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Prospects for solar only operation of the hybrid sulphur cycle for hydrogen production
James T. Hinkley a,*, Jessica A. OBrien a, Christopher J. Fell a, Sten-Eric Lindquist b
a b

CSIRO Energy Technology, P.O. Box 330, Newcastle, NSW 2300, Australia Uppsala University, Department of Physical Chemistry, Box 532, S-751 21, Uppsala, Sweden

article info
Article history: Received 12 January 2011 Received in revised form 5 May 2011 Accepted 7 June 2011 Available online 13 July 2011 Keywords: Hydrogen production Hybrid sulphur cycle Thermochemical cycles Electrolysis Solar cells

abstract
The hybrid sulphur process is one of the most promising thermochemical water splitting cycles for large scale hydrogen production. While the process includes an electrolysis step, the use of sulphur dioxide in the electrolyser signicantly reduces the electrical demand compared to conventional alkaline electrolysis. Solar operation of the cycle with zero emissions is possible if the electricity for the electrolyser and the high temperature thermal energy to complete the cycle are provided by solar technologies. This paper explores the possible use of photovoltaics (PV) to supply the electrical demand and examines a number of congurations. Production costs are determined for several scenarios and compared with base cases using conventional technologies. The hybrid sulphur cycle has promise in the medium term as a viable zero carbon production process if PV power is used to supply the electrolyser. However, the viability of this process is dependent on a market for hydrogen and a signicant reduction in PV costs to around $1/Wp. Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

1.

Introduction

It is now widely accepted that modern society must change its patterns of energy consumption to avoid a signicant negative effect on ecosystems through climate change. One of the key aspects of this challenge is reducing carbon dioxide emissions from stationary and transport energy systems. Hydrogen is a fuel and energy carrier widely considered for energy storage and transportation in the future. To reduce carbon dioxide emissions it must be produced using renewable energy sources, such as solar. Potential production routes have been widely researched over many years and various options based on solar-driven water splitting have been identied [1]. Recent screening programs have reviewed the many thermochemical cycles proposed over the years and identied

those with the greatest potential for large scale production of hydrogen [1]. One of the most promising is the hybrid sulphur (HyS) (or Westinghouse) cycle [2], based on redox reactions in which sulphur moves between the S(VI) and S(IV) valence states: SO3 =H2 SO4 #SO2 =H2 SO3 The HyS cycle redox reactions require both electrical and thermal energy inputs which could be supplied by two solar elds e one photovoltaic (PV) and one concentrating solar thermal, as shown in Fig. 1. Hydrogen is produced reductively in the cathodic compartment of an acid electrolyser, while aqueous SO2 is oxidised to H2SO4 in the anodic compartment. Dissociation of SO3 to SO2 and O2 requires high temperatures (1120e1220 K), which can readily be achieved with point-focus

* Corresponding author. Tel.: 61 249606128; fax: 61 249606021. E-mail address: jim.hinkley@csiro.au (J.T. Hinkley). 0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.ijhydene.2011.06.048

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Fig. 1 e Schematic of solar only production of hydrogen from HyS cycle.

solar thermal concentrators. The principal benet of the HyS cycle over conventional PV driven electrolysis is that a large proportion of the energy required to split water can be supplied by solar thermal energy, reducing the requirement for higher value (and higher cost) electricity. PV has been chosen as the solar electricity technology for this work in contrast to previous studies which have considered solar thermal or nuclear technologies [3e5]. This is because there are interesting synergies between the currentevoltage characteristics of the electrolyser unit and PV cells which could potentially result in good integration of the two processes, subject to practical engineering constraints [6]. Because the oxidation of SO2 in solution allows hydrogen evolution at a signicantly lower electrochemical potential than water (or alkaline) electrolysis, less power and hence PV area is required to produce hydrogen at a given rate and integration is more realistic. This paper explores the use of solar energy to drive this acid electrolysis, with particular emphasis on how PV cells and systems might be used. The relative merits of concentrating solar thermal electricity compared to PV are also briey discussed, and estimates are provided for the production costs of various alternatives.

