Applied Energy 202 (2017) 377–385

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Efficient solar power generation combining photovoltaics and mid-/low-

temperature methanol thermochemistry
Wenjia Li a,b, Yong Hao a,b,⇑
a
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, PR China
b
University of Chinese Academy of Sciences, Beijing 100049, PR China

h i g h l i g h t s

A PVT system integrating PV and thermochemistry is proposed, for the first time.

High efficiency, energy storage ability and temperature insensitivity are achieved.

Net solar-electric efficiency of 43% and overall efficiency of 55% are obtained.

Solar energy storage via syngas enables stable power supply all day long.

a r t i c l e i n f o a b s t r a c t

Article history: A hybrid solar power generation system integrating a solar photovoltaic (PV) module and a solar thermo-
Received 1 February 2017 chemical module is proposed based on methanol thermochemistry. Sunlight is concentrated by trough
Received in revised form 13 April 2017 mirror collectors and partially converted to electricity by PV cells overlain on the surface of a solar ther-
Accepted 9 May 2017
mochemical reactor. An endothermic chemical process of methanol (e.g., decomposition) within the reac-
Available online 1 June 2017
tor then absorbs the ‘‘waste heat” of the PV cells and simultaneously cools the cells. During this process,
the low-level thermal energy from the sunlight is upgraded to high-level chemical energy in syngas,
Keywords:
which is stored and burned to generate electricity when necessary. Analysis indicates that the theoretical
Solar
Photovoltaic
net solar-electric efficiency of the hybrid system could be as high as 45% and relatively insensitive to
Methanol thermochemistry operation temperature and pressure. Additionally, the system exhibit a good potential in solar energy
Hybrid storage, and capable of providing stable electricity supply around the clock. The PV–thermochemical
Power generation hybrid system might suggest a promising approach for efficient and stable power generation from solar
Efficiency energy.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Drastic increase in fossil fuel consumption and the consequen-
tial worldwide climate change have lead to a pressing demand on
low-cost, large-scale utilization technologies of renewable energy
to gradually phase out fossil fuels in a foreseeable future. Renew-
able energy sources that are commensurate with or far beyond
the scale of human energy demand, such as solar energy, are rare
and yet carry particularly important historical missions.
Solar energy utilization still faces a major cost barrier that par-
tially results from the relatively low conversion efficiency of sun-
light to power. Among a portfolio of current solar power
technologies, the efficiency of practically applicable photovoltaic
⇑ Corresponding author at: Institute of Engineering Thermophysics, Chinese
Academy of Sciences, Beijing 100190, PR China.
E-mail address: haoyong@iet.cn (Y. Hao).
(PV) cells is relatively low. Take crystalline silicon solar cells for
example, although the entire visible part of the solar spectrum
and some parts of the infrared spectrum fall well within their con-
version capability, efficiency of commercially available silicon cells
is usually 10–20% [1], while the majority of solar irradiation is
wasted in the form of low-temperature (e.g., 100 °C or lower)
thermal energy [2]–longer wavelength radiation that falls below
the band gap of silicon does not carry enough energy to excite elec-
trons and thus entirely turns into dissipated heat; shorter wave-
length radiation with photonic energy higher than the band gap
can only be partially converted to electricity by quantum principles
underlying photoelectric effects [3] and the rest is still converted to
heat. Although much higher efficiencies have been achieved
through advances in materials and configuration of solar cells
(e.g., 46.0% cell efficiency for III–V multi-junction solar cells [4]),
waste heat still accounts for more than half of the solar energy
input. Moreover, not only PV cells are practically used as modules

