Determining the preferred material requires
an understanding of how each material and design parameter influ-
ences performance. A better method for comparing the behaviour
of thermal storage devices is needed to quantify this interconnected
relationship between power and energy.
Here we seek to clarify this relationship by developing thermal
rate capability and Ragone plots, which together quantify the energy
and power performance of an energy storage device. Our methods
mimic the characterization approaches used in electrochemical
energy storage. We show how phase change storage, which acts as a
temperature source, is analogous to electrochemical batteries, which
act as a voltage source. Our results illustrate how geometry, material
properties and operating conditions all contribute to the energy and
power trade-off of a phase change thermal storage device. This ther-
mal storage Ragone framework enables a clear comparison method
between different thermal storage materials and designs.
Rate capability and Ragone plots
Our analysis leverages the extensive research on electrochemical
storage by using analogies between thermal and electrical transport.
For example, conduction heat transfer is driven by a temperature
potential difference and hindered by a thermal resistance in the
same way that electric current is driven by a voltage potential dif-
ference and hindered by an electrical resistance. Although this anal-
ogy is imperfect35 (Supplementary Note 1), it allows us to examine
similarities between solid–liquid phase change and electrochemical
energy storage (Fig. 1).
We focus our analysis on the PCM heat exchanger in Fig. 1b,
which is used for cooling a thermal load (for example, building
air conditioning). Here, a solid PCM defines the charged state,
which is achieved by removing energy from the device. During dis-
charge, a warm fluid is pumped through the heat exchanger channels

National Renewable Energy Laboratory, Golden, CO, USA. ✉e-mail: Jason.Woods@nrel.gov

