Sunny
Maye
a,
Hubert H.
Girault
a and
Pekka
Peljo
*ab
aLaboratoire d'Électrochimie Physique et Analytique, École Polytechnique Fédérale de Lausanne, EPFL Valais Wallis, Rue de l'Industrie 17, Case Postale 440, CH-1951 Sion, Switzerland
bResearch group of Physical Electrochemistry and Electrochemical Physics, Department of Chemistry and Materials Science, Aalto University, PO Box 16100, FI-00076 Aalto, Finland. E-mail: pekka.peljo@aalto.fi
First published on 9th June 2020
Low-grade heat (below 200 °C) is available in vast quantities from industry, or from standard roof-top solar thermal collectors. However, the production of electric power from these heat sources is challenging with existing technologies. Thermally regenerative batteries allow both the conversion and the storage of thermal energy into electric power, but they suffer from low operation voltages and low output power. Here, we propose a thermally regenerative nanoslurry flow battery based on copper complexation with acetonitrile in non-aqueous solutions operating at voltages above 1 V. The Cu(I) complex can be destabilized by the removal of acetonitrile by distillation, leading to the production of solid copper nanoparticles and Cu(II) in solution, thereby charging the battery. We demonstrate the electricity production at average power densities of 90 W m−2 and peak-power densities up to 150 W m−2, and estimate the theoretical efficiency of the full system at 2%. The results demonstrate a proof-of-concept for harvesting and storage of electricity from low-quality heat.
Broader contextLow-grade thermal energy (<200 °C) generated by industry, but also increasingly available from geothermal energy sources and rooftop solar thermal collectors, is an enormous underutilized resource. For example, as much as 20 to 50% of the energy consumed in the industrial manufacturing processes is lost as waste heat. Although waste heat recovery offers significant energy savings and improved energy efficiency, it is still not industrially exploited. This shows that the technical challenges for utilizing this energy are higher than for converting wind or solar energy into electricity. In this work, we have doubled the cell voltage of a thermally regenerative flow battery to 1.2 V. Although thermo-electrochemical systems have been demonstrated earlier, achieving a cell voltage larger than 1 V opens the way to practical electrochemical heat recovery systems. As this work envisages a major leap forward in terms of theoretical thermal conversion efficiency, cell voltage, and energy storage density, these improvements could make this technology industrially relevant. |
Thermoelectrochemical systems for heat-to-power conversion have been reviewed recently.5,14,15 Liquid-based thermoelectric systems, where a cell voltage is produced by a temperature gradient between the two electrodes,16,17 and salinity gradient energy systems, utilizing different salt concentrations obtained by evaporation to generate cell voltages,18,19 are only able to produce modest cell voltages (<300 mV) and output powers. On the other hand, higher cell voltages can be achieved with thermally regenerative batteries, where thermal reactions induce a chemical reaction to charge the battery. Most thermally regenerative batteries are based on copper20–22 or silver23 complexation with ammonia or acetonitrile24,25 in aqueous solutions. The removal or addition of the complexing agent is used to change or even inverse the cell voltage,20–22 or to induce disproportionation of a Cu(I) complex to produce Cu and Cu(II) as described below.24,25 Cu and Cu(II) can then be discharged in a battery to produce electricity. The advantage of these systems is that in addition to heat-to-power conversion, they are also able to store energy.24 However, almost all the concepts proposed in the literature show cell voltages below ca. 0.65 V, resulting in low output power. One exception is a Zn and Cu based system using ammonia to change the voltage of the positive Cu-electrode, enabling operation at high power densities but low thermal efficiencies of <1%.26
These recent reports show that exploitation of low-temperature heat sources by means of unconventional technologies is attracting significant interest from the scientific community. The main difficulty has been to reach a reasonable efficiency, of the order of 10%. Currently, only one technique reaches this goal (demonstrating efficiency of 8%)27–30 while the others are limited to 1% or less.5
One approach to increase the cell voltage is to remove water. Indeed, an all-copper battery in water-free acetonitrile has a cell voltage of 1.3 V31 in comparison to an aqueous system cell voltage of 0.62 V.24 It is important to note that the all-copper battery in non-aqueous acetonitrile reported by Kratochvil & Betty31 cannot be charged with heat, as removal of all the solvent would result in a mixture of solid copper powder and Cu(II) salt precipitate. Therefore, a higher boiling point co-solvent such as water24 or propylene carbonate utilized in this work is required to realize thermal charging. As acetonitrile forms an azeotrope with water (distillation results in removal of both water and acetonitrile),25 replacement of water with another high boiling point co-solvent allows reduction in the energy demand for the thermal regeneration step. While a thermally regenerative copper battery employing 30% aqueous acetonitrile solution has a maximum theoretical efficiency of ca. 6% mainly due to the low cell voltage and the energy demand to evaporate water, the non-aqueous systems described here show much higher theoretical efficiencies of up to 13%.