http://dx.doi.org/10.1016/j.apenergy.2017.05.086
0306-2619/Ó 2017 Elsevier Ltd. All rights reserved.
378 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385
(instead of single cells), but high-efficiency PV cells commonly
work in conjunction with concentrating optics (e.g., Fresnel lens;
CPV) to enhance power generation performance and lower gener-
ation cost. These facts, however, lead to a clear distinction between
cell efficiency and system efficiency; the module factor and optical
loss become inevitable factors that must be taken into account. For
example, if the optical efficiency of solar collection is 0.85 [5] and
the efficiency of a PV module to be 90% of that of a single cell [6],
the efficiency of a concentrated PV system consisting of 46.0% effi-
cient single cells [4] then translates to 35.2% (practical efficiency),
which means that nearly two-thirds of the incident solar energy is
dissipated to the ambient. By comparison, concentrated solar
power (CSP) exhibits similarly low or even lower efficiencies
(15% for solar thermal power generation systems with a central
tower receiver concentrator [7]) because significant losses (i.e.,
irreversibilities) typically occur during capture (e.g., from sunlight
to heat), transport (e.g., with heat transfer fluid), and conversion
(e.g., from heat to work) processes of solar energy.
Cascaded utilization of solar energy integrating solar PV and
CSP generation might achieve a synergistic effect between the
two approaches, aiming at higher efficiencies beyond the reach
of using either one alone. The basic rationale is that thermal
energy, which typically undermines solar PV generation due to
adverse temperature effect of solar cells [8], could be utilized for
driving various thermal processes. A photovoltaic/thermal hybrid
solar system (i.e., PVT system) utilizes dissipated thermal energy
from PV modules to supply heat, either for direct heating purposes
or to drive thermal power cycles. From the perspective of the ther-
mal utilization module, PV cells are used as the thermal absorbing
layer [9], with the capability of generating electricity while collect-
ing heat from the sun. The photonic energy of sunlight (at a rela-
tively high energy level) is first converted to electricity rather
than being converted directly to heat at a much lower energy level;
therefore, the exergy loss of the collection and conversion pro-
cesses could be reduced. The energy level is defined as the ratio
of the enthalpy change (Delta_H) to the exergy change (Delta_E)
of a process [10]:
DE
A¼ ð1Þ
DH
Theoretical and experimental studies on PVT systems were
reported as early as the 1970s [11,12]. In such systems, heat
rejected from PV modules serves as a heat source for space- or
water-heating [13,14]. Analytical studies [15,16] and numerical
modeling studies [17] on PVT systems were performed and verified
by experiments. Theoretical and experimental studies were carried
out on the influences of PV cooling channel geometrical parame-
ters [18,19], PVT collector orientation [20], cooling fluid flow rate
[21–23], cooling fluid temperature [23], frame shadow [24], and
solar irradiation [21,22] on PV temperature, system energy effi-
ciency, and exergy efficiency. System efficiencies based on the first
law of thermodynamics could reach as high as 60–80% [25,26].
However, from the perspective of the second law of thermodynam-
ics, it would be much more desirable for such systems to have effi-
cient power generation as energy output, because not only the
applicability of thermal energy is limited by many factors (e.g.,
space, time), but the energy level of PV-rejected thermal energy
is also quite low.
To this end, the concept of a hybrid power generation system
combining a heat engine and a photovoltaic module was put for-
ward by Chubb et al. [27] and analyzed by other researchers later
[6,28,29]. Simulation of a hybrid system combining Si-based CPV
with organic Rankine cycle (ORC) was carried out and the effi-
ciency was enhanced from 9.81% to 11.83% [30]. The relatively
low efficiency is mainly due to the low efficiency of the PV module
(Si solar cells with a cell efficiency of 12% at 25 °C) and that of the
ORC (due to the low temperature of the heat source, 140 °C).
Tourkov et al. [31] expanded this concept aiming at the best sce-
nario by combining the two technologies. As a result, efficiency
of the system combining a triple-junction PV cell and an ORC is
as high as 45%, a significant improvement compared with the effi-
ciency of 34% of triple-junction PV cells at a solar concentration
ratio of 200 and temperature of 25 °C. However, it must be pointed
out that the efficiency of 45% did not take the optical and heat
losses of the solar collector (including solar concentrator and
absorber) into account, which, however, significantly impacts the
performance of the system. If we took these factors into consider-
ation, the promotion of the hybrid system efficiency would be less
than 5% (rather than 11%).
Primary reasons for modest efficiency enhancement of PVT sys-
tems that combine PV modules and heat engines include negative
temperature coefficient of solar cells [8] and low efficiency of heat
engines at low temperatures (e.g., 12.3% for 150 °C [32]). The
potential contribution to efficiency promotion by heat engines is
partially offset by the decline in PV efficiency. Most importantly,
stable power output is essential for solar energy utilization tech-
nologies, but conventional PVT systems often fall short in this
respect due to the lack of an energy storage component. A new
PVT system that is not only capable of delivering high energy con-
version efficiency at relatively low temperatures, but can also
smooth out influences by both transient fluctuations and long-
term instabilities of solar irradiation through energy storage in
an appropriate form would be much more desirable.
In this study, we propose a hybrid PVT system, which is charac-
terized by high solar-electric efficiency and energy storage capac-
ity. A temperature-tolerant, high-efficiency PV module and a
low-temperature, high-efficiency solar thermal power module,
which is also capable of easily storing thermal energy, are both
indispensable for the hybrid system. For the former, GaAs PV cells
meet the requirements; for the latter, a power generation module
with solar methanol decomposition might be an appropriate
choice.
The idea of power generation with solar methanol decomposi-
tion was first proposed by Hong and Jin; it combines a solar ther-
mal driven, mid-temperature (200 °C) endothermic
decomposition reaction of methanol (CH3OH ? CO + 2H2,
DH200 C ¼ 97 kJ/mol) with a gas and steam combined cycle (GSCC)
[33–35]. The net solar-electric (NSE) efficiency of the solar metha-
nol decomposition system [33] is as high as 35% at a temperature