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Articles
a b
Electric load
–
–
+ –
+
+ +
+ +
+ +
+ +
+ + +
+ +
+ +
Cathode + +
Separator
Fig. 1 | Schematics of electrochemical and thermal energy storage devices, showing analogous inputs and outputs. a, Electrochemical battery during
discharge. b, PCM storage device for cooling during discharge. The PCM device consists of a stack of flat channels surrounded by a form-stable PCM
(pictured in black). Heat from the warm fluid melts the PCM as it passes through the device (discharging the cold storage), allowing the fluid to cool the
thermal load. During this process, the initially solid PCM begins to melt and the phase front (interface between the liquid-orange and solid-purple phases,
see inset) moves away from the fluid channel.
rejecting heat to, and melting, the PCM. The cooled fluid then
absorbs heat from a thermal load before returning to the storage
device at a warmer temperature. This direction of charge/discharge
is the same as electronics cooling (where the load is the heat gen-
erated by the electronics) but the opposite of solar-thermal or
pumped-heat electricity storage. While our selected use case nar-
rows the analysis to a specific example, the trends and insights
gained are relevant to the other heating and cooling applications
mentioned above, and for different device geometries. More infor-
mation about the baseline model geometry and design appears in
Supplementary Note 2.
The baseline analysis is for an organic PCM (n-tetradecane)
embedded in a thermally conductive graphite matrix36, and this
is used for the results below unless noted otherwise. Here, we use
the term PCM storage for materials that absorb or release heat
on a phase transition, including composites. Thermophysical
properties of the materials we considered are summarized in
Supplementary Note 6.
Before describing thermal Ragone plots, let us first consider
how to create rate capability and Ragone plots for batteries. A bat-
tery converts stored chemical energy into electrical energy through
oxidation–reduction reactions. The properties of the anode and
cathode define the capacity (ampere-hours) or the total electric
charge that can be withdrawn from a fully charged cell, and the
open-circuit voltage or the maximum voltage that can be deliv-
ered by the device. Under an electrical load, the supply voltage is
lower than the open-circuit voltage due to internal polarization and
electrical resistances (IRe losses)37. As the battery is discharged, the
supplied voltage eventually drops below the cutoff voltage, at which
point all remaining energy in the battery is no longer useful.
The rate capability curve of a cell is the supplied voltage during
discharge versus the state of charge (SOC), or the fraction of energy
that remains in the battery. Representative rate capability curves for
a lithium-ion battery are shown in Fig. 2a, where the C-rate is the
applied current normalized to the maximum capacity of the cell. For
example, discharging a 10-Ah battery at 20 A will deplete the battery
in half an hour, corresponding to a C-rate of 2. Increasing the C-rate
causes the voltage to drop below the cutoff at higher states of charge,
leaving more unused energy in the battery.
This trade-off between discharge power and the useful discharge
energy is shown in the Ragone plot in Fig. 2b. Each of the rate capa-
bility curves becomes a single point on the Ragone plot—the power
comes from the specific C-rate, and the energy is the cumulative
energy discharged before reaching the cutoff voltage. Figure 2b
NaTuRe EneRgy
High-temperature
fluid inlet
Thermal load
–
+
+
Liquid PCM
Tf,in Tf,out
Anode
Solid PCM Low-temperature
fluid outlet
also shows how the cutoff voltage influences the Ragone curves.
Electrochemical Ragone plots have been used extensively to char-
acterize and compare battery chemistries and for battery selection.
PCM storage is analogous to electrochemical storage (Table 1),
where the PCM sets the system capacity through its latent heat of
fusion and specific heat. The capacity in this case is the total amount
of heat that can be stored in (for hot storage) or gained by (for cold
storage) a device in watt-hours. The PCM also dictates the ideal
potential, in this case, the transition temperature. The actual sup-
ply temperature deviates from the transition temperature because
of thermal resistances in the device, as described in the next sec-
tion. The point where the fluid outlet temperature crosses the cutoff
temperature defines the useful discharge energy. For example, the
cutoff for electronics cooling would be the chip’s maximum allow-
able temperature or for building cooling the temperature that is too
warm to maintain occupant comfort.
Thermal rate capability curves can be generated for different heat
transfer rates (analogous to electric current), again defined using the
C-rate. For thermal storage, the C-rate is the applied heat transfer
rate divided by the maximum thermal energy capacity. Thermal rate
capability curves show the outlet fluid temperature versus the SOC.
Figure 2c shows examples of these thermal rate capability curves for
the cooling device in Fig. 1b. We generated these with a transient
finite-difference numerical model of a fluid channel surrounded
by PCM, which is initially subcooled at 0 °C (Methods). The fluid
temperature difference between the inlet and outlet is held constant
to ensure constant power. The shapes of the rate capability curves
were confirmed with experiments on a PCM storage device, which
is described in Supplementary Note 4. Although not the focus here,
rate capability and Ragone plots can also be generated for sensible
thermal storage devices, where the rate capability curve will be
approximately linear throughout the discharge process (similar to
the voltage response of an electrical capacitor).
The fluid outlet temperature from the PCM storage rises as it is
discharged, like when the voltage drops during discharge in a bat-
tery. Also, like batteries, the rate of temperature rise is faster as the
C-rate increases. This intrinsic trade-off between energy and power
is clearly shown in the corresponding thermal Ragone plot (Fig. 2d)
that quantifies the total amount of energy extracted from the device
before the outlet temperature exceeds the cutoff at different C-rates.
The rate capability curve (Fig. 2c) shows how power affects the
outlet temperature. For 16 C and 12 C, nearly all the energy stored
in the PCM can be extracted I before
I the fluid outlet temperature
exceeds the 12 °C cutoff. This results in a vertical line on the Ragone
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NaTuRe EneRgy Articles
a Rate capability curves b Ragone plots
4.4 500
Open circuit voltage
400
2C
4.1 300

Specific power (W kg–1)

Cell voltage (V) 3.8 200 1C
1
5
C 150
1
3.5 2
C 120
1C 1
C
Cutoff voltage 2C 90 2

3.2
60 Vcutoff = 2.9 V
2.9 Vcutoff = 3.2 V
1
Vcutoff = 3.5 V 5
C

2.6 30
100 80 60 40 20 0 40 60 80 100 150 200 240

c 16 d 160
120
14
Fluid outlet temperaure (°C)

Cutoff temperature 80 2C

Specific power (W kg–1)

12 3
C
2C 2

10 3
C 1C
2 40
8 1C
1
1
C 2
C
6 2 1 20
6
C
4 Tcutoff = 15 °C
Phase change
2 temperature range 10 Tcutoff = 12 °C
1
Tcutoff = 9 °C 6
C
0 6
100 80 60 40 20 0 10 20 30 40 50 60
State of charge (%) Specific energy (W h kg–1)

Fig. 2 | Rate capability and Ragone plots for electrochemical and thermal energy storage. a, Electrochemical energy storage rate capability curves for a
LiCoO2/graphite lithium-ion battery at C-rates of 0.2, 0.5, 1 and 2 (data taken from Thomas and Linden37). b, Corresponding gravimetric Ragone plot when
the cutoff voltage is 2.9, 3.2 and 3.5 V. c, Analogous thermal rate capability curves for a cooling application when the PCM is a n-tetradecane/graphite
composite discharged at C-rates between 1/6 and 3. d, Corresponding gravimetric Ragone plot when the cutoff temperature is 9, 12 and 15 °C. The dashed
lines in b and d are shown as guides for the eye between the evaluated C-rates. The PCM is 3.5 cm thick for all cases shown.

