Applied Energy 202 (2017) 377–385

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Efficient solar power generation combining photovoltaics and mid-/low-
temperature methanol thermochemistry
Wenjia Li a,b, Yong Hao a,b,⇑
Institute of Engineering Thermophysics, Chinese Academy of Sciences, Beijing 100190, PR China
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,
which is stored and burned to generate electricity when necessary. Analysis indicates that the theoretical
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 (PV) cells is relatively low. Take crystalline silicon solar cells for
example, although the entire visible part of the solar spectrum
Drastic increase in fossil fuel consumption and the consequen- and some parts of the infrared spectrum fall well within their con-
tial worldwide climate change have lead to a pressing demand on version capability, efficiency of commercially available silicon cells
low-cost, large-scale utilization technologies of renewable energy is usually 10–20% [1], while the majority of solar irradiation is
to gradually phase out fossil fuels in a foreseeable future. Renew- wasted in the form of low-temperature (e.g., 100 °C or lower)
able energy sources that are commensurate with or far beyond thermal energy [2]–longer wavelength radiation that falls below
the scale of human energy demand, such as solar energy, are rare the band gap of silicon does not carry enough energy to excite elec-
and yet carry particularly important historical missions. trons and thus entirely turns into dissipated heat; shorter wave-
Solar energy utilization still faces a major cost barrier that par- length radiation with photonic energy higher than the band gap
tially results from the relatively low conversion efficiency of sun- can only be partially converted to electricity by quantum principles
light to power. Among a portfolio of current solar power underlying photoelectric effects [3] and the rest is still converted to
technologies, the efficiency of practically applicable photovoltaic heat. Although much higher efficiencies have been achieved
through advances in materials and configuration of solar cells
⇑ Corresponding author at: Institute of Engineering Thermophysics, Chinese (e.g., 46.0% cell efficiency for III–V multi-junction solar cells [4]),
Academy of Sciences, Beijing 100190, PR China. waste heat still accounts for more than half of the solar energy
E-mail address: (Y. Hao). input. Moreover, not only PV cells are practically used as modules
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 ORC (due to the low temperature of the heat source, 140 °C).
work in conjunction with concentrating optics (e.g., Fresnel lens; Tourkov et al. [31] expanded this concept aiming at the best sce-
CPV) to enhance power generation performance and lower gener- nario by combining the two technologies. As a result, efficiency
ation cost. These facts, however, lead to a clear distinction between of the system combining a triple-junction PV cell and an ORC is
cell efficiency and system efficiency; the module factor and optical as high as 45%, a significant improvement compared with the effi-
loss become inevitable factors that must be taken into account. For ciency of 34% of triple-junction PV cells at a solar concentration
example, if the optical efficiency of solar collection is 0.85 [5] and ratio of 200 and temperature of 25 °C. However, it must be pointed
the efficiency of a PV module to be 90% of that of a single cell [6], out that the efficiency of 45% did not take the optical and heat
the efficiency of a concentrated PV system consisting of 46.0% effi- losses of the solar collector (including solar concentrator and
cient single cells [4] then translates to 35.2% (practical efficiency), absorber) into account, which, however, significantly impacts the
which means that nearly two-thirds of the incident solar energy is performance of the system. If we took these factors into consider-
dissipated to the ambient. By comparison, concentrated solar ation, the promotion of the hybrid system efficiency would be less
power (CSP) exhibits similarly low or even lower efficiencies than 5% (rather than 11%).
(15% for solar thermal power generation systems with a central Primary reasons for modest efficiency enhancement of PVT sys-