of merely 230 °C. The high efficiency is mainly due to the compre-
hensive utilization of physical and chemical energy (Fig. 1). From
the perspective of physical energy utilization, methanol decom-
poses at 200 °C and above; the low-energy level (0.36–0.40) of
solar thermal energy is converted to the high energy level (0.95)
1.0 B Methanol
D
Syngas C
Energy level
0.8
Heat at 1300
A
Methanol decomposition: A, B
0.6 Syngas combustion: C
Methanol combustion: D
0.4
Heat at 200
Fig. 1. Energy levels of methanol chemical energy, syngas chemical energy and
thermal energy at 200 °C and 1300 °C.
 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385
chemical energy of syngas. The solar thermal energy is then
released at the syngas combustion temperature (e.g., 1300 °C with
energy level of 0.81) for power generation. As for chemical energy
utilization, direct combustion of methanol for power generation
[36,37] leads to significant exergy losses due to the difference
between chemical energy level of methanol (i.e., 1.03 [33]) and
thermal energy level (e.g., 0.81) of the combustion products (at
1300 °C), which is the largest exergy loss in power generation sys-
tems [38]. Splitting methanol into syngas before combustion can
degrade the methanol energy level to the syngas energy level
(e.g., 0.95); the latter is closer to (and yet still above) the energy
level of thermal energy at combustion temperature and the exergy
loss during combustion is reduced by up to 7%, which accounts for
up to 23.6% of the exergy loss during methanol combustion [39].
Methanol solar thermochemistry makes it possible for low-level
solar thermal energy to be upgraded to and utilized at an elevated
energy level and to generate power at a significantly higher effi-
ciency. However, considerable irreversibility might still be
incurred during key steps such as collection, absorption, and con-
version of solar energy. Reducing the irreversibility during such
processes is important to further improve the efficiency of solar
power generation. One possible approach would be revisiting the
idea of PVT but replacing ‘‘thermal” with ‘‘thermochemical” for
the ‘‘T” part to help the thermal module of PVT systems out of
the low-efficiency dilemma of heat engines driven by PV-rejected
heat directly. In addition, the integration of thermochemistry into
a PVT system essentially adds energy storage capability as well, a
feature very important for addressing the instability issue of solar
energy, which however was usually not emphasized or even
ignored in previous PVT systems. The conceptual PVT system pro-
posed above could use syngas-driven power generation
approaches (e.g., internal combustion engines, or fuel cells) to
quickly offset fluctuations in PV outputs during daytime [40];
while completely rely on syngas power generation at nighttime
or whenever needed.
Given the complementary characteristics of PV and thermo-
chemical components with respect to temperature and energy
storage, we hereby propose a hybrid PVT system (Figs. 2 and 3a)
in this study, integrating a GaAs PV module and a power genera-
tion module with solar methanol decomposition. For comparison,
a solar thermochemical system similar to the system in Ref. [33]
is introduced as a reference system (Fig. 3b). Major differences
between them include the PV module and recycling of unreacted
methanol in the system proposed in this study. Thermodynamic
Fig. 2. Schematic diagram of the hybrid system.
379
analysis of the hybrid system shows that the synergy between
the PV and thermochemical power generation components could
lead to a win-win situation in terms of comprehensive generation
efficiency. Implications of key features of the novel system are dis-
cussed shortly.
2. Description of the system
The schematic diagram of the hybrid system and flow diagrams
of the hybrid and reference systems are shown in Figs. 2 and 3,
respectively. The major difference between the hybrid and refer-
ence systems is that the absorbers of the former are covered by
PV modules. In the hybrid system (Fig. 3a), methanol is sequen-
tially pumped from its storage tank into heat exchanger A, heater
A, heat exchanger B, and heater B. Methanol is heated and/or
vaporized by dissipated heat from PV modules and heat of reaction
products as well as unreacted methanol. Trickling out from heater
B, methanol flows to the reactor, in which a part of the methanol is
decomposed into syngas by the dissipated heat from PV modules.
The mixture of methanol and syngas is cooled in heat exchangers
A and B and finally flows into the syngas storage tank, in which
the mixture is cooled to ambient temperature and methanol is con-
densed and recycled to the methanol tank. In the end, the syngas in
the tank is compressed and fed into the GSCC as fuel. To ensure the
storage capacity of the hybrid system, the system is so designed
that syngas generated during daytime can last GSCC consumption
for up to 24 hours. The GSCC operates at rated operation conditions
unless the syngas supply is used up. Note that the GSCC employed
in this system could be replaced by internal combustion engines,
fuel cells or other devices fueled by syngas. Thus, the hybrid sys-
tem might be suitable for a large-scale, centralized power genera-
tion plant with a GSCC and/or a distributed power generation
system with internal combustion engines/fuel cells.
In the heaters (A and B) and reactor, sunlight is focused onto the
surface of PV modules by trough concentrators. Temperature for
methanol decomposition in the hybrid system is 150–250 °C, the
same as that in Ref. [33]; the PV component employed in the
hybrid system are InP/InGaAs/Ge triple-junction PV cells, which
can tolerate temperatures up to 250 °C [41].
3. Analytical methodology
Thermodynamic modeling and simulation are carried out on the
hybrid and reference systems.
The absorber tube is discretized into control volumes (Fig. 4)
and a random one is selected for study; its temperature is denoted
as Ti.
Sunlight is first concentrated by a trough solar concentrator.
Due to optical losses during concentration, only a part of the sun-
light is absorbed by the PV modules; it is given as:
dQ abs ðT i Þ ¼ dQ tot ðT i Þ  gopt ; ð2Þ
where dQ tot ðT i Þ is the total solar energy input of the point before
concentration and gopt is the collector optical efficiency. One part
of the absorbed sunlight is converted to electricity by the PV mod-
ule; the electrical power output is given as:
dW PV ðT i Þ ¼ dQ abs ðT i Þ  gT i ;PV ; ð3Þ
where gT i ;PV is the PV module efficiency at Ti. The efficiency of the
InP/InGaAs/Ge triple-junction PV module used in this study is given
as [6]:
gT i ;PV ¼ gT i ;cell  gmod ; ð4Þ
where gT i ;cell is the individual InP/InGaAs/Ge triple-junction PV cell
efficiency at Ti, and gmod is the ratio between the total PV module
380 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385