exceeds the cutoff at 27% SOC, meaning that 27% of the stored
Table 1 | Properties and definitions for electrochemical and energy cannot be accessed at this power.
thermal storage Figure 2d also shows the impact of the cutoff temperature, which
is specified to meet the requirements of the application. If the dif-
Electrochemical Phase change thermal
ference between the transition and cutoff temperature is small, the
storage storage
power is severely limited. At 32 C, decreasing the cutoff temperature
Ideal outputs Open-circuit voltage Transition temperature from 12 to 9 °C results in a 51%I reduction in the accessible energy.
(V) (K) When designing PCM storage, the cutoff temperature is a key
Maximum capacity Ce,max = nF (Ah) Cth,max = MPCMΔhc−d parameter for material selection and dictates the range of applicable
(Wh) transition temperatures for a target power rate.
Discharge current or I = ΔV/Re(A) q_ ¼ ΔT=Rth ðWÞ
power I Deviation of rate capability curves from ideal temperature
The transport equation for PCM storage helps elucidate why the
Internal resistance Re,int = Rion + d/σmat A Rth,int = d/kPCM A (K/W)
fluid outlet temperature deviates from the ideal transition tempera-
(V/A)
ture. The temperature difference between the PCM and the fluid
C-rate Crate = I/Ce,max (h−1) _ th;max ðh�1 Þ
Crate ¼ q=C is dictated by the required power and the resistance: ΔT ¼ qR _ th.
R I R
SOC SOC ¼ Idt=Ce;max ð%Þ SOC ¼ qdt=C
_ th;max ð%Þ Increasing power (C-rate) or resistance will increase theI required
I
A more detailed version of this table is provided in Supplementary Table 1. n is the number of
I ΔT. For cooling applications, this higher fluid temperature comes
electrons in the reaction (typically around 30% of the ideal number for Li ion because using more from the load (for example, electronic components get hotter).
would make it irreversible), F is Faraday’s constant, Δhc−d the enthalpy change between the charged These qR_ th temperature ‘losses’ are analogous to IRe voltage losses
and discharged states (latent + sensible heat), MPCM the PCM mass, Rion the ionic resistance
of the electrolyte, d the effective length, A the effective cross sectional area, σmat the electrical
for electrochemical
I storage—they cause a deviation from the ideal
conductivity of the battery materials (electrodes, current collectors and so on) and kPCM the thermal temperature or voltage. However, there is no loss of thermal energy
conductivity of the PCM. to ambient, as there is in batteries when electrical energy is con-
verted to waste heat.
In the rate capability plots, the different C-rate lines show how
ΔT is affected by power and the slope of the rate capability curves
plot (Fig. 2d) for specific powers below 12 C (roughly 28 W kg−1). shows how ΔT increases as a cold PCM storage is discharged.
As the C-rate increases, the rate capabilityI curves deviate further The internal resistance (R00th;int) is the key driver to the changes ΔT
from the transition temperature and reach the cutoff sooner. This during discharge. The internal
I conductive resistance is due to a
reduces how long the storage lasts and the amount of heat that can liquid layer that develops between the fluid channel wall and the
be rejected to the PCM. For example, at 32 C the outlet temperature melt front, which is at the transition temperature (for hot storage,
I
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a b
×10–3 SOC = 10%
6 3.5
100
Active area ratio 3

y position (cm)
2.5
5
2 Inactive
Thermal resistance (K m2 W–1)

80 1.5 area
1

Active area ratio (%)

4
0.5
60 0
3 Internal 0 5 10 15 20 25 30 35 40
T (°C)
resistance c 14
40 3
12

y position (cm)
2
2.5
Contact resistance 2 10
1 20 1.5 8
Fluid resistance 1
6
0.5
0 0 4
100 80 60 40 20 0 5 10 15 20 25 30 35 40
State of charge (%) x position (cm)

Fig. 3 | Thermal resistances and their relationship to temperature profiles in the PCM. a, Thermal resistances and active area ratio (defined as ratio
between the active and total heat exchanger area) during the discharge process at 1 C. The internal resistance is estimated as the average distance
between the channel wall and melt front in the active area of the device, divided by the liquid-phase PCM conductivity. The resistance through the channel
wall is also shown but is negligible compared to the other resistances and was therefore dropped from equation (1). The contact resistance could have
some dependence on the SOC due to thermal expansion, but it was not considered in this model. b, Phase distribution in the PCM at 10% SOC, where the
liquid is shown in yellow and the region undergoing phase change is shown in green. The channel wall that transfers heat into the PCM is at y = 0. A liquid
layer builds up between the fluid channel and the phase change region, which results in an internal thermal resistance. The inactive area is the fully liquid
region that sensibly heats and cannot accept a large amount of energy from the fluid stream. c, Temperature distribution in the PCM at 10% SOC.