innitesimal change to a higher value) and real electrolysers operate under substantially different conditions. A practical electrolyser needs to overcome mass transfer and kinetic limitations to achieve an acceptable current density to optimise the balance of capital and operating costs (i.e. power consumption). In practice, this is achieved by operating at considerably higher potentials than thermodynamics might suggest, with the difference between the actual operating potential and the thermodynamic value termed overpotential. Conventional commercial electrolysers, which use alkaline solutions to increase ionic conductivity, operate at potentials of around 1.9e2.6 V and current densities of 100e600 mA/cm2 [8]. These electrolysers therefore require an overpotential of around 0.7e1.4 V to achieve acceptable current densities. A number of earlier studies have considered the use of PV to provide the necessary potential to drive water electrolysis. Licht et al. used a multi-junction cell (using layers of AlGaAs and Si), which had an open circuit potential of 1.57 V and a maximum power point (MPP) voltage of 1.30 V [9]. However, this voltage only provides a small overpotential, and thus can only achieve low current densities at the electrolyser surface e the reported current density of about 0.5 mA/cm2 is 3 orders of magnitude lower than in commercial alkaline electrolysers. Other studies have considered the connection of proton exchange membrane (PEM) electrolysers to conventional PV cells. Rodriguez-Castellanos et al. [10] used a module of 36 series connected polycrystalline silicon cells to drive a stack of 10 PEM electrolyser assemblies. The electrolysis stack was operated close to the MPP of the solar module, at a potential of 14 V, or 1.4 V per electrolysis cell, again only marginally above the reversible potential. This conguration was capable of producing a current of 0.72 A in the electrolysis stack, equating to a current density of 80 mA/cm2. This experiment is analogous to a single electrolyser cell being driven by 3.6 PV cells connected in series. The issue of optimal direct coupling of PV cells and conventional PEM electrolysers has also been investigated by Paul and Andrews [11]. They assessed a number of series and parallel congurations to determine the optimal conguration for multiple PV modules and PEM electrolyser stacks, as well as the effect of solar irradiance on the process. Paul and Andrews predicted that a directly coupled system of four 75 W conventional silicon PV modules with ve 50 W PEM electrolyser stacks would extract 95% of the theoretical maximum energy. This compares favourably with the power extraction possible using an electronic coupling system with MPP tracking, which is around 90% [12]. This was identied as possible early market for remote hydrogen production, since costs of an electronic coupling system including MPP tracking, quoted as approximately $700/kWe, could be avoided [11].

2. Background to electrolysis and photovoltaics (PV)

2.1. Solar electrolysis of water

2.2.

Electrolysis in the HyS cycle

The theoretical potential required to produce hydrogen from the electrolysis of water is the reversible potential for oxygen production, 1.23 V for pure water under standard conditions [7]. However, this is a thermodynamic equilibrium potential for the reaction to proceed (innitely slowly for an

Initial work on the electrolysis step in the HyS cycle was conducted by the nuclear industry, and in particular the Westinghouse Electric Company, in the 1970s and early 1980s [2,13,14]. Renewed interest in hydrogen production resulted in the construction of new electrolysis equipment at Savannah River National Laboratories (SRNL) from 2004 [15]. This facility includes a prototype electrolyser capable of operation at

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elevated temperature (up to 353 K) and pressure (up to 600 kPa) [16]. Our paper utilises published results from this experimental electrolyser to build up scenarios for the cost evaluation of various potential congurations. A key feature of the HyS cycle is that the electrolysis of sulphurous acid has a signicantly lower reversible potential than water electrolysis (E0 0.17 V cf. 1.23 V) [2], and therefore the theoretical power requirement of the electrolyser is greatly reduced. This reduction is possible because of the storage of solar energy as chemical energy in the thermal dissociation step, where sulphur species are reduced from the (VI) oxidation state to the (IV) oxidation state in a strongly endothermic process. However, as with water electrolysis, the operation of a practical electrolyser is conducted far from standard conditions. Integration of the electrolysis step with the remainder of the cycle requires signicantly higher acid concentrations to minimise the amount of water that needs to be removed prior to acid decomposition. This results in solutions that are around 50% H2SO4 by weight (w6 M c.f. 1 M under standard conditions), increasing the reversible potential to around 0.24 V [17]. Additional overpotential is required to operate at acceptable current densities.

