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Phase-Change Materials and Biochar: Some New Composite Materials in

Recent Literature

Article · May 2021

DOI: 10.5281/zenodo.4767507

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Phase-Change Materials and Biochar: Some New Com-
posite Materials in Recent Literature

Amelia Carolina Sparavigna

Department of Applied Science and Technology, Politecnico di Torino, Torino, Italy
Email: [email protected]

Torino 17/05/2021; Zenodo - DOI: 10.5281/zenodo.4767507

Abstract
A phase change material (PCM) is a substance absorbing and releasing energy at phase
transition. The substance is therefore useful for heating and cooling applications. Here we
review the recent literature about the use of biochar and PCMs for composite materials, to
obtain phase change composites (PCCs).

Keywords: PCM, PCC, Biochar, Composite Materials, Biomass-Based Porous Carbon, Phase
Change Composites, Thermal Management, Latent Heat Storage Biocomposite, LHSBC.
Subject Areas: Materials Science.

1. Introduction
A phase change material, PCM, is a substance absorbing and releasing energy at phase transi-
tion. The substance is therefore useful for heating and cooling applications. Generally the tran-
sition is be between solid and liquid phases. However, phase transition may also be considered
between crystalline phase structures, which have different energy states. An example of PCM
based on fusion is the ice (heat of fusion, 333.55 J/g). Water/ice is therefore a well-known
phase change material, which can be used to store winter cold to cool buildings in summer [1].
By melting and solidifying at the given phase change temperature, a phase change material is
able to store or release energy. In the case of water, heat is absorbed or released when the mate-
rial changes from solid to liquid and vice versa. Therefore, PCM are latent heat storage (LHS)
materials.
In the past, water was considered the main, or let us tell, the only available PCM. In the last few
decades, several substances, such as hydrocarbons and paraffin, have been adapted to have fur -
ther applications to a wide temperature range. For instance, PCMs are used for Ultra Low Tem -

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 PCMs and Biochar A.C. Sparavigna

perature (ULT) freezers, so that the World Health Organization, WHO, is mentioning them in
its logistic guidance for vaccination [2]. In fact, PCMs are mainly used in ULT logistics, where
thermal energy storage is fundamental. This logistics takes advantage of the fast progress in
materials science, which is providing new substances for PCMs, and also of the technologies
which are receiving support from these materials.
Actually, several researched are aimed at enhancing PCM's performance. The main drive of
these researches is mainly the huge potential market for building heating and cooling [3]. For
buildings, other materials are under investigation, such as biochar, for CO 2 absorption [4]. Here,
let us consider literature about the use of biochar in PCMs. Let us remember that biochar is
charcoal produced by pyrolysis of biomass in the absence of oxygen, which has its main appli-
cation in soil management [5].
To see the microscopic structure of biochar, see please [6] (an example in given in the Figure
1). It is the biochar structure which is interesting for the encapsulation of phase-change sub -
stances.

Figure 1. From a FESEM image of a biochar sample, a 3D mesh can be obtained [6].

2. Literature
Objective of the research proposed in [7] was the characterization of a latent heat storage bio-
composite (LHSBC), based on biochar, which can be used as a novel material useful for latent
heat storage insulation. "In particular, this paper [7] analyzed the chemical stability, latent heat
storage performance, thermal conductivity, and thermal stability of LHSBCs". "As a result, the
LHSBCs showed a maximum latent heat storage capacity of 74.6 J/g and a low thermal conduc-
tivity of 0.030 W/mK at the maximum, confirming that LHSBCs have a high latent heat storage

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 PCMs and Biochar A.C. Sparavigna

capacity and thermal insulation performance".