it would be a solid layer). This layer increases in thickness during increase in the temperature, where the inflection point at 23% SOC
discharge, increasing the internal resistance (Fig. 3a) and therefore aligns with the steep drop in the active area in Fig. 3a. The prema-
the ΔT maintains the same power. ture loss in the active area can be minimized by increasing the fluid
The internal resistance is just one mechanism lowering the use- flow rate, which reduces the fluid temperature change, or by using a
ful energy capacity. The fluid outlet temperature can be approxi- boiling heat transfer fluid, which exchanges heat at a near-constant
mated with (Supplementary Note 3): temperature. The Supplementary Information includes videos
2 3 showing the progression of the phase front, temperature gradients,
 7 active area and surface heat fluxes in the device (Supplementary
6 q_ Videos 1 and 2).
Tf ;out  26  00 00 00
4T t þ Aact Rth;int þ Rth;f þ Rth;cont 5 � Tf ;in
7 ð1Þ
|fflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl{zfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflfflffl}
key resistances Effects of phase change properties
The proposed framework provides a method to directly compare the
where Tf,in and T t are the fluid inlet and average (midpoint) PCM power and energy densities of thermal storage devices. The internal
transition temperatures,
I Aact the active area and R00th the area-specific resistance is a function of the thermal conductivity, or how well a
thermal resistances (R00th ¼ Rth ´ A). Although this I is not an exact material transports heat, and the PCM thickness, which affects the
analysis and differs from I the finite-difference model used to create distance between the channel wall and the melt front. This resistance
the results, it highlights the main mechanisms causing the tempera- influences the shape of the rate capability curve and the relationship
ture to deviate from the transition temperature in PCM storage. between power and useful energy. This section quantifies how the
The second resistance in equation (1) is the fluid-side convec- internal resistance affects the Ragone curve and lends insight into
tive resistance (R00th;f ), which increases the temperature difference the trade-off between the conductivity and thickness.
between the bulkIfluid and the fluid–wall interface, further increas- If a low thermal-conductivity liquid layer develops between the
ing the outlet temperature. This resistance can be modified by melt front and the channel wall, large temperature gradients develop
changing the fluid channel design or the fluid flow rate, but these in the PCM (Fig. 4a), which then require higher fluid temperatures
factors must be weighed against parasitic pumping losses, which to maintain the desired C-rate (Fig. 4c). This limits the accessible
increase the required energy input. The contact thermal resis- storage capacity to that close to the channel surface, leaving much
tance (R00th;cont) arises due to imperfect contact between the channel of the energy unused. Increasing the thermal conductivity reduces
wall andI the PCM, which imparts a temperature drop across this the thermal resistance and flattens the rate capability curve. This
interface. The reduction in temperature potential due to these two increases the specific energy but has diminishing returns because it
resistances increases linearly with C-rate but is not directly affected is only lowering one of the resistances (R00th;int) in equation (1). High
by the SOC. thermal conductivity also results in a sloped
I phase front (Fig. 4b),
The active area (Aact) is the projected area of the melt front which reaches the insulated boundary opposite to the heated chan-
to the PCM-channel interface. Because the fluid is hottest at the nel wall at higher states of charge, reducing the active area sooner.
inlet, the PCM there melts first (Fig. 3b,c). This non-uniform heat In Fig. 4c, the inflection point due to a loss in the active area occurs
flux lowers the active area once this inlet section of the PCM fully near 40% SOC for 40 W m−1 K−1, but the inflection point shifts to
melts, resulting in an inactive heat transfer area within the device 23% and 10% SOC for 10 and 5 W m−1 K−1, respectively.
(Fig. 3b). This reduction in the active area must be balanced by an Each line in the 1C rate capability plot (Fig. 4c) becomes a single
increase in the driving temperature potential to maintain a con- point on a Ragone plot; additional rate capability curves at different
stant power. The 1C rate capability curve in Fig. 2c illustrates this C-rates complete the Ragone plot shown in Fig. 4d. This plot shows