the daylight hours and solar irradiance. Fig. 3 shows data obtained from a pyrheliometer on a relatively clear day, and shows both the total horizontal radiation (green), relevant to PV cells, and also the direct or beam irradiance (red), relevant to concentrating solar installations such as heliostat elds. The direct irradiance data shows how 2-axis tracking results in a more uniform energy output over the day. Matching thermal and PV output over the day needs to be considered if stationary PV modules are used to provide the power for the electrolyser.

3. Integration of solar electricity and electrolysis in the HyS cycle

A conventional PV module consists of around 32e50 cells connected in series to achieve an open circuit voltage of around 20e30 V. One approach for hydrogen production by electrolysis would be to only connect sufcient PV cells in series to achieve the necessary voltage for a single electrolysis cell. For example, the potential required to operate a conventional alkaline electrolyser (around 1.9 V) can be achieved by connecting four conventional silicon PV cells in series. The required current to supply a given electrolyser area would be achieved by connecting sufcient numbers of these series connected cells in parallel. If the electrolyser operates at a current density of 300 mA/cm2, the ratio of solar PV area to electrolyser area would therefore need to be (at least) 40:1 for a typical PV current density of 33 mA/cm2 (10 parallel sets of 4 series connected cells). The main opportunity of the solarised HyS cycle compared to alkaline electrolysis is that the PV area is signicantly reduced due to the reduction in voltage and hence power consumption. Fig. 4 shows recent data from SRNL electrolyser [18] compared with the output of both a single conventional PV cell and an optimised conguration. In the optimised case, the area ratio of PV cells to the electrolyser area is about 16, and the PV cells operate close to the maximum power point. The required voltage to operate (0.9 V) is achieved by series connection of PV cells in the ratio of 1.8:1 to the number of electrolyser cells (for instance 18:10). The current required is

2.3.

Current voltage characteristics of a PV cell

The current density versus voltage (J-V) characteristics of a typical single PV cell are shown in Fig. 2. A PV cell in its conventional use is optimised for the highest possible power output, which occurs where the product of current and voltage gives the highest value. This point is termed the maximum power point (MPP); a conventional crystalline silicon PV cell has an MPP current density of around 33 mA/ cm2 at a potential of around 0.50 V under one sun conditions (mean of data from four datasheets).

2.4.

Variable output of a PV cell

The output from a PV module varies signicantly over the course of a day, due to a range of effects including cosine effect, spectral effects, temperature and intermittency due to cloud cover. There are also seasonal variations in the time and magnitude of the power produced by PV panels in line with

Fig. 2 e Typical performance characteristics for a single PV cell.

Fig. 3 e Irradiance data from Newcastle, NSW for a relatively clear winters day.

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achieved by parallel connections of 9 such groups of series connected cells to scale the 33 mA/cm2 produced by a single cell to match the 300 mA/cm2 required by the electrolyser. The ratio of PV area to the electrolyser area is therefore about 41% of that required for a system using alkaline electrolysis. There are in fact a number of possible congurations in which PV cells could be coupled with the electrolysis step in the HyS cycle including:

intermittent operation as the self-tuning option, and would provide minimal improvement over a well matched directly coupled system.

3.4.

Totally integrated systems

3.1.

Grid connected (buffered) systems

PV cells generate power and feed into the grid. Power for the electrolyser is drawn from the grid. The advantage of this approach is that both systems can be independently optimised, and electrolyser capital costs are minimised. However, some power losses are incurred through conversion from DC to AC and back again.