As observed in [8], PCMs are a promising solution in the field of thermal energy storage.
"However, the low thermal conductivity and form stability over cycles of charging and dis-
charging of PCM are challenges to address". In [8], the authors are proposing a study concern-
ing a novel and low cost biochar-PCM hybrid latent heat energy storage material. According to
[8], the new composite material possesses superior thermal conductivity over pure PCM, "as
well as better stability due to the high carbon content and porosity of the developed biochar".
"The heat of fusion is calculated to be 179.4 J/g. The thermal conductivity of the PCM is en-
hanced up to 13.82 times with the addition of water hyacinth biochar as a supporting matrix.
The addition of aluminum metal powder further increases the thermal conductivity by 17.27
times higher than that of PCM alone" [8]. PCM is based on paraffin wax.
"To obtain high thermal performance composite phase change materials (PCMs), various other
supporting materials have been utilized to encapsulate organic PCMs" [9]. In the study pro -
posed in Ref. [9], four carbon materials (biochar, activated carbon, carbon nanotubes, and ex-
panded graphite) were introduced to support heptadecane. "The latent heat storage capacity
ranged from 53.3 J/g to 195.9 J/g. It was observed that the intermolecular interactions between
the PCM and supporting materials and the surface functionality of the encapsulating agents play
a leading role in the thermal performance of the composite PCMs. Furthermore, pore structures
such as specific surface area, total pore volume, and pore size distribution have a combined ef -
fect on the crystallinity of heptadecane in the composite PCMs" [9].
Data about four composite PCMs (carbon nanotube, CNT; expanded graphite, EG; biochar, BC;
activated carbon, AC; heptadecane, HD) are the following: HD/BC, HD/AC, HD/CNTs, and
HD/EG exhibited latent heat capacities of 53.3 J/g, 85.4 J/g, 163.3 J/g, and 195.9 J/g, respec-
tively [9]. All the composite PCMs exhibited a decrease in heat enthalpy when compared with
the pure PCM. "This is due to the pore structure of the supporting materials that restrict the nor-
mal movement of the HD chain" [9].
However, biochar is an environmentally friendly material. In [10], a composite material is stud-
ied, obtained by means of biochar derived from bamboo, multiwalled carbon nanotubes and liq-
uid n-dodecane for a new energy storage material. "The hybrid material provides favorable
morphological and interconnected framework structures for PCM encapsulation and energy
storage capacity in the composite PCMs. The PCM loading capacity of biochar, biochar-CNT,
and CNTs reached 51.3%, 70.6%, and 83.2% with latent heat of 93.4 ± 1.1, 127.3 ± 1.1, and
152.3 ± 1.3 J/g, respectively". "The obtained composite PCMs exhibited outstanding shape and
thermal stabilities and chemical compatibilities". The synthesis strategy proposed in [10] "is ex-
pected to create a platform for fabricating biochar-based multifunctional PCMs for desired ap-
plications".
Biochar, in general recognized as an environmentally friendly product, is consider for being
used in buildings too. "The spread of low-energy buildings increases the impact of embodied
energy in the life cycle of buildings. Moreover, environmental concerns push for the use of
biobased materials". Ref. [11] summarizes the literature on biobased phase change materials
(PCMs). "When implemented in testing huts, these biobased PCMs are able to perform as ex-
pected, decreasing the energy needed for cooling buildings" [11].
Ref. [12] tells that "Biochars have been suggested as cheap, eco-friendly, and commercially
available media for adsorbing various organic and inorganic target compounds". Further inves-

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 PCMs and Biochar A.C. Sparavigna