In this work, we demonstrate unprecedented cell voltage and high output power for a thermo-electrochemical battery, by utilizing a copper-acetonitrile system with propylene carbonate as a co-solvent due to its high boiling point (242 °C) and stability. The co-solvent is essential to solubilize the Cu(II) salt, allowing separation of solid copper from the Cu(II) electrolyte. We characterize all the thermodynamic parameters of the system to evaluate the theoretical full cycle efficiency, and demonstrate the heat-to-power production and storage with this system.
Here, we demonstrate that the theoretical efficiency can reach up to 2%, with a volumetric energy density of 2.6 W h L−1, and show how these numbers can be significantly improved. These values are higher than reported previously (0.5% and 0.65 W h L−1)20 whilst keeping a similar power density. This significant enhancement in comparison with previous studies on thermally regenerable systems is obtained because of increased cell voltage, from 0.5 V20 up to 1.2 V in this work.
The remaining challenge of this type of system has been the question of how to reintroduce the heat-charged electrolytes into the electrochemical cell. In this work we solve this issue by utilizing nanoslurry based copper electrolytes. Slurry-based flow batteries have been demonstrated before, but they require careful control of the particle size.32–34 In this work, nanosized copper slurry is used to promote nucleation of the copper recovered by the thermal regeneration. This allows separation of copper from the thermally regenerated solution by for example centrifugation. Addition of acetonitrile into the copper nanoparticles allows recirculation of the copper through the electrochemical cell as a slurry without compromising the power density or energy storage capacity, as demonstrated in this work.
Negative electrode (Cu):
Positive electrode (carbon felt):
The electrochemical kinetics of the negative electrode reaction has been investigated earlier,50 and the study of the positive electrode reaction is included in the ESI.† In short, both reactions have reasonably facile kinetics, with much higher reaction rates than obtained in the state-of-the-art vanadium flow batteries.
In Fig. 1, charge–discharge cycles of the RFB with a 0.5 M LiPF6 supporting electrolyte are shown, with improved efficiencies in comparison with the H-cell results included in the ESI.† The coulombic efficiency is stable during the battery test and its averaged value is 99% (Fig. 1b). However, the energy efficiency decreases with time, starting from 81% and reducing to 44% after 50 cycles (Fig. 1b). A similar trend is also observed for the state of charge (Fig. 1b) and is assigned to solvent crossover through the anionic membrane, which is observed as a significant change of the volume in both tanks (at the end of the cycling test: V− < V+). However, the state of charge and energy efficiency can be easily recovered if the discharge solutions (mainly Cu(I) species on both sides) are mixed and equally separated back between the positive and negative tanks (see the ESI† for more details). This behaviour is also observed in typical vanadium redox flow batteries, and electrolyte rebalancing systems have been developed to deal with this problem.51–55
Fig. 1 Cu redox flow battery with [Cu(CH3CN)4]PF6 (0.15 M) and LiPF6 (0.5 M) and i = 10 mA cm−2, (a) potential cycling (not iR corrected) with time and (b) efficiencies and normalized capacities of the battery for all cycles. The volume of both electrolytes was 25 mL. (c) Power output with Cu foam and nanoslurry electrolytes with a composition of 50 vol% ACN containing 0.15 M [Cu(CH3CN)4]BF4, at the flow rate of 40–45 mL min−1. The iR corrected data are shown in the ESI.† |
The energy storage density of the described system is 2.6 W h L−1 (0.15 M Cu(I)-species), but could be increased by increasing the concentration of copper.42
Another approach is to replace the copper electrode with carbon foam and flow a slurry composed of copper nanoparticles on the negative side. This transforms the system to a true flow battery, where the capacity of the system is independent of the electrode mass and depends only on the volume of the electrolyte. Polarization curves with 5 wt% and 15 wt% nanoslurry electrolytes are shown in Fig. 1c, displaying even higher power densities than could be obtained with copper foam.
