Thermochemical Energy Storage System Research Articles

Acceleration mechanisms of Fe and Mn doping on CO2 separation of CaCO3 in calcium looping thermochemical heat storage

The doping strategy with dark metallic oxide has proven effective in improving optical absorptions and heat storage performances of calcium-based materials for the direct solar-driven thermochemical energy storage system, but the microscopic mechanisms of accelerated decomposition of CaCO3 during heat storage process are still unclear. Carbide slag as an industrial waste with low cost and high CaO content is considered as a potential calcium-based precursor for large-scale thermochemical energy storage. Herein, the novel Fe-doped and Mn-doped calcium-based materials were synthesized from carbide slag and their optical absorption properties and heat storage performances were determined in the experiment. The optimum decomposition temperatures of CaCO3 during heat storage process decreased 10.5 °C and 18.6 °C due to Fe doping and Mn doping, respectively. The acceleration mechanisms by Fe doping and Mn doping for enhancing the CO2 separation of CaCO3 in the calcination stage of the heat storage process were investigated by density functional theory (DFT) calculations. The structural parameters, partial density of states, electron differential densities and energy barriers during CO32– dissociation in heat storage process on the doped CaCO3 and undoped CaCO3 surfaces were compared to clarify the effects of Fe doping and Mn doping on the CaCO3 decomposition. The energy barriers of Fe-doped material and Mn-doped material are 1.68 eV and 1.42 eV, respectively, which are 29.4 % and 40.3 % lower than that of undoped material. This work helps to understand the microscopic mechanisms of accelerated CaCO3 decomposition by Fe and Mn during heat storage process.

Methanol-based thermochemical energy storage (TCES) for district heating networks

With increasing volatility in natural gas markets and the need for residential heat, research for alternative thermal systems based on green hydrogen-based fuels is necessary. Massive implementation of hydrogen in the current fleet presents a challenge for the decarbonisation of conventional thermal processes. This paper presents the integration of green methanol from a seasonal thermochemical energy storage system (TCES) coupled with district heating networks (DHN). It allows for a solar-based storage and low-temperature heat generation from the exothermic discharge reaction. The system uses concentrated solar thermal energy to decompose methanol into syngas at moderate temperatures (<315 °C), reducing GHG emissions from combustion to meet residential heat. Its potential is assessed through an analysis of 458 rural municipalities in Spain, achieving a substitution of 3.1 % of the natural gas demand. The system allows the production of green fuels from syngas using an open-loop approach, offering new market pathways in primary sector. In a closed-loop configuration, roundtrip efficiencies exceeding 60 % and chemical conversion efficiencies exceeding 70 % are reached, resulting in a global efficiency of 12 % for the DHN and methanol-TCES. The results show a levelized cost of stored energy highly competitive with other storage systems (<200€/MWh), given its simplicity.

Modeling CO2 Adsorption in a Thin Discrete Packing.

Local dynamics of CO2 adsorption in a discrete packing contained in a thin tube was assessed by 3D modeling. Thin tube packed bed adsorbers are currently used over tube structures in thermochemical energy storage systems and atmospheric revitalization of confined spaces. Driven by the interplay between key factors such as the exothermicity and the fluid flow, the advective transport was found less effective than the diffusive one on the breakthrough trends of CO2 which displayed significant concentration gradients at both inter- and intraparticle scales. The lack of angular symmetry inside the particles by the reduction in resistance to mass transfer in the area of solid particles exposed to high velocities led to greater convective transports from the bulk of the gaseous phase to the pores. The result of the modeling agreed with the experimental data obtained at the exit of the adsorber, helping reduction in reliance on the empirical dispersion models used in the one-dimensional modeling.