In this conguration, the PV cell is sandwiched on top of the electrolyser, eliminating external circuitry. This arrangement would result in the lowest current density in the electrolyser and could result in much higher power extraction and hydrogen production per unit area of PV by operating with a much lower overpotential. However, the practicalities of circulating large volumes of concentrated sulphuric acid around a large area of integrated production (and a large active electrolyser area) make this system rather challenging to realise. The grid connected systems and direct coupled self-tuning stand-alone (off-grid) systems are considered further.

3.2.

Self-tuning stand-alone (off-grid) systems

Sufcient PV cells are series connected to provide the necessary potential to drive the HyS acid electrolyser. Because each component has a characteristic J-V curve, the connected system will nd an operating point at the intersection of these curves. This system can potentially have higher power efciency through the elimination of conversion losses, and avoids the cost of electronic coupling and MPP tracking, although the electrolyser capital cost is higher due to reduced operating hours. There is also a risk that variable operating conditions from intermittent supply may reduce the life of the catalysts used in the electrolyser.

4. Costing the production of hydrogen from PV & HyS cycle

Capital and operating costs have been estimated for ve basic scenarios. These scenarios were chosen to determine the relative cost of hydrogen for a HyS plant using electricity supplied from the grid compared with electricity supplied by present generation PV cells, as described in the rst two congurations outlined in Section 3. These congurations e the grid connected and direct coupled options e are expected to have the upper and lower bounds for system costs using PV cells. Three reference scenarios were also considered based on the potential use of alkaline electrolysis (AE) and retail electricity from the grid: Case 1: alkaline electrolysis, power from conventional grid (reference case 1) Case 2: alkaline electrolysis, grid connected PV (reference case 2) Case 3: HyS electrolysis, power from conventional grid (reference case 3) Case 4: HyS electrolysis, grid connected PV (grid buffered) Case 5: HyS electrolysis, direct coupled PV (cost of MPP tracking is subtracted from PV cost) Basic cost and performance parameters have been sourced from literature, as in Table 1. O&M refers to operating and maintenance costs. All costs are expressed in US dollars using an assumed exchange rate of $AU 1 $1 US and 1V $1.40 US. As can be seen, most values in Table 1 are from papers published in the last few years. However, it is critical to note that several of the costs are somewhat speculative, because no plants have been constructed for several of the key process steps in the HyS cycle. This is discussed in more detail below Table 1.
C

3.3.

Voltage controlled stand-alone systems

PV modules are optimised for power by operating at MPP, and the resulting power is converted to an appropriate operating point on the J-V curve of the electrolyser. This ensures that the power extraction from the PV cells is optimised, but increases PV costs through the electronic coupling and MPP tracking. The system would also be subject to the same limitations of

Fig. 4 e Direct coupling of an electrolyser and solar cell array, showing operation at high current density close to maximum power point of a well matched system [12].

AE electrolyser costs vary signicantly in the literature. Licht et al. [22] state that current state-of-the-art AE electrolyser technologies have costs of $425/kWe. This is comparable with Graf et al. [3], who state the cost of

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Table 1 e Key cost and performance parameters used in scenario modelling. Parameter
Average cost of water Cost of electricity (industrial tariff) AE electrolyser cost HyS electrolyser cost PV cost (full system) PV coupling and MPP tracking O&M cost PV Field O&M cost other unit ops Amortised capital cost PV capacity factor Electrolyser current density HyS electrolyser voltage AE electrolyser voltage

Value
$1.50 $100 $500 $1367 $3.50 $0.70 0.08% 5% 11.5% 25% 500 0.6 1.9

Unit
$US/kL $US/MWh $US/kWe $US/kWe $US/Wp $US/Wp of xed capital cost of xed capital cost of xed capital cost mA/cm2 V V

Reference
[19] [20] [3,21,22] [5,23] [5,24] [11] [25] [3,4,26] [21] [27] [23] [23] [8,22]