tower receiver concentrator [7]) because significant losses (i.e., tems that combine PV modules and heat engines include negative
irreversibilities) typically occur during capture (e.g., from sunlight temperature coefficient of solar cells [8] and low efficiency of heat
to heat), transport (e.g., with heat transfer fluid), and conversion engines at low temperatures (e.g., 12.3% for 150 °C [32]). The
(e.g., from heat to work) processes of solar energy. potential contribution to efficiency promotion by heat engines is
Cascaded utilization of solar energy integrating solar PV and partially offset by the decline in PV efficiency. Most importantly,
CSP generation might achieve a synergistic effect between the stable power output is essential for solar energy utilization tech-
two approaches, aiming at higher efficiencies beyond the reach nologies, but conventional PVT systems often fall short in this
of using either one alone. The basic rationale is that thermal respect due to the lack of an energy storage component. A new
energy, which typically undermines solar PV generation due to PVT system that is not only capable of delivering high energy con-
adverse temperature effect of solar cells [8], could be utilized for version efficiency at relatively low temperatures, but can also
driving various thermal processes. A photovoltaic/thermal hybrid smooth out influences by both transient fluctuations and long-
solar system (i.e., PVT system) utilizes dissipated thermal energy term instabilities of solar irradiation through energy storage in
from PV modules to supply heat, either for direct heating purposes an appropriate form would be much more desirable.
or to drive thermal power cycles. From the perspective of the ther- In this study, we propose a hybrid PVT system, which is charac-
mal utilization module, PV cells are used as the thermal absorbing terized by high solar-electric efficiency and energy storage capac-
layer [9], with the capability of generating electricity while collect- ity. A temperature-tolerant, high-efficiency PV module and a
ing heat from the sun. The photonic energy of sunlight (at a rela- low-temperature, high-efficiency solar thermal power module,
tively high energy level) is first converted to electricity rather which is also capable of easily storing thermal energy, are both
than being converted directly to heat at a much lower energy level; indispensable for the hybrid system. For the former, GaAs PV cells
therefore, the exergy loss of the collection and conversion pro- meet the requirements; for the latter, a power generation module
cesses could be reduced. The energy level is defined as the ratio with solar methanol decomposition might be an appropriate
of the enthalpy change (Delta_H) to the exergy change (Delta_E) choice.
of a process [10]: The idea of power generation with solar methanol decomposi-
tion was first proposed by Hong and Jin; it combines a solar ther-
A¼ ð1Þ mal driven, mid-temperature (200 °C) endothermic
DH decomposition reaction of methanol (CH3OH ? CO + 2H2,
Theoretical and experimental studies on PVT systems were DH200 C ¼ 97 kJ/mol) with a gas and steam combined cycle (GSCC)
reported as early as the 1970s [11,12]. In such systems, heat [33–35]. The net solar-electric (NSE) efficiency of the solar metha-
rejected from PV modules serves as a heat source for space- or nol decomposition system [33] is as high as 35% at a temperature
water-heating [13,14]. Analytical studies [15,16] and numerical of merely 230 °C. The high efficiency is mainly due to the compre-
modeling studies [17] on PVT systems were performed and verified hensive utilization of physical and chemical energy (Fig. 1). From
by experiments. Theoretical and experimental studies were carried the perspective of physical energy utilization, methanol decom-
out on the influences of PV cooling channel geometrical parame- poses at 200 °C and above; the low-energy level (0.36–0.40) of
ters [18,19], PVT collector orientation [20], cooling fluid flow rate solar thermal energy is converted to the high energy level (0.95)
[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- 1.0 B Methanol
ics, it would be much more desirable for such systems to have effi- D
Syngas C
cient power generation as energy output, because not only the
applicability of thermal energy is limited by many factors (e.g.,
Energy level