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NaTuRe EneRgy Articles
a b T (°C)
SOC = 50% k = 1 W m–1 K–1 SOC = 50% k = 10 W m–1 K–1
24
3 3
20
y position (cm)

y position (cm)
2.5 2.5
2 2 16
1.5 1.5 12
1 1
8
0.5 0.5
4
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
x position (cm) x position (cm)
c 1C d
16 200
–1 –1
160 40 W m–1 K–1
1Wm K
14
120
Cutoff temperature
12 80
Fluid outlet temperature (°C)

Specific power (W kg–1)

1C
10

40
8
1 W m–1 K–1
40 W m–1 K–1
6
20
1
4
C
4 –1 –1 –1 –1
1Wm K 10 W m K 1Wm –1 –1
K 10 W m –1
K–1

2 2.5 W m–1 K–1 20 W m–1 K–1 10 2.5 W m–1 K–1 20 W m–1 K–1
–1 –1 –1 –1
5Wm K 40 W m K 5Wm –1 –1
K 40 W m–1 K–1
0 6
100 80 60 40 20 0 10 20 30 40 50 60
State of charge (%) Specific energy (W h kg–1)

Fig. 4 | Effect of thermal conductivity on device performance for PCM thickness of 3.5 cm. a,b, The local PCM temperature at 50% SOC and a C-rate
of 1 are shown for thermal conductivity of 1 W m−1 K−1 (a) and 10 W m−1 K−1 (b). c, fluid outlet temperatures at 1 C. d, Ragone plot for a range of C-rates.
The lines in d are shown as guides for the eye between the evaluated C-rates. Differences in the available energy are primarily related to the PCM surface
temperatures, which increase as the thermal conductivity increases.

that an appropriate thermal conductivity for a device depends on the Ragone plots can be used to compare the performance between
target specific power or C-rate (Table 1 row 5). As an example, shift- different PCMs in a thermal storage device. Figure 6 shows the
ing the electric load for building air conditioning may require a 4-h relationship between the achievable energy and power densities for
discharge to align with the peak period for many electric utility rate PCMs with transition temperatures between 0 and 12 °C.
structures38. Since the baseline PCM storage device has a maximum These results are based on a specific design, including thickness,
capacity of 50.4 W h kg−1, this corresponds to 50.4/4 = 12.6 W kg−1 flow rates and flow channel dimensions, and are not meant to be
power density in Fig. 4d. At this power, a thermal conductivity of exhaustive. One important parameter is the PCM thickness, which
2.5 W m−1 K−1 is high enough to use nearly all of the capacity; how- affects the tube spacing and therefore the power density. For the
ever, if heat needs to be rejected to the PCM at 1 C (50.4 W kg−1), results in Fig. 6, we scaled the thickness to keep the total capacity
a minimum thermal conductivity of 20 W m−1 K−1 is required to constant and, therefore, PCMs with a higher volumetric latent heat
access the full storage capacity. are thinner. This comparison ensures that each device has the same
Another way to address high internal thermal resistance is number of channels and same total maximum capacity.
to reduce the PCM thickness. This reduces the capacity, mean- Although some materials are shown as pure without a conductive
ing a larger number of stacked, single-channel unit cells would matrix, the model excludes natural convection that may occur for
be needed to maintain total capacity. This leads to heavier and pure materials. Natural convection would increase the power density
more expensive devices because of the larger number of channels of these pure materials but is excluded to show trends more clearly.
and joints. A well-designed system needs to consider both the The PCM latent heat sets the maximum specific energy (verti-
power requirements and the additional costs associated with adding cal asymptote in Fig. 6a), while in Fig. 6b the asymptote is set by
more channels. the product of density and latent heat. Although water has a higher
The Ragone plots in Fig. 5 show a trade-off between thermal latent heat than the Department of Energy (DOE) target material,
conductivity and material thickness, where the thickness is half the they approach the same vertical asymptote in Fig. 6b because the
distance between adjacent tubes in the full module (treated as an DOE target material has a higher density (Supplementary Note 5).
adiabatic boundary due to symmetry). For 1 W m−1 K−1 (Fig. 5a), As the power increases, thermal transport affects the shapes of
the thickness of the storage material is extremely limited, especially the Ragone curves. For low thermal-conductivity materials such as
at high power. Pure organic or salt hydrate PCMs typically have n-tetradecane, the accessible energy is less than
 the
 maximum spe-
thermal conductivities below 1 W m−1 K−1, so enhanced materials cific energy, even when discharged over 8 h 18 C . Adding graphite
will be needed for most low-temperature applications. Embedding to tetradecane increases the thermal conductivity
I to 10 W m−1 K−1,
the material in a high thermal-conductivity matrix allows for which improves the specific power at high C-rates. Higher latent
higher power and larger channel spacings, but the matrix dis- heat materials can also improve rate capability because a high latent
places the PCM and therefore comes at the cost of latent heat. This heat allows for thinner PCM layers. The overall effect on the energy
lower latent heat means a lower maximum possible energy density density will depend on the magnitude of the PCM internal resis-
(Supplementary Fig. 6). tances, the total capacity and the desired discharge rate.