Fig. 3. Flow diagrams of (a) the hybrid system, and (b) the reference system.

Fig. 4. Diagram of energy transfer processes and energy balance on a selected control volume.

efficiency and individual PV cell efficiency (0.9) [6]. The individual shown in Tables 1 and 2, respectively. The rest of the absorbed sun-
PV cell efficiency at Ti is given as [6]: light is dissipated in the form of heat, and is given as:

dQ diss ðT i Þ ¼ dQ abs ðT i Þ  ð1  gT i ;PV Þ ð6Þ

gT i ;cell ¼ gT i ;0 þ 0:0142 ln C þ ð0:000715 þ 6:97  105 ln CÞ
 ðT i þ DT  25Þ C 6 200; ð5Þ
where gT i ;0 is the individual PV cell efficiency at a temperature of
25 °C and concentration ratio of 1 (0.298, according to Ref. [6],
which is a default option in the following discussion if not men-
tioned or 0.372 to approximate the PV cell in Ref. [4]), C is solar con-
centrating ratio, and DT is the temperature difference between PV
modules and flowing methanol. The PV efficiencies of the PV cell
in Refs. [4,6], calculated by Eq. (4) at different temperatures, are
A part of the dissipated solar heat is absorbed by the flowing
methanol; the rest is lost to the environment via convection and
thermal radiation. As a part of the dissipated solar energy, the con-
vective heat loss is given as [42]:
T i þ DT  T a 71:4
dQ con;loss ðT i Þ ¼ dQ tot ðT i Þ  ða þ c  V wind Þ  ; ð7Þ
DNI C
where Ta is ambient temperature; Vwind is velocity of wind, and DNI
is direct normal irradiance. Another part of the dissipated solar
energy, the radiative heat loss, is given as [42]:

Table 1 Table 2
Efficiencies of the PV cell in Ref. [6] at different temperatures. Efficiencies of the PV cell in Ref. [4] at different temperatures.

Temperature (°C) PV efficiency Temperature (°C) PV efficiency Temperature (°C) PV efficiency Temperature (°C) PV efficiency
25 0.322 150 0.275 25 0.389 150 0.342
50 0.313 175 0.266 50 0.380 175 0.333
75 0.304 200 0.257 75 0.370 200 0.323
100 0.294 225 0.247 100 0.361 225 0.314
125 0.285 250 0.238 125 0.351 250 0.304
 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385 381

