Investigation into the Hydration Behavior of K₂CO₃ Packed Beds:An NMR Study

K2CO3 is seen as a promising heat storage material, available for applications in the domestic sector. For practical purposes, the material is hereby often employed in a packed bed containing millimeter-sized particles. To gain more insight into the hydration behavior of these packed beds, quantitative NMR measurements, capable of following the in-situ hydration behavior, are presented for the first time. It is found that hydration behavior varies significantly, depending on the specific hydration conditions that are chosen. At low airflows hydration is found to proceed via a hydration front, while higher airflows cause the hydration front to widen. Since an increase in flow rate coincided with an increase in the supplied water vapor, hydration is eventually found to proceed in a uniform manner. A comparison between TGA and NMR measurements shows that the overall packed bed hydration kinetics hereby transition to the reaction kinetics of single K2CO3 particles. Graphical Abstract: [Figure not available: see fulltext.]</p

Hydration fronts in packed particle beds of salt hydrates:Implications for heat storage

Hydration of packed beds of salt hydrate particles underpins the working principle of low temperature thermochemical energy storage (TCES). Typically, the salt hydrate particles are millimeter sized. An isothermal model for packed bed hydration is formulated, and it is shown that for millimeter sized particles hydration can be described as an advection-reaction process. Traveling wave solutions have been obtained that describe a moving hydration front. The speed of the hydration front is about five orders of magnitude slower than the air velocity in the particle bed. The width of the hydration front is under relevant TCES conditions between 10 and 100 cm. Therefore, hydration fronts will only develop in meter-sized packed beds. A constant hydration rate (and power output) is related to the existence of a traveling hydration front. Therefore, constant hydration rates and power output can only be expected for meter sized TCES reactors. Finally, the influence of temperature gradients is analyzed for the case that the front width is smaller than the bed size. The temperature lift and power output are calculated. Future steps should involve a more detailed description of temperature gradients and a quantitative analysis of finite size effects.</p

Impact of cycling on the performance of mm-sized salt hydrate particles

Potassium carbonate is shown to be a promising salt for thermochemical heat storage. For a thermochemical reactor application, the salt hydrate is manufactured in mm-sized particles. It is known that salt hydrate particles undergo swelling and cracking during cyclic testing. Therefore, in this work the influence of cycling on structural and morphological evolution is investigated and the resulting impact on the hydration performance. It is found that the incremental volume increase during cycling is independent of the density at which a particle is produced. With lower starting relative density particles are found to be stable for more cycles compared to particles produced with high starting relative densities. Powder formation at the particle surface starts as soon as the particle density is close to values reported for percolation thresholds. The morphological changes during cycling result in formation of isolated pores and a highly tortuous pore system. As a result, the effective diffusion coefficient for cycled particles is lower compared to what is predicted for as produced particles with similar porosity resulting in lower power output than expected based on porosity. The results from this work help in understanding the reasons for swelling, cracking, powder formation and decreased performance with cycling, laying the foundation for mitigating these unwanted effects.</p

Impact of cycling on the performance of mm-sized salt hydrate particles

Potassium carbonate is shown to be a promising salt for thermochemical heat storage. For a thermochemical reactor application, the salt hydrate is manufactured in mm-sized particles. It is known that salt hydrate particles undergo swelling and cracking during cyclic testing. Therefore, in this work the influence of cycling on structural and morphological evolution is investigated and the resulting impact on the hydration performance. It is found that the incremental volume increase during cycling is independent of the density at which a particle is produced. With lower starting relative density particles are found to be stable for more cycles compared to particles produced with high starting relative densities. Powder formation at the particle surface starts as soon as the particle density is close to values reported for percolation thresholds. The morphological changes during cycling result in formation of isolated pores and a highly tortuous pore system. As a result, the effective diffusion coefficient for cycled particles is lower compared to what is predicted for as produced particles with similar porosity resulting in lower power output than expected based on porosity. The results from this work help in understanding the reasons for swelling, cracking, powder formation and decreased performance with cycling, laying the foundation for mitigating these unwanted effects.</p

A scaling rule for power output of salt hydrate tablets for thermochemical energy storage

Salt hydrates are thermochemical materials capable of storing and releasing heat through reversible reaction with water vapor. In a heat battery, salt hydrate tablets of millimeter size are necessary to ensure a sufficient permeability of the packed bed. A profound understanding of the hydration process of these tablets is required to improve their kinetic performance. In this study we show that the hydration timescale of salt tablets is transport limited and that it depends primarily on the porosity and on the driving force (Δp). From gravimetric measurements done on SrBr2·6H2O and CaC2O4 we derived the intrinsic reaction and effective diffusion coefficients (k and Deff) and found that they validate a front-diffusion limited hydration hypothesis. In particular, the obtained Deff values (0.8–4.5 mm2 s−1) only depend on the tablets' porosities. Based on these parameters, we calculated the second Damköhler number (DaII) and proved that many other hydration reactions are diffusion limited. In the case of identical structures, the power output is therefore controlled only by the driving force. Its variation could be predicted by calculation of a so-called power scaling factor (Λ) for a selection of salts. This power scaling factor depends on the enthalpy (ΔH) and entropy (ΔS) of the reaction. For a temperature output of 40 °C and at 12 mbar most hydration reactions fall in the interval 0&lt;Λ&lt;30 and Λ exceeds 30 only in very few cases. This parameter establishes therefore another important constraint to the selection of the most ideal salt. Suitable strategies to circumvent the diffusion limitation will lead to the development of next generation salt hydrate tablets for thermochemical energy storage.</p