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a k = 1 W m–1 K–1
a 200
200
160
160 th = 1.75 cm th = 4.38 cm
th = 2.63 cm th = 5.25 cm 120
120 DOE PCM Tetradecane–graphite
th = 3.50 cm th = 7.00 cm target composite
80
80

Specific power (W kg–1)

Specific power (W kg–1)

1.75 cm
40
40
TBAB hydrate
Water

20
20 Tetradecane

10
10
7.00 cm
6
6 6 10 20 40 60 80 120
10 20 30 40 50 60
Specific energy (W h kg–1)
Specific energy (W h kg–1)

b b 200
k = 10 W m–1 K–1
200 160
160 1.75 cm
120 DOE PCM target
120 Tetradecane–
Power density (kW m–3)
80 graphite composite
80
Specific power (W kg–1)

40
7.00 cm TBAB hydrate
40

Water
20
20

th = 1.75 cm th = 4.38 cm
10
th = 2.63 cm th = 5.25 cm
th = 3.50 cm th = 7.00 cm
6
10 20 30
Specific energy (W h kg–1)
Fig. 5 | Effect of PCM thickness on Ragone curves for two thermal
conductivities. Specific power and energy are shown for thicknesses
(th) between 1.75 and 7 cm. a, 1 W m−1 K−1. b, 10 W m−1 K−1. All other
thermophysical properties, including the latent heat, are kept the same.
The lines are shown as guides for the eye between the evaluated C-rates.
To access the full capacity of the system, the thickness of the PCM is
limited at high power rates and low thermal conductivities.
Discussion
PCMs are a promising thermal storage medium for many applica-
tions, but their low thermal conductivity often limits the achievable
power. Several recent publications discuss improving the thermal
conductivity of these materials12,29–31, but few focus on the relation-
ship between power and energy. Our research leverages analogies
between electrical transport in batteries and thermal transport in
PCMs to clearly describe the trade-off between energy and power
using thermal Ragone plots. We also show how the rate capability
and Ragone curves for thermal storage are affected by the PCM
properties, specifically the thermal conductivity, latent heat of
fusion, density and thickness of the material.
Previous work has attempted to quantify the performance of
different materials using figures of merit. A common example is to
represent power density as the square root of the product of thermal
conductivity, latent heat and density12,25,26, and energy density as the
latent heat. However, these metrics are not sufficient for material
Tetradecane
10
6
6 10 20 40 60 80 120
40 50 60 Energy density (kW h m–3)
Fig. 6 | Effect of material properties on gravimetric and volumetric
Ragone plots for building cooling energy storage. a,b, The gravimetric
(a) and volumetric (b) Ragone plots are shown for organic and inorganic
materials with a phase transition temperature between 0 and 12 °C. For
all cases, the temperature difference between the fully discharged and
charged states is 10 °C and the cutoff temperature difference ( Tcutoff  Tt)
is 7.4 °C. For simplicity, any effects from natural convection wereI ignored.
The DOE PCM target uses material properties that meet the targets
set by DOE’s Building Technologies Office in the 2019 BENEFIT funding
opportunity44. The DOE targets were based on the volumetric energy
density, and we assumed a latent heat of 250 kJ kg−1 and a density
of 1,330 kg m−3 to generate the gravimetric Ragone plot. All material
properties used to generate the data are included in Supplementary Table
2. The lines are shown as guides for the eye between the evaluated C-rates.
selection and design of a thermal storage device, as illustrated by
two examples.
First, consider water and graphite–tetradecane. The latter has a
power density figure of merit that is three times higher than that of
water, but a latent heat that is half that of water. But it is unclear how
to weigh the relative importance of the power figure of merit and
the latent heat. The proposed framework can directly  compare
 these
two materials, and shows that for higher powers 32 C , the graph-
ite–tetradecane design achieves twice the energy density
I to that of
water, but for lower power 14 C , water achieves twice the energy
density to that of graphite–tetradecane.
I
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NaTuRe EneRgy
Second, the proposed framework can be used to select the
appropriate level of thermal-conductivity enhancement for a PCM
in the device in Fig. 1b. One option is to use a low-enhancement
(1 W m−1 K−1) and use thin PCM layers with close spacing of the fluid
channels. Another option is to use high enhancement (10 W m−1 K−1)
and thicker PCM layers with larger spacings. The spacings could
be selected to give equivalent performance on the Ragone plot,
and the appropriate design will then depend on the relative cost of
the additional tubes compared to the cost of thermal-conductivity
enhancement. Thus, the proposed framework is a starting point for
cost optimization for thermal storage materials and devices that
can maximize economic and environmental benefits. However, the
focus of the thermal Ragone plots presented here, as in the Ragone
plots used for battery research, is not on cost-based optimization,
but rather on the performance trade-off between energy and power.
This framework sets a clear objective: push the Ragone curve up
(higher power) and to the right (higher energy). This allows for easy
comparisons between different thermal storage material or device
designs, whether it is used as an experimental characterization tech-
nique or to show potential improvements through modelling. This
provides a fundamental basis for defining material property targets
and can be a critical design and optimization tool for researchers
and practitioners developing thermal storage materials and devices.
Methods
Numerical model description. We developed a two-dimensional transient
numerical model using the finite-difference approach39 to model the progression
of phase change during the discharge process and its effects on the outlet fluid
temperature. This model was used to generate rate capability curves for a
representative cold storage device. The storage device consists of flat fluid channels
surrounded by PCM, as shown in Fig. 1b. For the baseline conditions shown in
Fig. 2c,d, the channels are 45.7 cm long (LHX), 25.4 cm wide (WHX) and the distance
between adjacent channels is 7 cm (2thPCM). The model takes advantage of symmetry
and includes half of a fluid channel and the PCM between the channel surface and
the midplane between adjacent channels. The symmetry condition dictates adiabatic
boundary conditions. In this work, the PCM thickness is defined as half the distance
between adjacent channel walls, or the distance between the channel wall and the
line of symmetry in the model. The PCM is discretized into 800 subvolumes, and
the fluid stream was divided into 40 subvolumes in the axial direction. The number
of nodes were chosen so that doubling them in any direction resulted in less than a
2% change in the specific energy. The heat transfer between adjacent PCM cells is
calculated with a discretized version of Fourier’s law40, accounting for directional
differences in the thermal conductivity for some materials (k|| and k⊥), and the
enthalpy change (dh) with time is calculated using an energy balance:
 