ðT i þ DTÞ4  T 4sky 71:4 These equations describe how solar energy is absorbed and
dQ rad;loss ðT i Þ ¼ dQ tot ðT i Þ  eab  b   ; ð8Þ stored in the syngas. The whole process, including methanol
DNI C
warm-up, methanol decomposition, methanol recycling, syngas
where eab is the emissivity of the absorber and Tsky is the sky tem-
storage, syngas combustion, and power generation is simulated
perature, which is given as [43]:
using Aspen Plus [44]. The schematic diagram of the simulation
T sky ¼ T a  8; ð9Þ is shown in Fig. 5.
The power generation efficiency of the hybrid system is defined
The heat loss parameters are: a = 1.92  10 W K m2, 2 1
as:
b = 2.02  109 W K4 m2, and c = 6.61  103 J K1 m3 [42].
The thermal energy absorbed by methanol is the difference W PVþME
ge ¼ ; ð16Þ
between the dissipated solar energy and the heat loss, which is Q tot þ n_  LHV
given as:
where WPV+ME is the overall work output of the hybrid system,
dQ ðT i Þ ¼ dQ diss ðT i Þ  dQ con;loss ðT i Þ  dQ rad;loss ðT i Þ ð10Þ which is the sum of the electricity from the PV modules and GSCC;
and LHV is the lower heating value of methanol.
The above-mentioned analysis describes how the sunlight is Similar to other solar hybrid power plants, the NSE efficiency is
utilized by the PV modules and methanol at one point with tem- defined as [45]:
perature Ti. To describe how the sunlight is utilized in the entire
W PVþME  W ME
hybrid system, the point-wise analysis stated above is taken to tra- gse;PVþME ¼ ; ð17Þ
verse individual points of the system. The next analysis is based on Q tot
methanol flowing through the whole system. where W ME is the work output of GSCC with the same amount of
The thermal energy absorbed by methanol either raises metha- methanol as the input.
nol temperature and vaporizes methanol in the heaters or decom- To compare the performance of the hybrid system (Fig. 3b) and
poses methanol in the reactor. When the thermal energy absorbed that of the reference system (Fig. 3a), the NSE efficiency of the ref-
by methanol raises the methanol temperature from Ti to Ti + dT in erence system is also defined:
heaters A and B, the thermal energy absorbed by methanol is given
as: W ref  W ME
gse;ME ¼ ; ð18Þ
8 Q 0tot
_
< n  C P;T i  dT
> ðT in;A ; T out;A Þ [ ðT in;B ; T out;B Þ=T v;P
where Wref is the overall work output of the reference system with
dQ ðT i Þ ¼ n_  r fT v;P g ; ð11Þ
>
:_ the same amount of methanol as the input. To compare the perfor-
n  DHP;T out;B fT out;B g
mance of the hybrid system with that of the PV-only and methanol-
only power generation systems, the electricity increment ratio is
where n_ is molar methanol flow rate, C P;T i is heat capacity of metha-
defined as:
nol when methanol is at Ti, r is latent heat of methanol vaporization,
Tin,A and Tin,B are inlet temperatures of methanol in heaters A and B, W PVþME  W PV  W ME
rincr ¼ ; ð19Þ
respectively, Tout,B and Tout,B are outlet temperatures of methanol in W PV þ W ME
heaters A and B, respectively, T v;P is vaporization temperature of
where WPV is the work output of the PV-only system (its area is the
methanol at pressure P, and DHP;T out;B is enthalpy change when
same as that of the hybrid system).
methanol decomposes and reaches an equilibrium at pressure P
To explore the reason for NSE efficiency promotion in the
and temperature Tout,B.
hybrid system, the exergy loss reduction between the hybrid and
When methanol flows through heaters (A, B) and reactor, the
reference systems is defined as the exergy difference between
total thermal energy absorbed by methanol is given as:
(R the electricity and exergy of waste heat during sunlight collection.
R
dQ ðT i Þ ¼ n_  C P;T i  dT þ n_  DHP;T out;B þ n_  r ðT v;P 6 T out;B Þ Furthermore, the exergy loss reduction ratio is defined as:
Q me ¼ R R Z   
dQ ðT i Þ ¼ n_  C P;T i  dT þ n_  DHP;T out;B ðT v;P > T out;B Þ T a þ 273:15
 1 W PV ðT i Þ  1  1 
ð12Þ Exheat T i þ 273:15
rlos;red ¼ 
DNI  C  A0 DNI  C  A
Accordingly, the total solar energy input before concentrating, Z  
T a þ 273:15
when methanol flows through the system, is given as:  1 dA  gopt  gPV ðT i Þ 
Z Exheat T i þ 273:15
¼  ; ð20Þ
Q tot ¼ dQ tot ðT i Þ ð13Þ DNI  C  A0 A

where Exheat is the exergy part of the thermal energy absorbed by

When the same amount of methanol flows through the refer-
methanol in the reference system; A0 and A are the areas of the ref-
ence system (Fig. 2a), the energy absorbed by methanol and the
erence and hybrid systems that absorb solar energy for the same
power produced by the GSCC are the same as that of the hybrid
amount of methanol flow through the system (symbolized by n), _
system. The only difference between them is that the thermal
respectively.
energy absorbed by methanol in the reference system is directly
obtained from sunlight, not the PV cells. The relation between
the solar energy input and thermal energy absorbed by methanol 4. Results and discussion
for at a control volume is given as:
The following assumptions are made for the simulation of
dQ ðT i Þ ¼ dQ 0tot ðT i Þ  gopt  dQ con;loss ðT i Þ  dQ rad;loss ðT i Þ ð14Þ methanol decomposition: (1) thermodynamic equilibrium is
reached within the reactor; and (2) the reaction products are CO
The total solar energy input in the reference system is given as: and H2 only (at stoichiometric ratio). The GSCC employed in the
Z simulation is a combination of a gas turbine, a triple-pressure heat
Q 0tot ¼ dQ 0tot ðT i Þ ð15Þ recovery steam generator (HRSG), and a steam turbine. Key param-
eters for the simulation are summarized in Table 3.
382 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385

Fig. 5. Schematic diagram of the simulation model in Aspen Plus.