Heat storage and release characteristics of a prototype CaCO3/CaO thermochemical energy storage system based on a novel fluidized bed solar reactor

CaCO3/CaO thermochemical energy storage (TCES) system has a high heat storage density (1780 kJ/kg) along with high heat storage and release temperature (650–850 °C), which can be applied to concentrated solar power (CSP) technology utilizing CO2 Brayton cycles to improve power generation efficiency. There are several problems to be urgently resolved in current CaCO3/CaO solar calciners, such as poor heat and mass transfer and low thermochemical efficiency. This paper proposed a prototype CaCO3/CaO TCES system based on a novel fluidized bed solar reactor, which has a serrated arc surface in alignment with the direction of the incident solar rays to receive concentrated solar energy. The natural limestone particles were used as the reactive particles. The effects of operating modes (intermittent/continuous), initial mass of reactive particles, and initial carbonation temperature Tcar,initial on the heat storage and release characteristics of the TCES system were experimentally explored. During the carbonation reaction stage, the effective carbonation degrees in the continuous mode were generally higher than in the intermittent mode under the experimental conditions and declined at a slower rate. The reactive particles were recovered from the reactor for microstructural characterization after completing the experiments, high-temperature particle agglomeration and pore structure clogging were directly responsible for the decrease of the effective carbonation degree. In the continuous mode, the average thermochemical and total thermal efficiencies of 24.7 % and 53.5 % were obtained in the 1st calcination reaction, respectively, which represents significant advantages over other CaCO3/CaO solar calciners. The novel fluidized bed reactor demonstrated excellent fluidization in the experiments and did not exhibit mechanical deformation after multiple experiments under non-uniform concentrated radiation provided by an 84 kWe high-flux solar simulator. Overall, this paper provides a successful gas-solid reactor design to be coupled with CSP technology.

Development of a Two‐Stage Hydrogen‐Based Thermochemical Energy Storage System

Both energy conservation and the use of renewable resources are necessary due to the global increase in energy demand. A useful technique for energy storage, when renewable energy sources are available, is a thermochemical energy storage system that relies on the interaction of gases with solids. From this vantage point, hydrogen offers a sustainable and regenerative response to this pressing issue. In line with that, herein, the operation of a novel two‐stage hydrogen‐based thermochemical energy storage system (TS‐H‐TCES) is proposed to attain a higher energy density and is analyzed with the help of the thermodynamic cycle. The proposed system operates at 298, 373, 403, and 423 K as atmospheric temperature (Tatm), waste heat input temperature (Tm), storage temperature (Ts), and upgraded/enhanced heat output temperature (Th), respectively. For the given operating temperature, the thermodynamic performance of TS‐H‐TCES is evaluated using experimentally measured pressure–concentration isotherms of LaNi4.7Al0.3, LaNi4.6Al0.4, and MmNi4.6Al0.4. The maximum coefficient of performance, second law efficiency (ηII), and thermal energy storage density are found to be 0.67, 0.70, and 220.98 kJ kg−1, respectively. The impact of operating temperatures on system performance is also investigated, which is important in choosing the best temperature range for a certain application.

Hybrid Biomass Fast Pyrolysis Process and Solar Thermochemical Energy Storage System, Investigation and Process Development

Hybrid Biomass Fast Pyrolysis Process and Solar Thermochemical Energy Storage System, Investigation and Process Development

Impacts, Barriers, and Future Prospective of Metal Hydride‐Based Thermochemical Energy Storage System for High‐Temperature Applications: A Comprehensive Review

This article summarizes various thermochemical energy storage (TCES) systems based on their thermochemical properties, operating temperature, and storage density. Metal hydride (MH)‐based TCES is a potential energy storage system due to its higher energy storage density (&gt;100 kWh m−3), higher operating temperature (&gt;500 °C), relatively better reaction kinetics, and minimal or no energy losses (theoretically). MHs operate at various temperature ranges, and based on temperature, they are classified as low‐temperature MH and high‐temperature MH. This article highlights potential metal alloys operating above 300 °C, with an energy storage density of more than 100 kWh m−3, suitable for concentrated solar thermal power generation and industrial process heating applications. Magnesium (Mg) alloy‐based hydrides have shown good cyclic stability (up to 1500 cycles) at a temperature above 400 °C. The lower cost of material, higher energy storage capacity, better reversibility, and higher thermal stability of Mg‐based alloys have been explored in several small‐scale experimental investigations. The thermal energy storage (TES) efficiency of MH‐based TCES systems is reported ≈ 90%, which is significantly higher than sensible and latent TES systems. Challenges associated with MH‐based TES systems, such as heat transfer enhancement, cost reduction, and chemical and thermal stability, have been discussed in detail.