dhi;j WHX kk dy   k? dx   maximum errors are 0.01 and 0.21%, respectively.
¼ Ti;j�1 þ Ti;jþ1 � 2Ti;j þ Ti�1;j þ Tiþ1;j � 2Ti;j ð2Þ
dt Mi;j dx dy
where i and j represent the node location, M is the node mass, T is the node
temperature, dx is the length of the node in the fluid flow direction and dy is
the length of the node in the direction perpendicular to fluid flow. This analysis
assumes that the PCM is static and that conduction is the only mode of heat
transfer in the PCM material. Buoyancy-induced liquid motion is possible,
particularly in pure materials, which would help mix the liquid layer and reduce
fluid outlet temperatures. More work is needed to quantify the effects of buoyancy
on the rate capability curves of non-composite PCM materials. However, this
analysis primarily focuses on high thermal conductivity PCMs (>1 W m−1 K−1),
which usually contain a matrix structure. This high thermal-conductivity structure
will limit buoyancy-induced fluid motion and result in primarily conductive heat
transfer throughout the material.
Heat transfer between the fluid stream and the PCM ( q_ f ) is calculated by
considering all relevant resistances, including fluid convection, I conduction
through the channel wall, contact and conduction through the PCM in the node
adjacent to the wall (Supplementary equation (S1)). The fluid temperature change
with time is then calculated with an energy balance accounting for heat transfer
to the PCM, heat conduction through the fluid and fluid advection using an
upwinding scheme41, as shown in equation (3). In this equation cp,f is the fluid
specific heat, m_ f is the fluid mass flow rate, kf is the fluid thermal conductivity and
Hch is the channel
I height.
 