Table 3 are achieved using the PV cells from Ref. [6] when the reaction
Summary of key parameters. temperature is 225 °C and the reaction pressure is 7 bar.
Parameters Value To evaluate the benefits of the concept of integration between
DNI 800 W/m2
the PV-only and reference systems, a comparison between the
Emissivity of PV modules (eab) 0.5 hybrid system and the reference system is performed. The NSE effi-
Absorptivity of PV modules (a) 1 ciency of 40.2–42.9% of the hybrid system is approximately one-
Collector optical efficiency (gopt) 0.73 fifth higher than that of 32.0–35.9% of the reference system
Velocity of wind (Vwind) 4 m/s
(Fig. 6); if a 46.0% efficiency PV cell [4] were used instead, the effi-
Concentrating ratio (C) 80
Reaction pressure 3.0  105–2.3  106 Pa ciency of the hybrid system could be further boosted from 42.9% to
Reaction temperature 225 °C 45.4%. However, the seemingly marginal difference between the
Turbine inlet temperature 1250 °C NSE efficiency of 45.4% of the hybrid system and the efficiency of
Pressure ratio of gas turbine 17 46.0% of the PV cells disguises the real difference in practically
Fuel inlet pressure 2.5  106 Pa
Ambient temperature (Ta) 15 °C
achievable efficiencies at the system level; PV cells have to work
Exhaust temperature from HRSG 85 °C as modules and multi-junction cells have to work together with
Temperature of syngas storage tank 15 °C solar concentration systems, which inevitably incurs a modular
Minimum heat transfer temperature difference (DT) 10 °C efficiency coefficient of 0.9 and an optical efficiency of 0.85
[5] (both multiplied to single-cell efficiency). When taking both
factors into account, we reach a practically achievable (i.e.,
system-level) efficiency of 35.2% for the PV cells with 46.0%
4.1. Performance of the hybrid system single-cell efficiency. On the other hand, the 45.4% peak efficiency
of the hybrid system already takes both factors into account, and
4.1.1. Efficiency promotion resulting from integration the true difference therefore is that the NSE efficiency of 45.4% of
Numerical simulation is carried out with the model and param- the hybrid system is more than one-quarter higher than the PV-
eters described above. Fig. 6 shows the NSE efficiency of the hybrid only system efficiency of 35.2%.
and reference systems and various components of electricity out- The significant promotion in efficiency compared with the ref-
put. The NSE efficiency of the hybrid system first increases and erence system is mainly due to the fact that the absorber in the
then declines as the reaction pressure increases. The NSE efficiency hybrid system is covered by PV modules; hence, sunlight is con-
of up to 42.9% and the system electricity efficiency of up to 54.5% verted into electricity first and only the rest degrades to low-
energy level heat, which results in the alleviation of exergy loss
during sunlight collection and thus efficiency promotion in the
hybrid system. According to Eq. (20), the exergy loss reduction
0.80 0.46 ratio reaches up to 49%, indicating that the hybrid system obtains
PV[4]+Methanol almost one half more exergy from solar energy than the reference
Net solar-electric efficiency

PV[6]+Methanol 0.44 system. For the same amount of solar energy input, savings in
0.75 0.42 exergy always lead to more electricity output and thus higher
Electricity ratio