Year
2010 2011 2008,2010,2006 2007 2010 2008 2008 2007,1977,2008 2006 2003 2005 2005 1990,2010

a Norsk Hydro (now Hydrogen Technologies, a subsidiary of Statoil) electrolyser is 1.5 MV; the installed cost including piping and connection equates to $498/kWe. Lahoda et al. [21] quote a price of $1.5 M US for the same module, equating to a cost of $719/kWe at the stated power per module. A mid range value of $500/kWe was used in our analysis. HyS electrolyser costs are very difcult to estimate as they do not presently exist at scale. Kolb et al. [4] predict a cost of $380/kWe by 2020, although this is based on the US Department of Energy (DOE) target of $300/kWe for AE. Lahoda et al. [21] assumed that module costs would be similar to AE electrolysers, but at higher current densities; the equivalent cost was $601/kWe. Summers et al. [23] assumed a baseline cost of $2000/m2 of active cell area, which they noted was between DOEs advanced PEM water electrolyser cost goal of $1025/m2 and the current cost of chlor-alkali cells of $3500e7000/m2. This is equivalent to a cost of $762/kWe at the stated cell voltage of 0.525 V and an assumed current density of 500 mA/cm2. Leybros et al. [5] also based their estimates of 2920 V/m2 (w$4088/m2) on current AE electrolyser costs, assuming electrodes were made of platinum coated carbon-steel. However, Leybros et al. assumed more conservative operating parameters of 200 mA/cm2 and 0.6 V, resulting in a signicantly higher specic cost of $3430/kWe. Graf et al. [3] also based their estimates on AE electrolysers, but have a slightly higher specic cost of $4300/kWe (calculated from data provided for operating hours, production, electrical power and capital cost). In this work we have assumed that the electrolyser has a cost of $4100/m2 but achieves the SRNL target performance of 0.6 V at 500 mA/ cm2. This yields a cost of $1367/kWe. This is a compromise between the US and European study assumptions. Similarly, the cost of the solar eld and decomposition reactor is somewhat speculative. Graf et al. [3] do not separate the eld costs or thermal requirements for the two solar duties of electricity generation and sulphuric acid decomposition. Costs are estimated at $66.4 million for the solar equipment and $41.0 million for the chemical plant, for an annual production of 3740 tonnes of hydrogen. This plant does not have storage but operates for 4089 h per year (47% capacity factor). The solar eld

costs are based on a 2006 estimate of the then current expected costs for manufacturing large heliostats at a moderate scale of 5000 units per year [28]. Assuming the split of solar component costs for the two duties is proportional to their respective receiver areas results in a combined cost of $67.6 million for the HyS solar components and chemical plant ($18 million per 1000 tonnes of hydrogen). Kolb et al. [4] estimate the cost of the 2020 solar plant to be $311 million for an annual production of 34,000 tonnes of hydrogen ($9 million per 1000 tonnes). The 2020 plant has 13 h of storage to allow round the clock operation of the chemical plant. In this paper, we have used the higher of the two estimates, $18 million per 1000 tonnes annual output. For Cases 3 and 4, we have added a further 5% to the capital cost to provide the necessary storage to allow interfacing with an electrolysis plant that operates around the clock. This is considered realistic as the storage of sulphur dioxide and sulphuric acid can be readily accomplished with conventional engineering materials. The costs for a plant producing 100,000 kg of hydrogen per day for each scenario are summarised in Table 2. It is assumed that sufcient PV capacity is installed to supply all of the electrolyser power requirements, and that the production rate is allowed to vary from season to season without signicantly affecting electrolyser performance. Amortised capital costs have been approximated by assuming an annual after tax xed charge rate of 11.5% of the initial capital cost, as per Lahoda et al. [21]. This equates to a real discount rate of 9.75% and a 20 year loan period. The discount rate is near the upper bound of estimates used in the evaluation of energy technologies (e.g. 5% or 10% used in [29]) and is deemed appropriate given the new process being examined.

5.

