Citation: Grigorova, E.; Markov,P.;
Tsyntsarski, B.; Tzvetkov,P.;
Stoycheva, I. Hydrogen Storage
Properties of Ball Milled MgH
2
with
Additives- Ni, V and Activated
Carbons Obtained from Different
By-Products. Materials 2023, 16, 6823.
https://doi.org/10.3390/
ma16206823
Academic Editor: Ting Zhang
Received: 29 September 2023
Revised: 12 October 2023
Accepted: 20 October 2023
Published: 23 October 2023
Copyright: © 2023 by the authors.
Licensee MDPI, Basel, Switzerland.
This article is an open access article
distributed under the terms and
conditions of the Creative Commons
Attribution (CC BY) license (https://
creativecommons.org/licenses/by/
4.0/).
materials
Article
Hydrogen Storage Properties of Ball Milled MgH
2
with
Additives- Ni, V and Activated Carbons Obtained from
Different By-Products
Eli Grigorova
1,
*, Pavel Markov
1
, Boyko Tsyntsarski
2
, Peter Tzvetkov
1
and Ivanka Stoycheva
2
1
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences, Acad. G. Bonchev Str., Bld. 11,
1113 Sofia, Bulgaria; pvlmarkov@svr.igic.bas.bg (P.M.); ptzvetkov@svr.igic.bas.bg (P.T.)
2
Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G.
Bonchev Str., Bld. 9, 1113 Sofia, Bulgaria; boiko_sf@yahoo.com (B.T.); ivanka.stoycheva@orgchm.bas.bg (I.S.)
* Correspondence: egeorg@svr.igic.bas.bg
Abstract: The hydrogen sorption of materials based on 80 wt.% MgH
2
with the addition of 15 wt.%
Ni or V and 5 wt.% activated carbons synthesized from polyolefin wax, a waste product from
polyethylene production (POW), walnut shells (CAN), and peach stones (CPS) prepared by milling
under an inert Ar atmosphere for a period of 1 h, is investigated. All precursors are submitted
to pyrolysis followed by steam activation in order to obtain the activated carbons. The hydrogen
sorption evaluations are carried out for absorption at 473 and 573 K with pressure of 1 MPa and
for desorption at 623 and 573 K with pressure of 0.15 MPa. The composition of the samples after
milling and hydrogenation is monitored by X-ray diffraction analyses. The 80 wt.% MgH
2
–15 wt.
%Ni–5 wt.% POW or CAN after absorption–desorption cycling and in a hydrogenated state at 573 K
and 1 MPa are analyzed by TEM.
Keywords: sorption; hydrogen storage; metal hydrides; carbon materials
1. Introduction
Materials based on solid-state hydrogen storage include adsorbents, liquid organ-
ics, complex and interstitial hydrides as well as chemical hydrogen. Each of them has
advantages and disadvantages. Some of these materials have higher capacity but poor
reversibility, and some have an elevated explosive risk such as, for example, in the case
of complex hydrides. Other materials such as ammonia store hydrogen in an irreversible
way, and their toxicity and recycling problems are very important. The highly porous
adsorbents such as carbon nanotubes and MOFs adsorb hydrogen at a temperature below
100 K and high pressure [1]. Hydrogen storage in the form of metal hydrides provides
important safety and high energy density advantages over the gas and liquid storage
methods. Among a lot of metals and intermetallics that are capable to react with hydrogen
in a reversible way magnesium–based materials as hydrogen storage media are more per-
spective. There has been intensive research regarding their hydrogen storage application
due to the high theoretical hydrogen absorption capacity of magnesium (7.6 wt.%), very
good reversibility, abundance, and low cost. These materials have also some fallibilities,
such as slow kinetics, necessity of activation, and increased sorption temperatures, es-
pecially for the desorption process. Using a variety of dopants combined with milling
in a planetary or vibratory mill leads to a decrease in hydrogen sorption temperatures
and enhanced kinetics, and in general, to an improvement in the hydrogen absorption–
desorption properties. Depending on the nature of the additives, their catalytic effect is
different. Some of the additives can easily form hydrides; especially non-stoichiometric
and others like iron, for example, act as active sites during the dissociative chemisorption
of hydrogen. The amount of additives should be carefully balanced. A larger amount
Materials 2023, 16, 6823. https://doi.org/10.3390/ma16206823 https://www.mdpi.com/journal/materials