tigations are necessary for the "design of shape and thermally stable organic phase-change ma-
terials (PCMs)". In [12], composite PCMs based on standard biochars and organic PCMs (1-do-
decanol and n-dodecane) have been developed. "Among these biochar-derived composites, one
from oilseed rape exhibited high heating enthalpy of 73.7 and 90.5 kJ/kg for 1-dodecanol and n-
dodecane, respectively". "The synthesis of 1-dodecanol-based composite appeared to be influ-
enced by specific surface areas of the biochars and intermolecular interactions owing to the
highly sensitive hydroxyl group of the organic PCM".
Biochar belongs to the family of the bio-carbons. Some of them, obtained from walnut shell
(WS) as "lightweight, porous, low-cost and environmental friendly supporting matrix", have
been studied too [13]. "The produced walnut shell carbon (WSC) and activated WSC (AWSC)
were evaluated as novel shape stabilizer and thermal conductivity enhancer for methyl palmi -
tate (MP) preferred as phase change materials (PCM) for thermal controlling applications in
buildings". "The DSC measurements indicated that the melting temperatures of WSC/MP and
AWSC/MP were 26.27 and 26.65°C, and corresponding fusion enthalpies were 108.3 and 138.1
J/g, respectively". "All findings revealed that the leak-free composite PCMs can be used as ad-
mixture in the manufacture of lightweight, cost-effective, eco-friendly and energy-saving con-
struction elements utilized for solar thermal controlling of buildings" [13].
In [14], we find stressed that the practical application requires a shape-stable phase change
composite (PCC). "A shape-stable PCC was fabricated by incorporating poly(ethylene glycol)
(PEG) with biomass-based porous carbon that was produced via freeze-drying and carboniza-
tion using a low-cost and environmentally friendly fresh towel gourd. ... The shape-stable PCC
demonstrated excellent thermal reliability and a high melting latent heat of ∼164.3 J/g". The
study in [14], as told by the authors, "provided an innovative strategy for the design and devel-
opment of shape-stable PCCs for great potential in heat-insulating protective textiles, solar ther-
mal energy storage, energy-saving buildings, and infrared stealth of military targets".
Also in [15], we can find a new form-stable composite phase change material (PEG/ASB) com-
posed of almond shell biochar (ASB) and polyethylene glycol (PEG). "The supporting material
ASB, which was cost effective, environmentally friendly, renewable and rich in appropriate
pore structures, was produced from agricultural residues of almond shells by a simple pyrolysis
method, and it was firstly used as the matrix of PEG". "The thermogravimetric analysis (TGA)
and thermal cycle tests demonstrated that PEG/ASB possessed favorable thermal stability. The
differential scanning calorimetry (DSC) curves demonstrated that the capacities for latent heat
storage of PEG/ASB were enhanced with increasing PEG weight percentage. ... All the study
results indicated that PEG/ASB had favorable phase change properties, which could be used for
thermal energy storage" [15].
Pinecone biochar is used in [16]. A "form-stable phase change material (PA/PB) was fabricated
using pinecone biochar (PB) as the supporting material of palmitic acid (PA)". Analyses
demonstrated "that the PA was physically absorbed by the PB and the crystal structure of the
PA was not destroyed. The results of DSC showed that the fusing and crystallization points of
the form-stable phase change material with the maximum content of PA (PA/PB-4) were 59.25
°C and 59.13 °C, and its fusing and freezing latent heat were 84.74 kJ/kg and 83.81 kJ/kg, re-
spectively. ... Thus, the study results indicated that the PA/PB-4 had great potential for thermal
energy storage applications" [16].

4
 PCMs and Biochar A.C. Sparavigna

Ref. [17] is studying infiltration properties of PCMs in biochar. "Three different n-alkanes
(such as dodecane, tetradecane, and octadecane) are used as PCMs. The PCMs were infiltrated
in the biochar network via the vacuum impregnation method. Among the biochar/n-alkane com-
posites, one from octadecane exhibited a high latent heat storage capacity of 91.5 kJ/kg, 15.7 %
and 25.9 % higher than that of dodecane and tetradecane-based composites, respectively. The
molecular length of the PCMs and intermolecular interaction between the functional groups
play an imperative role. The infiltration ratio of PCM in the biochar reached 50.1 % with im -
proved thermal stability and chemical compatibility".
As previously told, a very important application of PCMs is in the enhancement of the energy
efficiency of buildings. The base is in the integration of common construction materials with la-
tent heat storage biocomposites [18]. These composites are prepared "by vacuum impregnating
the phase change material into biochar. Biochar is used because it is highly utilized and envi-
ronmentally-friendly, and the selected phase change materials are fatty acid type which are bio-
based material and have a low risk of depletion". In [18], authors tells that "results of the nu -
merical analysis showed further that latent heat storage biocomposite efficiently reduced the
maximum energy consumption of reference building models by 531.31 kWh per year. Thus,
both results validate the claim that latent heat storage biocomposite is a promising building ma-
terial".

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