Differential scanning calorimetry (DSC) measurements shown in the ESI,† demonstrate that the disproportionation step can be distinguished from the acetonitrile vaporization at 82 °C, taking place at ca. 160 °C for solid Cu(CH3CN)4BF4. This indicates that the disproportionation reaction cannot simply be induced by the distillation of the acetonitrile solvent close to 81 °C, but a surplus of heat is required to destabilize the Cu(I) complex. Further investigations indicate that Cu(I) disproportionation could be realized at temperatures near 120 °C for a 30% acetonitrile–70% propylene carbonate solution. The thermodynamic parameters including enthalpies of vaporization and heat capacities for various ratios of Cu(I) containing acetonitrile–propylene carbonate mixtures have been measured with DSC, and are reported in the ESI.† These results also confirm that it is necessary to consider the excess energy of destabilizing the complex, as it is clearly not accurate to consider simple evaporation of the complexing agent as suggested previously.21 This issue was also highlighted recently.22
The Cu(I) solution was heated under nitrogen at 120 °C to induce thermal regeneration. In order to keep a solution after the disproportionation, the solvent is partially composed of propylene carbonate, which remains in the liquid state (b.p. = 242 °C). The completion of the reaction and the formation of Cu particles and Cu(II) solution was confirmed by the colour transition from the transparent Cu(I) solution to the Cu(II) and with the appearance of some metallic Cu particles. We analysed the resulting solution with different techniques to verify and describe the presence of Cu(II) and metallic Cu. The acetonitrile condensate removed during thermal regeneration is collected to be introduced back in the system for the electrochemical discharge.
Dynamic light scattering (DLS) was used to analyse the size distribution of the thermally regenerated Cu particles, found to be between 70 and 460 nm in diameter, as shown in Fig. 2a. The average value for the diameter of the synthesised Cu particles is 187 ± 1 nm with a peak of population around 122 nm. TEM analysis shown in Fig. 2b indicates that smaller Cu particles down to 5 nm in diameter are also present. This implies that many different sizes of metallic Cu are produced during the thermal treatment of Cu(I). The complete conversion of Cu(I) to Cu and Cu(II) was confirmed by UV/Vis spectroscopy and bulk electrolysis, as shown in the ESI.†
Fig. 2 After thermal regeneration from [Cu(CH3CN)4]BF4, (a) Cu NP size distribution from DLS measurement and (b) TEM images of Cu particles produced upon thermal regeneration. |
A flow cell was assembled to demonstrate that the system can be used to realize heat-to-power conversion. Four different methods were tested: (1) discharge of the positive side only, (2) 1st discharge of the full cell with nanoslurry electrolyte, (3) followed by a second cycle, and (4) discharge of the full cell, with Cu particles filtered off and added into the cell. In the first case copper particles were separated from the solution by filtration, and the recovered Cu(II) electrolyte was introduced into the positive side of the cell. A fraction of the distilled acetonitrile was introduced back in the Cu(II) solution to obtain the positive electrolyte, and copper foam was used as the negative electrode. In the fourth case the filter with Cu particles was introduced between the carbon foam current collector and the anionic membrane. In the second case, copper nanoslurry particles were separated by centrifugation. A large fraction (ca. 15 mL) of the recovered acetonitrile was added into the slurry, resulting in ca. 90% CH3CN solution, and ca. 10 mL was added into the positive electrolyte (30% v/v CH3CN). For the third case, discharged electrolyte from the first cycle was heat regenerated again, and the discharge was performed as during the first cycle.
The electrochemical discharge of the thermally charged battery at a constant current is shown in Fig. 3, and polarization curves in Fig. 4. When heat-regenerated solution was used on the positive side, with Cu foam as the negative electrode, the cell voltage is around 1 V and the capacity of the discharge corresponds to 85–90% of the theoretical capacity of the battery. This difference might come from the loss of some Cu(II) solution during the thermal regeneration process, but it could be also due to an incomplete thermal treatment of the initial Cu(I) solution. In this case the cell was limited by the Cu(II)/Cu(I) couple. For the last case, much lower discharge voltages and capacities are obtained, because also the negative electrode reaction limits the cell performance, and at some point contact between the Cu-particles and the electrode is lost. Higher discharge voltage and capacity is reached when 15 wt% Cu nanoslurry electrolyte is used in the second and third cases. The first cycle allowed utilization of 80% of the nominal capacity, while this number was reduced to 70% for the second discharge. Further cycling is required to evaluate the long term stability of the system, but the use of the nanoslurry electrode allows envisaging a full process based on this concept. These curves also prove that heat storage is possible inside a Cu RFB through a chemical energy conversion, with average power of 75 W m−2.