space, time), but the energy level of PV-rejected thermal energy Heat at 1300
is also quite low. Methanol decomposition: A, B
To this end, the concept of a hybrid power generation system 0.6 Syngas combustion: C
combining a heat engine and a photovoltaic module was put for- Methanol combustion: D
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- Heat at 200
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 Fig. 1. Energy levels of methanol chemical energy, syngas chemical energy and
(Si solar cells with a cell efficiency of 12% at 25 °C) and that of the thermal energy at 200 °C and 1300 °C.
W. Li, Y. Hao / Applied Energy 202 (2017) 377–385 379

chemical energy of syngas. The solar thermal energy is then analysis of the hybrid system shows that the synergy between
released at the syngas combustion temperature (e.g., 1300 °C with the PV and thermochemical power generation components could
energy level of 0.81) for power generation. As for chemical energy lead to a win-win situation in terms of comprehensive generation
utilization, direct combustion of methanol for power generation efficiency. Implications of key features of the novel system are dis-
[36,37] leads to significant exergy losses due to the difference cussed shortly.
between chemical energy level of methanol (i.e., 1.03 [33]) and
thermal energy level (e.g., 0.81) of the combustion products (at 2. Description of the system
1300 °C), which is the largest exergy loss in power generation sys-
tems [38]. Splitting methanol into syngas before combustion can The schematic diagram of the hybrid system and flow diagrams
degrade the methanol energy level to the syngas energy level of the hybrid and reference systems are shown in Figs. 2 and 3,
(e.g., 0.95); the latter is closer to (and yet still above) the energy respectively. The major difference between the hybrid and refer-
level of thermal energy at combustion temperature and the exergy ence systems is that the absorbers of the former are covered by
loss during combustion is reduced by up to 7%, which accounts for PV modules. In the hybrid system (Fig. 3a), methanol is sequen-
up to 23.6% of the exergy loss during methanol combustion [39]. tially pumped from its storage tank into heat exchanger A, heater
Methanol solar thermochemistry makes it possible for low-level A, heat exchanger B, and heater B. Methanol is heated and/or
solar thermal energy to be upgraded to and utilized at an elevated vaporized by dissipated heat from PV modules and heat of reaction
energy level and to generate power at a significantly higher effi- products as well as unreacted methanol. Trickling out from heater
ciency. However, considerable irreversibility might still be B, methanol flows to the reactor, in which a part of the methanol is
incurred during key steps such as collection, absorption, and con- decomposed into syngas by the dissipated heat from PV modules.
version of solar energy. Reducing the irreversibility during such The mixture of methanol and syngas is cooled in heat exchangers
processes is important to further improve the efficiency of solar A and B and finally flows into the syngas storage tank, in which
power generation. One possible approach would be revisiting the the mixture is cooled to ambient temperature and methanol is con-
idea of PVT but replacing ‘‘thermal” with ‘‘thermochemical” for densed and recycled to the methanol tank. In the end, the syngas in
the ‘‘T” part to help the thermal module of PVT systems out of the tank is compressed and fed into the GSCC as fuel. To ensure the
the low-efficiency dilemma of heat engines driven by PV-rejected storage capacity of the hybrid system, the system is so designed
heat directly. In addition, the integration of thermochemistry into that syngas generated during daytime can last GSCC consumption
a PVT system essentially adds energy storage capability as well, a for up to 24 hours. The GSCC operates at rated operation conditions
feature very important for addressing the instability issue of solar unless the syngas supply is used up. Note that the GSCC employed
energy, which however was usually not emphasized or even in this system could be replaced by internal combustion engines,
ignored in previous PVT systems. The conceptual PVT system pro- fuel cells or other devices fueled by syngas. Thus, the hybrid sys-
posed above could use syngas-driven power generation tem might be suitable for a large-scale, centralized power genera-
approaches (e.g., internal combustion engines, or fuel cells) to tion plant with a GSCC and/or a distributed power generation
quickly offset fluctuations in PV outputs during daytime [40]; system with internal combustion engines/fuel cells.
while completely rely on syngas power generation at nighttime In the heaters (A and B) and reactor, sunlight is focused onto the
or whenever needed. surface of PV modules by trough concentrators. Temperature for
Given the complementary characteristics of PV and thermo- methanol decomposition in the hybrid system is 150–250 °C, the
chemical components with respect to temperature and energy same as that in Ref. [33]; the PV component employed in the
storage, we hereby propose a hybrid PVT system (Figs. 2 and 3a) hybrid system are InP/InGaAs/Ge triple-junction PV cells, which
in this study, integrating a GaAs PV module and a power genera- can tolerate temperatures up to 250 °C [41].
tion module with solar methanol decomposition. For comparison,
a solar thermochemical system similar to the system in Ref. [33] 3. Analytical methodology
is introduced as a reference system (Fig. 3b). Major differences
between them include the PV module and recycling of unreacted Thermodynamic modeling and simulation are carried out on the
methanol in the system proposed in this study. Thermodynamic 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
Fig. 2. Schematic diagram of the hybrid system. 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
A part of the dissipated solar heat is absorbed by the flowing
 ðT i þ DT  25Þ C 6 200; ð5Þ
methanol; the rest is lost to the environment via convection and
thermal radiation. As a part of the dissipated solar energy, the con-
where gT i ;0 is the individual PV cell efficiency at a temperature of vective heat loss is given as [42]:
25 °C and concentration ratio of 1 (0.298, according to Ref. [6],
T i þ DT  T a 71:4
which is a default option in the following discussion if not men- dQ con;loss ðT i Þ ¼ dQ tot ðT i Þ  ða þ c  V wind Þ  ; ð7Þ
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 where Ta is ambient temperature; Vwind is velocity of wind, and DNI
modules and flowing methanol. The PV efficiencies of the PV cell is direct normal irradiance. Another part of the dissipated solar
in Refs. [4,6], calculated by Eq. (4) at different temperatures, are 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
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
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
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.
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
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

0.40 Compared with the PV-only system, the improvement is
0.70 obtained by taking advantage of the complementary nature
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.
(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) 377–385 383