Comparison of solarisation cost scenarios

The projected cost of hydrogen produced from the incumbent reference technology, alkaline electrolysis, using electricity sourced from fossil and renewable PV energy is $5.57 and $11.54/kg respectively. It is hardly surprising that the cost of

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Table 2 e Evaluation of hydrogen production costs by different technology scenarios. Case 1: Alkaline electrolysis, grid power (retail)
Electrolyser Operating hrs/day Voltage, V Current density, Acm2 Area, m2 Power, MW Capital cost, $m Decomposition Capital cost, $m Photovoltaics PV area required, m2 PV peak power, MW PV Capital cost, $m Total capital cost, $m Operating Costs ($m/yr) Electricity Water O&M electrolyser O&M decomposition O&M PV Total operating Operating Cost, $/kg H2 Amortised Capital Electrolyser Decomposition Photovoltaics Total Total cost of H2, $/kg 22.8 1.9 0.5 23,326 222 111 e e e e 111 184.5 0.5 5.5 e e 190.6 5.22 0.35 e e 0.35 5.57

Case 2: Alkaline electrolysis, grid connected PV

22.8 1.9 0.5 23,326 222 111 e 5,671,000 936 3275 3386 e 0.5 5.5 e 26.2 32.2 0.88 0.35 e 10.31 10.66 11.54

Case 3: HyS electrolysis, grid power (retail)

22.8 0.6 0.5 23,236 70 96 690 e e e 786 58.3 0.5 4.8 34.5 e 98.1 2.69 0.30 2.17 e 2.47 5.16

Case 4: HyS electrolysis, grid buffered PV

22.8 0.6 0.5 23,326 70 96 690 1,791,000 295 1034 1820 e 0.5 4.8 34.5 8.3 48.1 1.32 0.30 2.17 3.26 5.73 7.05

Case 5: Direct coupled HyS electrolysis and PV

5.04 0.6 0.5 88,638 266 364 658 1,696,000 280 784 1805 e 0.5 18.2 32.9 6.3 57.8 1.58 1.14 2.07 2.47 5.68 7.27

hydrogen production is signicantly higher when the power is supplied by PV rather than conventional grid supplied electricity, as this is dominated in Australia by fossil fuel combustion. Future increases in the cost of electricity are estimated to contribute $0.51/kg H2 per $10/MWh increase in the retail price. If the PV was replaced by concentrating solar thermal electricity, at present costs estimated between 190 and 250 $/MWh [30], this would result in a renewable hydrogen production cost from alkaline electrolysis of $10.12e$13.15. The third reference case e a HyS electrolyser powered by retail electricity from the grid e is estimated to have a hydrogen production cost marginally below (about 7%) that of conventional electrolysis using retail electricity (Case 1). This indicates that the thermal energy embedded in the sulphur dioxide produced from sulphuric acid cracking is potentially cheaper than electrical energy sourced from the grid, because there is no inefcient conversion of thermal energy to electricity as in a conventional power cycle. While this is certainly likely to be true in the mid to long term, it is important to note that neither the sulphuric acid cracking or sulphur dioxide electrolysis have yet been demonstrated beyond laboratory scale. However, the work of Kolb et al. [4] clearly shows that the HyS process can be expected to be competitive with alkaline electrolysis once the technology is mature. Perhaps the most signicant point to consider is that the HyS cycle would use signicantly less electrical power than alkaline electrolysis, should hydrogen demand be sufcient to warrant large scale production. The reduction in voltage from 1.9 V to 0.6 V translates to a 68% decrease in electrical power

consumption from about 51 kWh/kg to 16 kWh/kg. Regardless of the source of the electricity, this reduction in consumption may prove a signicant driver for the future uptake of the HyS cycle for large scale hydrogen production. The PV driven HyS cases are strongly inuenced by the capital components of the PV and decomposition plants. The direct coupled option appears inferior to the grid buffered case due to the increased size and cost of the electrolyser as a consequence of lower utilisation (daylight only operation). It is possible that this cost is slightly exaggerated since the balance of plant, a signicant component of the hydrogen plant, was not assumed to have any economies of scale. Similarly, it was assumed that there is no penalty for using the grid to buffer the system. This is probably a reasonable assumption, however, as PV tends to match the peak load prole, and in fact there may be some net benet accrued if off peak power is acquired at other times. Steady state operation would also be far more favourable in terms of the long term stability of the electrolyser units and especially the activity of the catalyst on the electrodes [31]. PV driven systems have some positive characteristics on the surface in terms of the good match with performance curves of an electrolyser and the ability to build a simple and self-tuning system. However, the present high cost of PV (and signicant ongoing associated O&M costs) means that the present generation cells cannot realistically be regarded as a potential energy source for hydrogen production. Further analysis of the amortised capital cost can be used to consider the longer term prospects for PV driven electrolysis in the HyS cycle. Breaking