Fig. 3 (a) Discharge curves of the heat-regenerated RFB at 10 mA cm−2. The positive electrolyte is composed of heat-regenerated Cu(BF4)2 (0.15 M) and TEABF4 (0.15 M) in acetonitrile–propylene carbonate mixture and the negative electrolyte of TEABF4 (0.15 M) in acetonitrile–propylene carbonate mixture. The acetonitrile is collected from the distilled fraction during the thermal disproportionation of the Cu(I). Additionally, on the negative side, the filter with the Cu particles is added in parallel to the membrane. Volumes of the electrolytes on the positive side are 20, 10, 10 and 8 mL, respectively. (b) Average power density output of the RFB during discharge vs. the cumulative energy output per mol of Cu2+. Area of the membrane is 8 cm2. The iR corrected data are shown in the ESI.† |
The performance of the Cu-RFB is described in Fig. 4 by the power production for the three different cases. The highest power density of 200 W m−2 is achieved with a Cu-foam electrode, but a nanoslurry system is able to show power densities of ca. 150 W m−2. These values compare favourably with the earlier report of 136 W m−2 for the aqueous ammonia based Cu-system,21 and of 236 W m−2 for the same system at increased temperatures.20 According to these results, the power that can be produced from a thermal treatment is promising and allows considering this Cu-RFB as a potentially efficient tool to convert heat into stored electricity. Furthermore, if the resistance of the system could be decreased, much better performance could be obtained (see iR-corrected polarization and power curves in the ESI,† showing significant increase in power density). Such improvements are expected in the future, considering that the membranes developed for non-aqueous systems are inferior in comparison to the membranes used for aqueous systems.56
(1) |
It is also worth noting that these values are theoretical efficiencies, calculated based on the measured or estimated thermodynamic properties. Therefore losses due to the pumping, overpotentials etc. are not included in this number. Commercial flow batteries are able to demonstrate stack level energy efficiencies of 70–80% depending on the discharge currents.57 As this number takes into account the inefficiencies in both charging and discharging, the energy efficiency of the discharging step would be ca. 80–90%. Furthermore, about 5% of the energy in a typical flow battery is lost in pumping during discharge (2.5% loss assumed for both sides).57 In this case the negative side is a slurry with twice the specific density of only the electrolyte. The viscosity is also significantly higher, up by a factor of 5 reported for carbon nanotube slurry.36 Therefore the pump consumption of the negative side could be 25% of the discharge energy, while the number for the positive side would be 2.5% (this pumping loss may actually be an overestimation, as a recent paper suggests that pumping losses in a slurry system can be reduced to <1% of the energy output58). This would result in the heat-to-power conversion efficiencies of 8%. The total efficiency depends also on the energy required for separation of solid copper. Energy required by centrifugation could become unreasonable, so other more cost-effective methods such as hydrocyclones could be envisaged for solid–liquid separation.
We acknowledge that there are many uncertainties behind these assumptions. For example, it is questionable if the performance of the Cu flow battery will be able to match the performance of the vanadium system. Also, the effect of the increased viscosity for the pump power consumption would require more detailed studies. In the present system the nanoslurry is flowing through a porous electrode, resulting in significant pressure losses. This geometry should be optimized to realize a system with the best performance, both in terms of fluid flow and electrochemical performance. Additionally, open questions include what the efficiency of the thermal regeneration step is, and how much energy the solid/liquid separation will take.
A further challenge is to match the timescale of the discharge and thermal charge, as thermal charge appears to take considerably more time than electrochemical discharge. There are two options, batch-wise operation where thermal charge is realized independently of the discharge, or continuous operation. In batch-wise operation heat is utilized only occasionally, resulting in non-optimal utilization of heat and variable power output, although these effects could be minimized by incorporating heat storage into the system. Continuous operation would require larger volume of the liquids due to the hold-up in the heat regeneration step, but steady power output would be possible.
Comparison of the current system with recent techniques proposed in the literature in terms of efficiency and power density is given in Fig. 5. Our system has now demonstrated a theoretical efficiency of 2.2% at the average power of 75 W m−2 and maximum power density of 150 W m−2. We believe that increasing the concentration of the copper salt would allow increasing the efficiency close to 10% while also increasing the power density.
Fig. 5 Energy efficiency and power density of recent methods reported in the literature. Data and detailed evaluation of the other techniques are provided in ref. 19. D-PRO, distillation-pressure-retarded osmosis; D-RED, distillation-reverse electrodialysis; TEC, thermoelectrochemical cells; T-O, thermo-osmosis; TRCB, thermally regenerable complexation-based battery; TREC, thermally regenerative electrochemical cycle; T-RED, thermolysis-reverse electrodialysis; TRB, thermally regenerative batteries. |
Overall, this work opens the way to thermo-electrochemical electricity generation to exploit industrial waste heat and thereby provide new alternative routes of renewable energy generation.
Footnote |
† Electronic supplementary information (ESI) available: Synthesis and characterization of Cu(I) salts, viscosity of acetonitrile–propylene carbonate mixtures, electrochemistry of copper, flow battery experiments, thermal regeneration and differential scanning calorimeter measurements. See DOI: 10.1039/d0ee01590c |
This journal is © The Royal Society of Chemistry 2020 |