Investigation of water adsorption characteristics of MgCl2 salt hydrates for thermal energy storage: Roles of hydrogen bond networks and hydration degrees

Thermochemical energy storage holds great promise in solar energy applications, and MgCl2 hydrate salt is considered a promising material for medium and low-temperature thermochemical energy storage. Understanding the adsorption behavior of water molecules in MgCl2 hydrate salts and uncovering the underlying mechanisms are crucial for designing efficient thermochemical energy storage systems. This paper investigated the water adsorption characteristics of MgCl2 hydrate salt utilizing the Grand Canonical Monte Carlo (GCMC) method and captured the adsorption isotherm and concentration distributions of water molecules in MgCl2 hydrate salts pores at various temperatures. The results demonstrate that at low temperatures, particularly when the pore size is small (D < 0.8 nm), the interconnected hydrogen bond network plays a crucial role in enhancing the water adsorption capacity of pure MgCl2. As the temperature increases, the influence of hydrogen bond networks diminishes, and their impact on the water adsorption capacity becomes negligible. Moreover, the hydration degrees of MgCl2 salt significantly influence their water adsorption capacity. MgCl2·6H2O exhibits the best water-uptake performance, followed by MgCl2·4H2O, while MgCl2·2H2O displays the worst water-uptake performance. These findings shed light on the adsorption behavior of water molecules in MgCl2 hydrate salt and offer valuable insights into the design and optimization of efficient thermochemical energy storage systems. Such knowledge is essential for advancing the utilization of thermochemical energy storage in solar energy applications.

Incorporation of CaZrO3 into calcium-based heat carriers for efficient solar thermochemical energy storage

Calcium-based materials (CaCO3/CaO) have shown significant potential for use in thermochemical energy storage systems for concentrated solar power generation due to their low-cost, high-energy storage efficiency, and operational temperature range. However, the energy storage performance of calcium-based heat carriers degrades rapidly over cycles due to high-temperature sintering, limiting practical applications. In this study, we incorporated Zr into CaO using both heat-drying and freeze-drying methods, forming CaZrO3 as a physical barrier to prevent agglomeration and sintering of calcium particles at elevated temperatures. Experimental results demonstrated that Zr incorporation markedly improved cyclic energy storage stability, particularly for heat carriers derived from freeze-drying. Cao incorporated with 10 % CaZrO3 (FD-Zr10) showed a high energy storage density of 2161.75 kJ/kg over ten storage/release cycles, which was 25.89 % higher than that of pure CaO sample. Even over an extended operation of 30 cycles, FD-Zr10 still possessed the high energy storage density of 1939.76 kJ/kg. CO2-containing harsh storage conditions caused more sintering for the heat carriers, thus resulting in the performance reduction, but FD-Zr10 performed much better than other samples in resisting sintering. Various characterization analyses were conducted to investigate the reasons for the samples' cyclic stability. It was discovered that freeze-drying incorporation generated a dendritic surface with a more abundant pore structure, and the incorporated CaZrO3 functioned as a metal skeleton to mitigate high-temperature sintering.

Experimental investigation of a thermochemical energy storage system based on MgSO4-silica gel for building heating: adsorption/desorption performance testing and system optimization

