Journal of the Chinese Ceramic Society, Volume. 52, Issue 1, 56(2024)

Preparation and Performance Characterization of Cross-Linked Carbon Nanotubes Shaped Na2SO4·10H2O Based Composite Phase Change Energy Storage Materials

LIU Xin1... TIE Jian2, WANG Chang-an1,3 and TIE Shengnian1,* |Show fewer author(s)
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  • 1[in Chinese]
  • 2[in Chinese]
  • 3[in Chinese]
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    Introduction Mirabilite as a phase change energy storage material becomes a research hotspot because of its high latent heat, low material cost, and high thermal conductivity. However, the problems of supercooling, phase delamination, and easy leakage in the phase transition cycle seriously restrict its application. Some work indicate that stereotype-phase change materials can effectively solve these problems. In this paper, crosslinked carbon nanotubes (CL-CNTs) were prepared via the Friedel-Craft alkylation and high-temperature carbonization. The CL-CNTs shaped Na2SO4·10H2O based phase change materials were prepared via melting, and their properties were investigated. Methods Pyrene (1×10-3 mol), 1, 2-dichloroethane (20 mL), and FeCl3 (3×10-3 mol) were added into 100 mL beakers. After FeCl3 was dissolved, methyl acetal (3×10-3 mol) was added and stirred magnetically at room temperature for 5 h. At the end of the reaction, the solution was filtered, and the solid obtained was alternately rinsed with methanol, distilled water, methylene chloride, and acetone. The cleaned solid material was extracted with methanol Soxhlet for 48 h and then dried in vacuum for 7 h. The yellow powder was heated to 650 ℃ in a tube furnace with a nitrogen atmosphere for 4 h. Finally, it was cooled to room temperature and carbonized to obtain a black powder. 4.0% NaCl, 1.0% borax, and 0.1% sodium metaphosphate were added into a mixture of Na2SO4·10H2O and Na2CO3·10H2O (9:1) to prepare a phase change energy storage material of mirabilite. Afterwards, CL-CNTs were added into the phase change material with a mass fraction of 0, 1%, 2%, 3%, 4%, and 5%, respectively, and the phase change material was prepared by a melting intercalation method. These samples were ultrasonically treated for 24 h in the molten state and then stirred in a mixer for 2 h, which were labeled as PCMs-0, PCMs-1, PCMs-2, PCMs-3, PCMs-4, and PCMs-5, respectively. Results and discussion Most CL-CNTs prepared show a tubular structure, and a few carbon spheres grow on the carbon nanotubes. Hydrophilic CL-CNTs were prepared with hydroxyl and benzene ring groups on the CL-CNTs. Na2SO4·10H2O shaped phase change materials were prepared via melting intercalation at different mass fractions of carbon nanotubes (i.e., 1%, 2%, 3%, 4%, and 5%).The samples at >4% CL-CNTs show a superior stereotyped state. According to the analysis by SEM, a uniform mixture of PCMs-4 phase change material and the crystalline particles of the mirabilite phase change material exist around the carbon nanotubes, indicating that CL-CNTs shaped Na2SO4·10H2O phase change material can be prepared. The thermal conductivity of PCMs-4 is greater than that of PCMs-0, and the thermal conductivity increases with the increase of temperature at 0-20 ℃ and at 30-50 ℃. At 20 ℃, the thermal conductivity has the maximum value. At 20-30 ℃, the thermal conductivity of PCMs-0 and PCMs-4 decreases due to the heat absorption during the solid-liquid phase change of hydrated salt. Based on the DSC data of PCMs-0 and PCMs-4 before and after 500 phase transition cycles, PCMs-4 has better cyclic stability than PCMs-0. The enthalpy loss rate of melting and crystallization before and after phase transition cycles of PCMs-0 is 18% and 25%, respectively, indicating that a phase stratification occurs as phase transition cycle increases. The latent heat release of phase change decreases, and the Na2SO4·10H2O-based hydrate salt gradually fails. The melting enthalpy loss rate of sample PCMs-4 before and after the phase transformation cycle is 2%, and the crystallization enthalpy loss rate is 2.3%, indicating that, the potential heat of phase transformation is not significantly reduced as the number of phase transformation cycle is increased. It is indicated that adding CL-CNTs to PCMs-4 can effectively reduce the phase stratification and improve the cycle stability of mirabilite phase change materials. Conclusions The shaped Na2SO4·10H2O based phase change materials were prepared, thus effectively solving the problems of supercooling and phase stratification of materials. The sample PCMs-4 had a good shape. The thermal conductivity reached a maximum value of 1.008 W·m-1·K-1 at 20 ℃. There was still a high melting latent heat of 230.1 J/g and solidification latent heat of 205.2 J/g after the phase transformation cycle, indicating that the latent heat of phase transformation was not reduced as the number of phase transformation cycle was increased.

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    LIU Xin, TIE Jian, WANG Chang-an, TIE Shengnian. Preparation and Performance Characterization of Cross-Linked Carbon Nanotubes Shaped Na2SO4·10H2O Based Composite Phase Change Energy Storage Materials[J]. Journal of the Chinese Ceramic Society, 2024, 52(1): 56

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    Paper Information

    Received: May. 3, 2023

    Accepted: --

    Published Online: Jul. 30, 2024

    The Author Email: Shengnian TIE (tieshengnian@163.com)

    DOI:

    CSTR:32186.14.

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