NMR Profiling of Reaction and Transport in Thin Layers:A Review

Reaction and transport processes in thin layers of between 10 and 1000 µm are important factors in determining their performance, stability and degradation. In this review, we discuss the potential of high-gradient Nuclear Magnetic Resonance (NMR) as a tool to study both reactions and transport in these layers spatially and temporally resolved. As the NMR resolution depends on gradient strength, the high spatial resolution required in submillimeter layers can only be achieved with specially designed high-gradient setups. Three different high-gradient setups exist: STRAFI (STRay FIeld), GARField (Gradient-At-Right-angles-to-Field) and MOUSE (MObile Universal Surface Explorer). The aim of this review is to provide a detailed overview of the three techniques and their ability to visualize reactions and transport processes using physical observable properties such as hydrogen density, diffusion, T1-and T2-relaxation. Finally, different examples from literature will be presented to illustrate the wide variety of applications that can be studied and the corresponding value of the techniques.</p

Boosting thermochemical performance of SrBr₂·6H₂O with a secondary salt hydrate

This work systematically investigates the effect of 9 inorganic salt hydrates on the performance of strontium bromide (SrBr2) a thermochemical material (TCM). The goal is to boost the performance of this base salt by enhancing the reaction kinetics of the SrBr2 6-1 transition or by shrinking the reaction hysteresis. The study shows that the added salts that do not share a common ion with SrBr2 (LiCl, LiF, ZnF2, ZnI2, K2CO3) give limited to no benefits. The lack of improvement is due to a side reaction between SrBr2 and the added salt leading to the formation of new salt hydrate with low hygroscopicity that does not contribute to the thermochemical reaction. The addition of hygroscopic bromide salts with divalent cations (ZnBr2, CaBr2, MnBr2) gave mixed results depending on the sample history. The most likely cause is cation exchange between bromide salts occurring during exposure to high vapour pressures which promote ionic mobility. The overall best performance was achieved with the addition of LiBr, which we attribute to its high hygroscopicity.</p

Stabilization of salt hydrates using flexible polymeric networks

The use of salt hydrates for thermochemical energy storage is associated with mechanical instabilities during cyclic hydration/dehydration. On the other hand, some salt hydrates do not suffer from these drawbacks, but manufacturing of mm-sized particles is still a challenge. In this work a one pot synthesis method is presented which results in composites using poly (dimethyl siloxane) (PDMS) as binder. Energy densities of 1.14 GJ/m3 and 0.67 GJ/m3 are achieved for a K2CO3 and CaC2O4 composite, respectively. Swelling upon hydration decreases compared to non-stabilized particles. The best K2CO3 composite shows mechanical stability for at least 35 cycles, and the average power output at 50 % conversion increases with cycling to 50–55 kW/m3 at 20 °C and 33 % relative humidity. Also, a stable CaC2O4 composite is made suitable for heat storage. The particle volume and hydration kinetics remain constant for at least 20 cycles. An average power output at 50 % conversion of 5 kW/m3 at 20 °C and 33 % relative humidity is generated. The results from this work show how a one-pot fabrication method can be used to obtain mm-sized particles with enhanced mechanical stability during cycling. Stabilization can be achieved independent of the salt hydrate solubility or material properties.</p

Accelerating the hydration reaction of potassium carbonate using organic dopants

Potassium carbonate has recently been identified as a promising candidate for thermochemical energy storage. However, as for many salt hydrates, the reaction kinetics is limited, and moreover, the hydration transition is kinetically hindered due to a metastable zone, involving limited mobility. This work aims to improve mobility by using organic potassium dopants, it shows that doping with potassium-formate and -acetate, can accelerate the hydration reaction. It has been shown that these dopants can enhance the hydration rate by two mechanisms i.e. introducing mobility due to adsorption of more water or introducing more surface area, where water adsorption can occur. This work opens up new possibilities for organic dopants to enhance the performance of salt hydrates.</p

Elucidating the Dehydration Pathways of K₂CO₃·1.5H₂O

Potassium carbonate sesquihydrate has previously been identified as a promising material for thermochemical energy storage. The hydration and cyclic behavior have been extensively studied in the literature, but detailed investigation into the different processes occurring during dehydration is lacking. In this work, a systematic investigation into the different dehydration steps is conducted. It is found that at higher temperatures, dehydration of pristine material occurs as a single process since water removal from the pristine crystals is difficult. After a single cycle, due to morphological changes, dehydration now occurs as two processes, starting at lower temperatures. The morphological changes open new pathways for water removal at the newly generated edges, corners, and steps of the crystal surface. The observations from this work may contribute to material design as they elucidate the relation between material structure and behavior.</p