硅酸盐学报

交联碳纳米管定型Na₂SO₄·10H₂O基相变储能材料制备及性能表征

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柳馨 ¹ , 铁健 ² , 汪长安 ¹^,³ , 铁生年 ¹

硅酸盐学报 | 研究论文 2024,52(1): 56-64

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硅酸盐学报 |研究论文 2024 , 52 (1) : 56 -64

交联碳纳米管定型Na₂SO₄·10H₂O基相变储能材料制备及性能表征

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柳馨¹, 铁健², 汪长安¹^,³, 铁生年¹

作者信息

^1．青海大学新能源光伏产业研究中心，西宁 810016

^2．青海师范大学物理与电子工程学院，西宁 810016

^3．清华大学材料科学与工程学院，北京 100084

通讯作者:

铁生年（1965—），男，教授。

作者简介:

柳馨（1993—），女，硕士，讲师。

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

Xin LIU¹, Jian TIE², Chang-an WANG¹^,³, Shengnian TIE¹

Affiliations

^1.New Energy (Photovoltaic) Industry Research Center, Qinghai University, Xining 810016, China

^2.College of Physics and Electronic Information Engineering, Qinghai Normal University, Xining 810016, China

^3.Tsinghua University, School of Materials Science and Engineering, Beijing 100084, China

Corresponding Author:

TIE Shengnian (1965-), male, Professor. E-mail: tieshengnian@163.com

LIU Xin (1993-), femal, Master, Lecturer. E-mail: qhuliuxin@163.com

出版时间: 2024-01-20 doi: 10.14062/j.issn.0454-5648.20230290

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摘要

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针对于Na₂SO₄·10H₂O相变储能材料的过冷、相分层及易泄露等问题，通过Friedel-Crafts烷基化和高温碳化的方法制备交联碳纳米管（CL-CNTs），采用熔融法制备了交联碳纳米管定型Na₂SO₄·10H₂O基相变材料并研究其性能。结果表明：大多数交联的CL-CNTs呈现管状结构，管状结构表面生长有少量碳球，交联碳纳米管上具有羟基和苯环等基团，成功制备出亲水性交联碳纳米管。分别添加质量分数为1%到5%的碳纳米管制备定型相变储能材料，当样品质量分数达到4%时（标记为样品PCMs-4），样品呈现最佳定型状态。对样品PCMs-0和样品PCMs-4的导热系数和相变潜热进行了分析，其中样品PCMs-4的导热系数显著提升，在20 ℃时导热系数最高值为1.008 W·m^-1·K^-1。芒硝相变储能材料相变循环500次后，样品PCMs-4较之样品PCMs-0表现良好的循环热稳定性，PCMs-0的相变循环前后的熔化焓损失率为18%，结晶焓损失率为25%，样品PCMs-4的相变循环前后的熔化焓损失率为2%，结晶焓损失率为2.3%，综合分析可知样品PCMs-4相变储能材料有效减少相分层现象，提高芒硝相变材料的循环稳定性。

关键词

交联碳纳米管 / 定型相变储能材料 / 芒硝相变储能材料 / 共晶盐

Abstract

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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.

Key words

cross-linked carbon nanotubes / shaped phase change energy storage materials / Na₂SO₄·10H₂O based composite phase change energy storage material / eutectic salt

引用本文

柳馨, 铁健, 汪长安, 铁生年. 交联碳纳米管定型Na₂SO₄·10H₂O基相变储能材料制备及性能表征. 硅酸盐学报, 2024 , 52 (1) : 56 -64 . DOI: 10.14062/j.issn.0454-5648.20230290

Xin LIU, Jian TIE, Chang-an WANG, Shengnian TIE. 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 -64 . DOI: 10.14062/j.issn.0454-5648.20230290

基金

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青海省自然科学基金项目(2021-ZJ-906)

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2024年第52卷第1期

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文章信息

doi: 10.14062/j.issn.0454-5648.20230290

接收时间：2023-05-03
首发时间：2026-10-22
出版时间：2024-01-20

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出版历史

收稿日期：2023-05-03
修回日期：2023-10-18

基金

青海省自然科学基金项目(2021-ZJ-906)

作者信息

^1．青海大学新能源光伏产业研究中心，西宁 810016

^2．青海师范大学物理与电子工程学院，西宁 810016

^3．清华大学材料科学与工程学院，北京 100084

通讯作者:

铁生年（1965—），男，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20230290

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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