Halloysite-based aerogels for efficient encapsulation of phase change materials with excellent solar energy storage and retrieval performance

Abstract

Developing low-cost composite phase change materials with good shape stability, excellent mechanical strength, high thermal conductivity, large encapsulation ratio, strong light absorption and eminent solar-to-thermal conversion capacity is of great challenge to solve the scaling-up related issues of organic solid–liquid phase change materials during the utilization of solar energy. In this work, halloysite/poly(vinyl alcohol) and halloysite/poly(vinyl alcohol)/reduced graphene oxide aerogels with rich three-dimensional honeycomb structure were prepared by a freezing and freeze-drying method, which can significantly promote the encapsulation ratio of lauric acid in the pores of both aerogels and halloysite nanotube. Halloysite nanotube with high aspect ratio can improve the compressive strength of the aerogels and shape stability of the composite phase change materials, while reduced graphene oxide can reinforce the thermal conductivity and light absorption ability. After encapsulation of lauric acid, the halloysite/poly(vinyl alcohol) 9:1 and halloysite/poly(vinyl alcohol)/reduced graphene oxide 9:1 phase change composites demonstrate extraordinarily high latent heat of 195.4 J/g and 197.0 J/g, respectively, leading to high encapsulation ratios of 97.2 % and 98.1 % respectively, accompanied by good chemical and thermal stability over 300 thermal cycles. The thermal conductivity of lauric acid@halloysite/poly(vinyl alcohol)/reduced graphene oxide is remarkably elevated to 0.343 W/m∙K, exceeding 39.4 % that of pure lauric acid (0.246 W/m∙K). Besides, the lauric acid@halloysite/poly(vinyl alcohol)/reduced graphene oxide realizes a conspicuous solar-to-thermal conversion with solar absorption capacity of 95 % throughout the full spectrum of solar light. The marvelous improvement in the solar-to-thermal conversion efficiency can be attributed to thermally conductive interconnected network of halloysite nanotube and reduced graphene oxide. Thus, lauric acid@halloysite/poly(vinyl alcohol)/reduced graphene oxide and lauric acid@halloysite/poly(vinyl alcohol) are tentatively used in the catalytic hydrolysis of ammonia borane, and they can efficiently harvest, convert and store solar energy in the form of thermal energy and release it for the reaction, which obviously accelerates the extent of reaction with turnover frequency increasing from 29.50 (molH2/molcatalyst·min) at 25 °C to 59.18 and 41.74 (molH2/molcatalyst·min) under the heating of solar energy stored lauric acid@halloysite/poly(vinyl alcohol)/reduced graphene oxide and lauric acid@halloysite/poly(vinyl alcohol), respectively. This work paves a way for fabricating halloysite-based aerogel and composite phase change materials for thermal/solar energy saving application.