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the capital cost down by plant area (Table 2) shows how the overall cost is determined by the relative contributions of the electrolyser, PV and decomposition components. A sensitivity analysis was conducted to determine the PV cost required to meet the DOE target of $2e3/kg [32]. Reference Case 2 e PV supplied alkaline electrolysis e was found to require a signicant reduction in installed PV costs from around $3.50 to $0.79/ peak watt to achieve a production cost of $3/kg. The HyS cases were strongly impacted by the amount of capital required for the decomposition and electrolysis sections. In these cases, the amortised capital cost of the decomposition section contributes $2.07e2.17/kg. The associated O&M cost (5% of the xed capital) of $0.90e0.95/kg essentially preclude attainment of the $3/kg target. However, if solar eld costs decrease in line with the expectations of Kolb et al. [4], these costs would be halved to around $1.50/kg. The direct coupled case would still be unable to meet the $3/kg target due to the signicant cost of the electrolyser, which has widely varying predictions of capital cost. However, in the grid buffered case, the $3/kg target could be achieved at a PV cost of $1.07/Wp. While these costs remain rmly in the future, they illustrate how a combination of solar thermochemical cracking and low cost PV may one day offer a realistic and economically attractive large scale path for hydrogen production.

Fully solarised production is considerably more expensive, and the cost of PV cells remains a major barrier to hydrogen production from this technology; for alkaline electrolysis, substantial decreases from the present $3.50 to $0.79 per peak watt are required to meet the DOE target of $2e3/kg H2. The HyS process is a promising option for the medium to long term, but requires greater technical maturity and reduced costs for the solar decomposition section in particular. If these costs do indeed decrease as projected, the $3/kg H2 production cost target could be attained at a PV cost of around $1.07 per peak watt. Direct connection of the PV and solar thermochemical plants does not appear promising due to the higher capital costs associated with part time operation of the electrolyser. It is also likely that intermittent operation is unfavourable for the lifetime of the catalysts employed.

Acknowledgements
This work was funded by CSIROs Energy Transformed Flagship along with support for Professor Sten-Eric Lindquist under CSIROs Distinguished Visiting Scientist Scheme.

references

6.

Conclusions
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While interest in hydrogen may have waned somewhat recently, it is clear that low carbon intensity processes will be needed for large scale production in the future. This paper has explored some of the issues associated with the integration of two solar technologies in the HyS process for water splitting. Initially, it was speculated that signicant benets would be obtained from the direct integration of PV cells and the electrolyser in the HyS cycle, resulting in a simple and self-tuning system. This analysis, however, identies two signicant issues. Firstly, utilisation of the electrolyser proves to be an important consideration, with the capital cost of the electrolyser making a signicant contribution to the levelised cost of hydrogen. Secondly, from an operational point of view, it is preferable to run the electrolyser under steady state conditions to maximise component life and simplify operation of ancillary operations. The HyS cycle appears to have signicant promise as a future production pathway compared to alkaline electrolysis. Alkaline electrolysis is a relatively mature technology with low technical risk and moderate production costs of around $5.57/kg H2. However, one of the barriers to large scale production is simply the amount of electrical energy that would be required. While the HyS cycle still includes electrolysis e and therefore consumes electrical energy e the amount of electrical energy is decreased by about 68%. Initial cost estimates presented in this paper also indicate that the thermal energy required to complete the cycle in the solar thermochemical step can be supplied more economically than present grid sourced electrical energy, reducing the production cost to $5.16/kg H2, although this is reliant on maturation of the solar thermal cracking technology.

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 5 9 6 e1 1 6 0 3

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