Lithium Hydroxide Reaction for Low Temperature Chemical Heat Storage: Hydration and Dehydration Reaction

Li, Jun; Zeng, Tao; Kobayashi, Noriyuki; Xu, Haotai; Bai, Yu; Deng, Lisheng; He, Zhaohong; Huang, Hongyu

doi:10.3390/en12193741

Cited by 5 publications

(3 citation statements)

References 26 publications

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“…The hydration of LLZO in humid air according to eq with a constant water content as a function of temperature was recorded in the TG-DTA device between 100 and 250 °C. The temperature of dehydration of lithium hydroxide monohydrate is ∼60 °C, and therefore, its formation was not considered in reaction for the investigated temperature range. Using the chosen Ar/H 2 O mixture, LLZO carbonation can be decoupled from the hydration process. …”

Section: Results and Discussionmentioning

confidence: 99%

Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

et al. 2022

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Li-ion conducting oxides (Li 7 La 3 Zr 2 O 12 , LLZO) with a cubic garnet-type structure are among the most promising candidates to be used as solid electrolytes in all-solid-state Li batteries. However, the environmental instability of the electrolyte, induced by interaction between the material and gas molecules commonly found in air, namely, water and carbon dioxide, poses challenges for its manufacture and application. Herein, a combined experimental kinetic and thermodynamic study was performed as a function of temperature to clarify the mechanism of hydration of a garnet-type LLZO electrolyte in moist air. It was found that the kinetics of LLZO hydration is diffusion-limited and the hydration mechanism at room temperature and at higher temperatures differs. The hydration of LLZO increases up to 200 °C. Above this temperature, stagnation of water uptake is observed due to the onset of a competing dehydration process. The dehydration of LLZO takes place up to 400 °C. The partial pressure of water significantly affects the extent of hydration. Expanding this combined kinetic and thermodynamic approach to LLZO materials with a variety of chemical compositions and morphologies would allow prediction of their reactivity in a humid atmosphere and adjustment of the processing conditions accordingly to meet the requirements of technological applications.

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Section: Results and Discussionmentioning

confidence: 99%

Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

et al. 2022

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“…Several publications indicate that a metastable transition of hydration processes exist. − The cause for this metastable transition could be kinetic effects such as nucleation limitations. The equilibrium pressure of the hydration of LiOH corresponds to an RH of 16% and ∼1.5 °C dew-point temperature at 30 °C.…”

Section: Resultsmentioning

confidence: 99%

Increased Water Uptake of Li[Ni_0.6Co_0.2Mn_0.2]O₂ for Lithium-Ion Batteries in Humid Nitrogen above a Critical Gas Dew Point

Heckmann,

Madlindl,

Scharfer

et al. 2024

ACS Appl. Energy Mater.

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Moisture management in the production of Li-ion batteries is a cost-driving and performance-affecting factor in mass production. The sorption processes that govern the interaction of cell components and the atmosphere need to be understood to optimize moisture management and mitigate degradation of electrode materials, therefore enhancing overall production efficiency. The sorption and its kinetics of the cathode active material (CAM) Li[Ni 0.6 Co 0.2 Mn 0.2 ]O 2 (NMC-622) in a humid otherwise inert atmosphere is the focus of this experimental study via a sorption apparatus in perfusion mode. The CAM NMC-622 has a similar water uptake as a cathode with the same active material, showing the significance of the sorption of the CAM for the sorption behavior of the cathode. The kinetics of water sorption and the corresponding reversibility in NMC-622 at various distinct relative humidity (RH) have been observed. A significant increase in water uptake starts at a certain RH, showing that multiple sorption mechanisms occur. The reversibility of the sorption indicates that species other than hydroxides (e.g., Lihydroxide) form.

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“…For chemical heat storage materials, CaCl 2 and H 2 O were selected as the reactant and working medium, assuming the utilization of low-grade waste heat [6]. Li et al investigated the hydration and dehydration reaction of lithium hydroxide (LiOH) for low temperature heat sources [7]. Ryu et al Figure 1 shows the operating principle of a CaO/H 2 O/Ca(OH) 2 chemical heat pump.…”

Section: Introductionmentioning

confidence: 99%

Possibility of Calcium Oxide from Natural Limestone Including Impurities for Chemical Heat Pump

Lai

Imai²,

Umezu³

et al. 2020

Energies

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Improving energy recycle is an important way to save energy resources and preserve the global environment. Chemical heat pump (CHP) is a technology for saving energy, which utilizes chemical reactions to store thermal energy such as waste heat and solar heat, then release it to provide heat for heating/cooling/refrigeration. For a practical CHP, it is necessary to find cheaper and more stable supply materials. In order to evaluate the possibility of calcium oxide from natural Ofunato natural limestone including impurities, we compare Ofunato limestone with Kawara natural limestone and Garou natural limestone from Japan. These calcium oxides worked as a reactant for CaO/H2O/Ca(OH)2 CHP by repeated hydration/dehydration reaction cycle experiments in a thermogravimetric analyzer. As a result, Ofunato CaO exhibits a high hydration reaction rate after decarbonization at 1223 K for 5 h. The reactivity increased by the repeated hydration reaction although the first hydration rate was low. Furthermore, the sintering of impurities in Ofunato limestone occur easier than that in Kawara limestone with lower impurities. The impurities adhered to the surface of the CaO particle to make specific surface area of CaO particle smaller, which could inhibit hydration reaction of CaO particle. Even if Ofunato limestone contains some impurities, it can be utilized as a raw material for chemical heat pumps.

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Lithium Hydroxide Reaction for Low Temperature Chemical Heat Storage: Hydration and Dehydration Reaction

Cited by 5 publications

References 26 publications

Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

Increased Water Uptake of Li[Ni_0.6Co_0.2Mn_0.2]O₂ for Lithium-Ion Batteries in Humid Nitrogen above a Critical Gas Dew Point

Possibility of Calcium Oxide from Natural Limestone Including Impurities for Chemical Heat Pump

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Lithium Hydroxide Reaction for Low Temperature Chemical Heat Storage: Hydration and Dehydration Reaction

Cited by 5 publications

References 26 publications

Competing Effects in the Hydration Mechanism of a Garnet-Type Li7La3Zr2O12 Electrolyte

Competing Effects in the Hydration Mechanism of a Garnet-Type Li7La3Zr2O12 Electrolyte

Increased Water Uptake of Li[Ni0.6Co0.2Mn0.2]O2 for Lithium-Ion Batteries in Humid Nitrogen above a Critical Gas Dew Point

Possibility of Calcium Oxide from Natural Limestone Including Impurities for Chemical Heat Pump

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Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

Competing Effects in the Hydration Mechanism of a Garnet-Type Li₇La₃Zr₂O₁₂ Electrolyte

Increased Water Uptake of Li[Ni_0.6Co_0.2Mn_0.2]O₂ for Lithium-Ion Batteries in Humid Nitrogen above a Critical Gas Dew Point