To address the gap between the thermochemical energy storage (TCES) performance of MgSO4-porous matrix composites in small-scale prototypes and their practical application, a TCES system with an output power of 50 kW was designed and constructed to investigate the feasibility of using MgSO4-silica gel composites in large-scale storage systems for long-term heating applications. Thirty consecutive sets of experiments were performed on both the reactor and the system. Aiming at energy storage system for space heating and hot water supply, four parameters (energy consumption, energy storage density, energy storage efficiency, and specific energy storage capacity) were investigated as the key performance evaluation indicators. The experiment results indicated the energy consumption of the heater and humidifier account for approximately 80 % of total energy consumption. The findings also demonstrated the potential to increase the ESD from 0.47 GJ/m3 to 0.76 GJ/m3 by exploiting the heat generated from the additional circulation water in the reactor’s shell. The optimized system achieved an efficiency increase of ∼ 11 %, reaching over 60 %, and the specific energy storage capacity can reach up to 198.15 Wh/kg. In addition, the supply water temperature can stay above 50 °C for roughly 4 h, with a maximum value from 70.1 °C to 82.4 °C, and the water temperature lift was found to as high as 57.4 °C. Additionally, the adsorption heat accounted for approximately 44 % of the total energy storage.

Performance study of a thermochemical energy storage reactor embedded with a microchannel tube heat exchanger for water heating

Thermochemical energy storage (TCES) provides a promising solution to addressing the mismatch between solar thermal production and heating demands in buildings. However, existing air-based open TCES systems face practical challenges in integrating with central water heating systems and controlling the supply temperature. To overcome these limitations, a novel water-based TCES-HEX-HRU system is proposed in this study, which integrates a water-to-air microchannel tube heat exchanger (HEX) and an air-to-air heat recovery unit (HRU). A comprehensive evaluation of the TCES-HEX-HRU system is conducted numerically using a COMSOL model, including a comparative assessment for different TCES system configurations. The results demonstrate that the TCES-HEX-HRU system achieves an overall thermal efficiency of 82.35 %, marking a substantial 69 percentage points improvement over the TCES-HEX system. Although slightly lower than the typical air-based TCES system without HEX and HRU by 15.44 percentage points, the TCES-HEX-HRU system can be a practically promising and viable choice for applications in central heating systems. Numerical investigations indicate that the thermal performance of the system is influenced by the inlet conditions of airflow and waterflow. Moreover, increasing the number of water channels in the HEX of the TCES-HEX-HRU system enhances heat transfer but reduces the amount of heat released by TCES composite materials, resulting in a maximum overall thermal efficiency of 92.09 % with 35 channels and a peak outlet water temperature of 33.67 °C at with 30 channels. However, further increases in the number of channels lead to a decline in overall thermal efficiency and outlet water temperature. Changes in the width of water channels in the HEX have a minor impact on the highest outlet water temperature and overall thermal efficiency, while affecting the volume of the TCES composite materials.

A flexible methanol-to-methane thermochemical energy storage system (TCES) for gas turbine (GT) power production

This study introduces an innovative solution to address the challenges arising from the volatile natural gas market and the growing integration of renewable energy sources within the industrial sector. The research strives to confront this challenge by including renewable methanol (CH3OH) and converting it into methane (CH4), with an intermediate step involving synthesis gas (CO/H2) by using concentrating solar power. This approach provides a sustainable and adaptable solution to reduce dependence on natural gas. The process entails a methanol decomposition reaction at moderate temperatures (<350 °C). Subsequently, the synthesis gas is compressed to 40 bar, stored, and discharged through a methanation process that can be conducted at high temperatures (>500 °C). The resulting methane is used as fuel for gas turbines and can also serve as feedstock in the chemical industry. The simulations were conducted in ASPEN HYSYS and yielded overall system efficiencies exceeding 29% and roundtrip efficiencies of 44%. Through techno-economic optimisation of the reaction conditions, competitive levelized fuel costs (LCOF) of €172/MWh and future LCOE values of €145/MWh were achieved. These findings present an innovative strategy for integrating gas turbine cycles and additional conversion pathways for green methanol.