(1) the solar energy in the hybrid system is utilized by the solar PV an optimization function of both parameters, is plotted in Figs. 7
module and thermal module (i.e., methanol decomposition) as and 8, respectively.
opposed to being only used in a cascaded way by the PV module As can be observed from the dashed lines in Figs. 7 and 8, the
in the PV-only system; (2) the methanol in the hybrid system is optimal NSE efficiencies for different reaction temperatures/pres-
decomposed before combustion, which results in a lower exergy sures remains quite stable (i.e., 42.9%). This implies that the influ-
loss during combustion compared with direct methanol combus- ence of temperature variation can be offset by changing the
tion system. pressure, which is essentially a system operation strategy to coun-
teract solar irradiation fluctuation. On the other hand, the optimal
4.1.2. Fossil fuel saving and energy storage reaction temperature for lower reaction pressure is also lower due
Analysis of the electricity composition reveals that the majority to heat absorption and volume expansion during methanol decom-
of the electricity originates from methanol, the share of which var- position. In other words, it is possible to keep the maximum NSE
ies around three-quarters (73.3–76.6% in Fig. 6), while the electric- efficiency of the hybrid system stable even though temperature
ity from solar energy accounts for approximately one quarter of the and pressure both change, which makes it possible to lower the
total electricity. By comparison, the electricity from solar energy in requirements on system operation, including temperature (related
the reference system (Fig. 3b) only accounts for 16% of the total to solar energy collection) and pressure (related to pump work),
electricity. This means that the hybrid system needs less fossil fuel without sacrificing system performance. According to Leest et al.
to generate the same amount of electricity. It is also noteworthy [46], with PV cells operating at 200 °C for 1320 h, no significant
that the electricity from the PV modules approximately equals that influences on the GaAs structure and PV efficiency are observed.
from solar thermal energy. This indicates that in the hybrid system, Thus, PV temperature in the range of 150–200 °C is reasonable
syngas carrying sufficient solar energy can be stored first during for present PV cells and PV temperature in the range of 200–
daytime (while the PV module simultaneously supplies electric- 250 °C might also be reasonable considering advancement in PV
ity); the energy is later released (e.g., by GSCC) for power genera- technologies. The major limiting factor of the system performance
tion. This means that syngas-driven power generation would then primarily shift to the kinetic side, which might inspire
approaches (e.g., internal combustion engines or fuel cells) could further studies on materials (e.g., catalysts) and reaction mecha-
be used to quickly offset fluctuations in PV outputs during daytime, nisms. For example, the latest studies by Ma et al. [47] demon-
while syngas power generation could be completely relied on at strated decomposition of methanol at a respectable rate with 2%
nighttime or whenever needed. Thus, the goal of steadily supplying Pt/a-MoC catalyst at 150 °C. It could therefore be envisaged that
electricity by solar energy all day could be achieved by using solar with advances in materials science and chemical engineering, the
energy storage via syngas. Furthermore, the solar energy stored in temperature for methanol decomposition to occur at respectable
syngas is relatively stable, which implies that the solar energy can rates could be further lowered. The developments of PV cell and
be stored for a relatively long time, transported to where it is catalyst shall provide a broader and more solid basis for the PV-
needed, and released when it is needed. In contrast, the storage thermal(chemical) hybrid concept presented to be widely applica-
of solar energy in previously described PVT systems based on heat ble with not only III-V solar cells, but other types of solar cells as
engines was not explicitly considered; even if considered, solar well.
energy storage in the form of low-level explicit or latent heat might A close inspection on the influence of temperature shows that
be inefficient and uneconomic. 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
4.2. Impact of reaction pressure and temperature 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
Major thermodynamic parameters for methanol decomposition to better illustrate the impact of reaction temperature on effi-
in the hybrid system, including reaction pressure and temperature, ciency. When pressure is in the range of 15–23 bar, the NSE effi-
influence methanol conversion rate to syngas, as well as the tem- ciency increases as temperature increases; when pressure is in
perature of the heaters and the reactor. To reveal the impact of the range of 2–11 bar, an optimum NSE efficiency is observed in
both parameters on system performance and determine optimum the range of 175–250 °C and the optimum remains virtually
operating conditions, the NSE efficiency of the hybrid system, as

0.450 0.44 Optimal efficiency
Net solar-electric efficiency

Net solar-electric efficiency

Optimal efficiency
0.425 ar
0.40 ar 2bar
0.400 7b
ar 1bar
0.375 11
0.36 r
0.350 15
0.325 ba
0.32 19
150 r
0.300 175 225 ba
200 250
0.275 0.28
1 3 5 7 9 11 13 15 17 19 21 23 150 175 200 225 250
Pressure/bar Temperature/
Fig. 7. Net solar-to-electric efficiency of the hybrid system at different reaction Fig. 8. Net solar-to-electric efficiency of the hybrid system at different reaction
temperatures versus reaction pressure. pressures versus the reaction temperature.
384 W. Li, Y. Hao / Applied Energy 202 (2017) 377–385

unchanged with respect to variations in temperature; and when
the pressure is as low as 1 bar, the efficiency declines as the tem- 0.04 Ratio to solar energy input