dTf;i 1   kf Hch WHX  
¼ _ f cp;f Tf;i�1 � Tf;i � 2q_ f þ
m Tf;i�1 þ Tf;iþ1 � 2Tf ;i
dt cp;f Mf ;i dx
ð3Þ
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Articles
All thermodynamic properties of the fluid are based on a 10% mixture of
propylene glycol-water by volume42. The PCM enthalpy and the fluid temperature
are numerically integrated to calculate the thermodynamic properties in the next
time step using the Euler approach39. Finally, the PCM phase and temperature are
calculated using material-specific enthalpy-temperature relations.
In this study, the thermal storage device was discharged at a constant heat
transfer rate to generate Ragone plots, which  was set bymonitoring the heat
transfer out of the fluid stream, q_ f ¼ mc_ p Tf ;in � Tf ;out . A constant heat transfer
rate can be achieved in several ways, I but in this study, we kept the fluid temperature
difference ðTf ;in � Tf ;out Þ constant throughout the simulation by adjusting the inlet
temperatureI as the outlet temperature increased with the internal resistances. The
fluid temperature difference was set to 4.5 °C for the cases shown. The mass flow
rate ( m
_ ) was set to achieve the desired C-rate and changed only slightly during each
run to account for changes in the specific heat (cp) with temperature. The required
heat transfer into the PCM is related to the total capacity, which is a function of the
difference between the enthalpy when the device is fully charged and discharged
(Δhc−d) and the mass of the PCM (ρthPCMAcs):
Δhc�d ρthPCM Crate Acs
q_ f ¼
3; 600
ð4Þ
Several parameters were tracked through time during the simulation, including
the fluid outlet temperature and the SOC, defined using the average enthalpy of the
PCM ( h) at a given time step:
 
SOC ¼ 100 ´ 1 �
hðt Þ � hcharged
ð5Þ
hdischarged � hcharged
where hcharged and hdischarged are the enthalpy at the fully charged and fully discharged
temperatures, respectively. This information was used to construct the rate
capability curves shown in Figs. 2c and 4c. The gravimetric energy and power
densities (often called the specific energy and specific power, respectively) are then
calculated during postprocessing. First, the cutoff time (tcutoff ), defined when the
outlet fluid temperature exceeded the cutoff temperature, is recorded. The specific
power is calculated by dividing the heat transferred to the PCM by the total PCM
mass, and the specific energy is calculated by integrating the specific power from
t = 0 to t = tcutoff. This information was used to construct the Ragone plots presented
throughout the paper.
Model validation. First, the model was modified to simulate freezing of a
semi-infinite PCM with a constant temperature boundary condition. The results
were compared to the classical Neumann’s solution for two-phase solidification43.
To allow for direct comparison, the numerical model was terminated when the
boundary condition started to affect the temperature at the insulated boundary
opposite from the cooled surface and pure water was used as the PCM because its
phase transition occurs at a single temperature. The results from the numerical
model match the analytical solution well where most of the local temperatures
fall within 0.05% of the analytical solution. The largest deviations occurred at
the location closest to the melt front. With 24 nodes in the heat flow direction,
the average error is 0.02% (ΔTlocal = 0.06 K) and the maximum error is 0.62%
(ΔTlocal = 1.66 K). With 72 nodes in the heat flow direction, the average and
The full model was also validated experimentally using a microchannel heat
exchanger. A description of the experiments and a comparison between the model
and experimental results is provided in the Supplementary Note 4.
Data availability
All data generated or analysed during this study are included in the published
article, its Supplementary Information and Source Data files
Code availability
The numerical model developed for this work was generated in MATLAB R2019b.
Unrestricted access to the source code is available at https://github.com/NREL/
ThermalRagone.
Received: 17 June 2020; Accepted: 5 January 2021;
Published: xx xx xxxx
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Acknowledgements
This work was authored by the National Renewable Energy Laboratory (NREL), operated
by Alliance for Sustainable Energy, LLC, for the US DOE under contract no. DE-AC36-
08GO28308. Funding provided by US DOE Building Technologies Office. The views
expressed in the article do not necessarily represent the views of the DOE or the US
Government. We thank S. Mumme from the DOE Building Technologies Office for his
support and insight on this paper. We also thank J. Vidal and M. Bianchi from NREL for
their feedback on our work.
Author contributions
J.W. developed the concept of thermal rate capability and Ragone plots and oversaw
the project, A.M. developed the numerical model, performed experiments on the
thermal storage device, analysed the data and created the figures, A.G. and E.K. helped
design the thermal storage device experiments and contributed to developing the
concept, A.O. measured material properties and contributed to developing the concept,
R.J. helped develop the idea and provided guidance during the project. J.W. and A.M.
wrote the paper.
Competing interests
The authors declare no competing interests.
Additional information
Supplementary information The online version contains supplementary material
available at https://doi.org/10.1038/s41560-021-00778-w.
Correspondence and requests for materials should be addressed to J.W.
Peer review information Nature Energy thanks Patrick Shamberger and the other,
anonymous, reviewer(s) for their contribution to the peer review of this work.
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