Exploring a novel tubular-type modular reactor for solar-driven thermochemical energy storage

Thermochemical energy storage (TCES) has gained extensive attention as a potential solution to address the mismatch between solar thermal energy production and demand. In this study, a novel tubular-type modular TCES reactor is introduced. COMSOL modelling of the system is developed and experimentally validated using a laboratory-scale TCES system. Both types of reactors show similar temperature increases, intensifying with higher inlet relative humidity. Their maximum temperature lifts exceeding 26 °C at 90 % RH. Tubular designs offer better axial flexural strength and dispersion of TCES composite materials compared to plate structures. This property of tubular structures beneficial reducing bed thickness and pressure drop and enhancing equivalent thermal efficiency. Simulations show tubular-type modular reactors reduce pressure drop by 4–5 times compared to plate-type modular reactors, increasing equivalent thermal efficiency by nearly 7% points. Increasing the number of reactor beds and inner tube radius improves equivalent thermal efficiency due to reduced bed thickness and pressure drop. As the number of matrix rows and columns in the reactor bed increases from 2 to 10, bed thickness decreases from 0.058 m to 0.012 m, reducing pressure drop from 845.53 Pa to 38 Pa and increasing equivalent thermal efficiency from 78.82 % to 96.61 %.

Experimental investigation on thermochemical heat storage using CaO/CaCO3 in a cyclone reactor

In this study, a cyclone reactor with a secondary flow effect was applied to the CaCO3/CaO thermochemical energy storage system. An experimental platform for thermochemical energy storage with a cyclone reactor was built. A cold-state experiment was performed to study the feeding and conveying performance of CaCO3 and CaO particles. The experimental results reveal that the average feeding speeds of CaCO3 and CaO were 25.7–29.6 g/min and 3.5–11.0 g/min, respectively. The effects of different heating temperatures (750–950 °C) and inlet air velocities (4–14 m/s) on the reaction performance were studied. The results indicate that CaCO3 decomposes above 750 °C. The reaction degree increased with increased reaction temperature, and the peak value of the outlet CO2 concentration peaked (4.72 %) when the heating temperature was 950 °C, where the reaction degrees under different air velocities were similar. In addition, the inlet air velocity and the outlet relative humidity decreased owing to the formation of CO2 and CaO. In the energy release experiment, it was difficult to smoothly feed CaO into the cyclone reactor for synthesis owing to its characteristics, and no obvious change in the CO2 concentration was observed at the outlet. The energy storage reaction and flow characteristics were experimentally studied to provide a reference for the design of thermochemical energy storage reactors.

A cascaded thermochemical energy storage system enabling performance enhancement of concentrated solar power plants

Calcium looping (CaL) thermochemical energy storage (TCES) exhibits promising potential for application in concentrated solar power (CSP) plants. However, the CSP-CaL integrating system encounters challenges related to elevated heat loss and diminished power generation efficiency. Herein, for the sake of a more rational heat management and enhanced energy utilization, we propose a cascaded energy storage and utilization strategy. Accordingly, a cascaded TCES system model consisting of Calcium looping and Magnesium looping (MgL)-MgCO3/MgO thermochemical cycle subsystem is developed. The energy analysis and exergy analysis results show that the solar power efficiency and exergy efficiency of the considered system are 41.7% of 44.7%, which are 2.6% and 2.8% higher than the single CaL energy storage CSP system, respectively, demonstrating the superiority of the proposed strategy and system for CSP application. Furthermore, the operation strategy of the system under off-design conditions is proposed by considering the real solar irradiation, and the yearly overall solar power efficiency is 39.2%. The economic analysis of the proposed system indicates that the levelized cost of electricity ranges from 179–156 $/MWh for different plant sizes and is superior in large-scale CSP plants. The cascaded energy storage and utilization strategy of thermochemical cycles with different working temperatures provides better dispatchability to meet the different thermal energy demands.

Experimental investigation of CaCO3/CaO reaction pair in a fixed bed reactor for CSP application

CaCO3/CaO thermochemical energy storage (TCES) system has been widely studied on laboratory scale for its potential in concentrated solar power (CSP) plants. However, there is still need for the large-scale experiments based on which a detailed analysis can be obtained to improve this system for real-time applications. In this study, we developed a packed bed reactor capable of operating at high temperature and pressure providing the carbonation and decarbonation reactions of CaCO3/CaO reaction pair. The heat storage process is studied with the aspect of different decarbonation temperatures and different sample sizes (amount of sample in grams) placed in the reactor. Furthermore, we compared the heat storage performance of pure and composite samples. The heat release process is performed by varying the concentration of CO2 and the sample size of the loaded material. The results showed that the heat storage rate and efficiency improve by increasing the temperature of the decarbonation, implying that this reaction must be carried out above 925 °C for better performance. The heat is released smoothly and at a good rate when the concentration of CO2 is high in the reactor. Also, carbonation reaction (heat release process) depicts that CaCO3/CaO TCES system has a great potential to be used as a heat pump and is capable of upgrading the temperature of the released heat from lower to higher value.