Net solar-electric efficiency
Net solar-electric efficiency 0.43

Ratio to solar energy
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- 0.03
sure on system performance, further analysis is carried out on
components of the system: 0.02 Sum of all losses
(a) Reaction pressure influences the average temperature of 0.41
heaters, for it directly influences the vaporization tempera- 0.01
Heat exergy loss
ture of methanol. Because evaporation heat accounts for a P&C Ex loss
large part of the methanol-absorbed heat (30%), the change 0.40
0.00 PV electricity loss
of the vaporization temperature has a considerable effect on
the average temperature of the heaters. This means that
3 7 11 15 19 23
higher methanol vaporization temperature leads to higher
PV module temperature, which in turn lowers the PV and Pressure/bar
solar collector efficiencies.
Fig. 10. PV electricity loss, P&C exergy loss and heat exergy loss versus reaction
(b) Reaction pressure affects the performance of methanol
pressure at reaction temperature of 225 °C.
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 exchangers leads to exergy loss. On the other hand, the out-
methanol flowing through the pump for the production of let temperature of the mixture of heat exchanger A is higher
the same amount of syngas and thus the increase in both than the ambient temperature (e.g., 15 °C); therefore, the
pump work and exergy loss, which results from the work thermal energy of the mixture is lost to the environment,
difference between the actual compression work and ideal which leads to energy (exergy) loss. In other words, increas-
compression work. On the other hand, higher reaction pres- ing reaction pressure leads to the rise of energy (specifically
sure leads to lower pressure ratio of the syngas compressor exergy) loss during the mixture heat recycling process and
and thereby to less work consumption and less exergy loss. thus poses a negative impact on system performance.
In brief, as the reaction pressure increases, the changing
trends of the pump exergy loss and compressor exergy loss Lastly, by combining all analyses, the major exergy losses are
are opposite. The exergy loss of the pumps/compressors is plotted versus reaction pressure in Fig. 10 to illustrate individual
defined as the difference between the power consumption and combined influences of major irreversible factors on the sys-
of the pumps/compressors and the exergy increase of the tem performance. The PV electricity loss in Fig. 10 is defined as
fluid. Fig. 9 shows comparison between the exergy loss vari- the difference between the PV electricity at reaction pressure of
ation of the pump and compressor as the reaction pressure 3 bar (i.e., the maximum PV electricity of this study) and that at
changes. Compared with the compressor exergy loss varia- selected reaction pressure; the pump and compressor (P & C)
tion, changes of methanol pump exergy loss can be ignored. exergy loss is defined as the sum of the exergy loss in the methanol
The sum of exergy losses of the pump and compressor decli- pump and syngas compressor; and the heat exergy loss is defined
nes with increasing pressure. as the exergy loss due to the temperature difference between the
(c) Reaction pressure affects the degree of heat recovery in heat temperature of the cooled mixture of heat exchanger A and the
exchangers. As mentioned before, more methanol is recycled ambient temperature. Fig. 10 shows that the ratio of PV electricity
at higher reaction pressures. Methanol recycling not only loss to solar energy input increases from 0% to 0.4% when the reac-
consumes pump work, but also dissipates a considerable tion pressure increases from 3 bar to 23 bar; the ratio of heat
amount of heat to the ambient. With respect to the latter, exergy loss increases from 0% to 3.5%, while the ratio of P & C
the heat transfer temperature difference in the heat 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-
1.6 peratures are similar to that presented in Fig. 10 (at 225 °C),
Ratio to net solar electricity/%

Pump exergy loss
1.4 thereby establishing the universality of the analysis methodology
Compressor exergy loss
and validity of the conclusions within the primary range of operat-
Sum of them
1.2 ing conditions of the hybrid system.

0.8 5. Conclusions

0.6 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-
0.2 electric efficiency of the hybrid system (after taking all major
losses into account) reaches up to 45.4% at operating temperature
0.0 of 225 °C and pressure of 7 bar. Compared with conventional PV-
3 7 11 15 19 23
only systems, PVT systems and thermochemical-only systems
(e.g., the reference system), such a combination significantly
Fig. 9. Exergy losses in methanol pump and syngas compressor versus reaction enhances the efficiency for two major reasons. The first reason is
pressure at reaction temperature of 225 °C. the ‘‘cascaded” utilization of solar energy, which results in the
W. Li, Y. Hao / Applied Energy 202 (2017) 377–385 385

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