efficiency.
0.40 Compared with the PV-only system, the improvement is
0.70 obtained by taking advantage of the complementary nature
0.38
0.15 between the PV modules and solar thermochemical module and
0.36 the ‘‘leverage” effect (Fig. 1) of the latter, which promotes low-
0.10 level thermal energy to high-level chemical energy (e.g., syngas)
Methanol 0.34 at the cost of even higher-level chemical energy (e.g., methanol).
Solar thermal A comparison of the electricity generation between the tandem
0.05 0.32
Solar PV hybrid system and parallel system (i.e., a PV-only system and a
Methanol methanol-only system arranged in parallel), with the area of the
0.00 0.30
3 7 11 15 19 23 collector and amount of methanol being the same, is also carried
out. Selected as the indicator, the electricity increment ratio (Eq.
Pressure/bar
(19)) is in the range of 17–18% while the reaction pressure varies
Fig. 6. Net solar-to-electric efficiency of the hybrid and reference systems; from 3 to 23 bar, indicating that the hybrid system generates more
composition of electricity of the hybrid system. electricity than the parallel one. This is mainly due to two reasons:
 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385
(1) the solar energy in the hybrid system is utilized by the solar PV
module and thermal module (i.e., methanol decomposition) as
opposed to being only used in a cascaded way by the PV module
in the PV-only system; (2) the methanol in the hybrid system is
decomposed before combustion, which results in a lower exergy
loss during combustion compared with direct methanol combus-
tion system.
4.1.2. Fossil fuel saving and energy storage
Analysis of the electricity composition reveals that the majority
of the electricity originates from methanol, the share of which var-
ies around three-quarters (73.3–76.6% in Fig. 6), while the electric-
ity from solar energy accounts for approximately one quarter of the
total electricity. By comparison, the electricity from solar energy in
the reference system (Fig. 3b) only accounts for 16% of the total
electricity. This means that the hybrid system needs less fossil fuel
to generate the same amount of electricity. It is also noteworthy
that the electricity from the PV modules approximately equals that
from solar thermal energy. This indicates that in the hybrid system,
syngas carrying sufficient solar energy can be stored first during
daytime (while the PV module simultaneously supplies electric-
ity); the energy is later released (e.g., by GSCC) for power genera-
tion. This means that syngas-driven power generation
approaches (e.g., internal combustion engines or fuel cells) could
be used to quickly offset fluctuations in PV outputs during daytime,
while syngas power generation could be completely relied on at
nighttime or whenever needed. Thus, the goal of steadily supplying
electricity by solar energy all day could be achieved by using solar
energy storage via syngas. Furthermore, the solar energy stored in
syngas is relatively stable, which implies that the solar energy can
be stored for a relatively long time, transported to where it is
needed, and released when it is needed. In contrast, the storage
of solar energy in previously described PVT systems based on heat
engines was not explicitly considered; even if considered, solar
energy storage in the form of low-level explicit or latent heat might
be inefficient and uneconomic.
4.2. Impact of reaction pressure and temperature
Major thermodynamic parameters for methanol decomposition
in the hybrid system, including reaction pressure and temperature,
influence methanol conversion rate to syngas, as well as the tem-
perature of the heaters and the reactor. To reveal the impact of
both parameters on system performance and determine optimum
operating conditions, the NSE efficiency of the hybrid system, as
0.450
0.429
Net solar-electric efficiency
Optimal efficiency
0.425
0.400
0.375
0.350
0.325
150
0.300 175 225
200 250
0.275
1 3 5 7 9 11 13 15 17 19 21 23
Pressure/bar
Fig. 7. Net solar-to-electric efficiency of the hybrid system at different reaction
temperatures versus reaction pressure.
383
an optimization function of both parameters, is plotted in Figs. 7
and 8, respectively.
As can be observed from the dashed lines in Figs. 7 and 8, the
optimal NSE efficiencies for different reaction temperatures/pres-
sures remains quite stable (i.e., 42.9%). This implies that the influ-
ence of temperature variation can be offset by changing the
pressure, which is essentially a system operation strategy to coun-
teract solar irradiation fluctuation. On the other hand, the optimal
reaction temperature for lower reaction pressure is also lower due
to heat absorption and volume expansion during methanol decom-
position. In other words, it is possible to keep the maximum NSE
efficiency of the hybrid system stable even though temperature
and pressure both change, which makes it possible to lower the
requirements on system operation, including temperature (related
to solar energy collection) and pressure (related to pump work),
without sacrificing system performance. According to Leest et al.
[46], with PV cells operating at 200 °C for 1320 h, no significant
influences on the GaAs structure and PV efficiency are observed.
Thus, PV temperature in the range of 150–200 °C is reasonable
for present PV cells and PV temperature in the range of 200–
250 °C might also be reasonable considering advancement in PV
technologies. The major limiting factor of the system performance
would then primarily shift to the kinetic side, which might inspire
further studies on materials (e.g., catalysts) and reaction mecha-
nisms. For example, the latest studies by Ma et al. [47] demon-
strated decomposition of methanol at a respectable rate with 2%
Pt/a-MoC catalyst at 150 °C. It could therefore be envisaged that
with advances in materials science and chemical engineering, the
temperature for methanol decomposition to occur at respectable
rates could be further lowered. The developments of PV cell and
catalyst shall provide a broader and more solid basis for the PV-
thermal(chemical) hybrid concept presented to be widely applica-
ble with not only III-V solar cells, but other types of solar cells as
well.
A close inspection on the influence of temperature shows that
the efficiency of the hybrid system at the lowest temperature of
150 °C monotonically declines with the increase of pressure
(Fig. 7), while the efficiency curves start to peak at appropriate
pressures in the temperature range of 175–250 °C. The same data
set as in Fig. 7 is presented in a different manner in Fig. 8 in order
to better illustrate the impact of reaction temperature on effi-
ciency. When pressure is in the range of 15–23 bar, the NSE effi-
ciency increases as temperature increases; when pressure is in
the range of 2–11 bar, an optimum NSE efficiency is observed in
the range of 175–250 °C and the optimum remains virtually
0.44 Optimal efficiency
Net solar-electric efficiency
ar
3b
0.40 ar 2bar
7b
ar 1bar
b
11
0.36 r
ba
15
r
ba
0.32 19
r
ba
23
0.28
150 175 200 225 250
Temperature/
Fig. 8. Net solar-to-electric efficiency of the hybrid system at different reaction
pressures versus the reaction temperature.
384
unchanged with respect to variations in temperature; and when
the pressure is as low as 1 bar, the efficiency declines as the tem-