A scaling procedure for designing thermochemical energy storage system

Thermochemical energy storage (TCES) technology offers a promising avenue for achieving prolonged thermal energy storage through reversible gas-solid reactions. In the present work, a scaling analysis approach is presented to derive the relevant length and time scales for heat charging and discharging processes occurring inside a porous reactor bed of a TCES system. The processes involved are vapour flow through the porous bed, coupled heat and mass transfer, and heat and mass absorption/release in conjunction with reaction kinetics, for the case of water vapour and potassium carbonate as the gas-solid pair. This analysis employs an order-of-magnitude approach on mass, momentum, and energy conservation equations. The scaling analysis of continuity and momentum equations derives the scale for critical vapour penetration depth. It signifies the length scale beyond which pressure drop becomes significant, leading to a significant reduction in the reaction rate. Similarly, a critical thermal diffusion length scale is derived from the scaling analysis of the energy equation. This scale signifies the length beyond which the reaction rate drops significantly due to limited thermal diffusion. The derived scales characterize the performance of the energy storage bed and help in determining bed dimensions for an effective flow of heat and water vapour through the bed.

Energetic and exergetic performance analyses of mobile thermochemical energy storage system employing industrial waste heat

With an expanding urban population and increasing energy consumption, the demand for air conditioning is projected to reach 45 % of total energy demand by 2050. Based on projections, there will be a massive demand for air conditioning purposes, and energy consumption for air conditioning will also increase. Mobile thermo-chemical energy storage (MTES) offers an alternative by utilizing waste heat from power plants for heating and cooling via sorption heat storage. MTES proves advantageous due to its portability and phase change material transport capability. This study focuses on an MTES system applied in District Energy Networks (DEN) for cooling application. An analytical model has been developed to evaluate the system performance by considering energy efficiency ratio, round-trip efficiency, coefficient of performance, energetic efficiency, exergy destruction rate, and exergetic coefficient of performance as the performance parameters. Results show that an average round-trip efficiency of 53 %, maximum COP of 1.74, and exergy efficiency of 46.7 % is obtained for the year 2022. Notably, the MTES truck achieves a 50 % exergy efficiency. This study contributes insights into efficient waste heat utilization for sustainable cooling solutions.

A perspective on high‐temperature heat storage using liquid metal as heat transfer fluid

AbstractEnergy storage systems are essential to secure a reliable electricity and heat supply in an energy system with high shares of fluctuating renewable energy sources. Thermal energy storage systems offer the possibility to store energy in the form of heat relatively simply and at low cost. In concentrating solar power systems, for instance, molten salt‐based thermal storage systems already enable a 24/7 electricity generation. The use of liquid metals as heat transfer fluids in thermal energy storage systems enables high heat transfer rates and a large operating temperature range (100°C to &gt;700°C, depending on the liquid metal). Hence, different heat storage solutions have been proposed in the literature, which are summarized in this perspective. Based on these, future technical advances are suggested such as reducing the liquid metal share in the heat storage, using waste material as storage medium or using liquid metal as heat transfer fluids not only in sensible, but in latent or thermochemical energy storage systems. The use of waste material in a packed bed configuration with 5% porosity, for example, can bring down the storage material costs to 2%–3% of the costs of a liquid metal‐only storage system. Furthermore, future application fields beyond concentrating solar power are proposed: supply of industrial process heat, waste heat integration and power‐to‐heat‐to‐power processes.

Experimental investigations to measure thermodynamic properties of MWCNT/MnCl2 composite material for thermochemical energy storage system

Experimental investigations to measure thermodynamic properties of MWCNT/MnCl2 composite material for thermochemical energy storage system