perature increases. The optimal reaction temperature is deter-
mined to be 225 °C and the optimal reaction pressure is 7 bar.
To reveal the underlying reason of the impact of reaction pres-
sure on system performance, further analysis is carried out on
components of the system:
(a) Reaction pressure influences the average temperature of
heaters, for it directly influences the vaporization tempera-
ture of methanol. Because evaporation heat accounts for a
large part of the methanol-absorbed heat (30%), the change
of the vaporization temperature has a considerable effect on
the average temperature of the heaters. This means that
higher methanol vaporization temperature leads to higher
PV module temperature, which in turn lowers the PV and
solar collector efficiencies.
(b) Reaction pressure affects the performance of methanol
pump and syngas compressor. On one hand, higher pressure
leads to higher pressure ratio of methanol pump and lower
methanol conversion rate, which then results in more
methanol flowing through the pump for the production of
the same amount of syngas and thus the increase in both
pump work and exergy loss, which results from the work
difference between the actual compression work and ideal
compression work. On the other hand, higher reaction pres-
sure leads to lower pressure ratio of the syngas compressor
and thereby to less work consumption and less exergy loss.
In brief, as the reaction pressure increases, the changing
trends of the pump exergy loss and compressor exergy loss
are opposite. The exergy loss of the pumps/compressors is
defined as the difference between the power consumption
of the pumps/compressors and the exergy increase of the
fluid. Fig. 9 shows comparison between the exergy loss vari-
ation of the pump and compressor as the reaction pressure
changes. Compared with the compressor exergy loss varia-
tion, changes of methanol pump exergy loss can be ignored.
The sum of exergy losses of the pump and compressor decli-
nes with increasing pressure.
(c) Reaction pressure affects the degree of heat recovery in heat
exchangers. As mentioned before, more methanol is recycled
at higher reaction pressures. Methanol recycling not only
consumes pump work, but also dissipates a considerable
amount of heat to the ambient. With respect to the latter,
the heat transfer temperature difference in the heat
1.6
Ratio to net solar electricity/%
Pump exergy loss
1.4
Compressor exergy loss
Sum of them
1.2
1.0
0.8
0.6
0.4
0.2
0.0
3 7 11 15
Pressure/bar
Fig. 9. Exergy losses in methanol pump and syngas compressor versus reaction
pressure at reaction temperature of 225 °C.
W. Li, Y. Hao / Applied Energy 202 (2017) 377–385
0.04 Ratio to solar energy input
Net solar-electric efficiency
Net solar-electric efficiency 0.43
Ratio to solar energy
0.03
0.42
0.02 Sum of all losses
0.41
0.01
Heat exergy loss
P&C Ex loss
0.40
0.00 PV electricity loss
3 7 11 15 19 23
Pressure/bar
Fig. 10. PV electricity loss, P&C exergy loss and heat exergy loss versus reaction
pressure at reaction temperature of 225 °C.
exchangers leads to exergy loss. On the other hand, the out-
let temperature of the mixture of heat exchanger A is higher
than the ambient temperature (e.g., 15 °C); therefore, the
thermal energy of the mixture is lost to the environment,
which leads to energy (exergy) loss. In other words, increas-
ing reaction pressure leads to the rise of energy (specifically
exergy) loss during the mixture heat recycling process and
thus poses a negative impact on system performance.
Lastly, by combining all analyses, the major exergy losses are
plotted versus reaction pressure in Fig. 10 to illustrate individual
and combined influences of major irreversible factors on the sys-
tem performance. The PV electricity loss in Fig. 10 is defined as
the difference between the PV electricity at reaction pressure of
3 bar (i.e., the maximum PV electricity of this study) and that at
selected reaction pressure; the pump and compressor (P & C)
exergy loss is defined as the sum of the exergy loss in the methanol
pump and syngas compressor; and the heat exergy loss is defined
as the exergy loss due to the temperature difference between the
temperature of the cooled mixture of heat exchanger A and the
ambient temperature. Fig. 10 shows that the ratio of PV electricity
loss to solar energy input increases from 0% to 0.4% when the reac-
tion pressure increases from 3 bar to 23 bar; the ratio of heat
exergy loss increases from 0% to 3.5%, while the ratio of P & C
exergy loss decreases from 1.4% to 0.1%. As a result, the sum of
these losses exhibits a minimum at 7 bar and the shape of the
curve is nearly opposite to that of the NSE efficiency. Our simula-
tion results further show that the curve trends at all studied tem-
peratures are similar to that presented in Fig. 10 (at 225 °C),
thereby establishing the universality of the analysis methodology
and validity of the conclusions within the primary range of operat-
ing conditions of the hybrid system.
5. Conclusions
A novel hybridization between solar PV and solar thermochem-
ical power generation modules integrating methanol decomposi-
tion has been proposed and analyzed. Theoretical net solar-
electric efficiency of the hybrid system (after taking all major
losses into account) reaches up to 45.4% at operating temperature
of 225 °C and pressure of 7 bar. Compared with conventional PV-
19 23
only systems, PVT systems and thermochemical-only systems
(e.g., the reference system), such a combination significantly
enhances the efficiency for two major reasons. The first reason is
the ‘‘cascaded” utilization of solar energy, which results in the
 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385
decrease of exergy losses during solar energy collection and con-
version by way of both the power generation of solar cells and
endothermicity of methanol decomposition. The second reason is
the ‘‘leverage” effect of energy levels between high energy level
fossil fuel (i.e., methanol) and low energy level thermal energy
from solar cells; the latter is upgraded to the energy level of syngas
chemical energy, at the cost of the decrease of methanol energy
level during methanol decomposition. The hybrid system also
exhibits its capability of uninterrupted and stable electricity sup-
ply due to the combination of solar PV cells (for daytime power
generation) and solar energy storage through syngas (for nighttime
power generation). Sensitivity analysis of key operation parame-
ters of the hybrid system indicates its relative insensitivity to the
operation pressure and temperature, which brings tremendous
benefits in system design and system operation, due to opposite
responses of PV cells and methanol thermochemistry to tempera-
ture. Based on all above-mentioned advantages, the PV–thermo-
chemical hybrid system proposed in this work could provide a
promising approach for effective solar energy utilization in the
near future.
Acknowledgments
This study is partially supported by the National Natural
Science Foundation of China under award number 51590904 and
51236008, partially by the Chinese Academy of Sciences Innovative
and Interdisciplinary Team Award, and partially by the Chinese
Government Award of the Recruitment Program of Global Experts.
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