Magnetic and hydrogen storage properties under the action of a sinusoidal electromagnetic field by the LaNi_3.6A_l0.4Co_0.7Mn_0.3 alloy

Received: 11-Jun-2023, Manuscript No. puljpam-23-6524; Editor assigned: 15-Jun-2023, Pre QC No. puljpam-23-6524 (PQ); Accepted Date: Jul 09, 2023; Reviewed: 20-Jun-2023 QC No. puljpam-23-6524 (Q); Revised: 05-Jul-2023, Manuscript No. puljpam-23-6524 (R); Published: 31-Jul-2023, DOI: 10.37532/2752-8081.23.7(4).219-224.

Citation: Belkhiria S, Chaker B, Dhaou MH, et al. Magnetic and hydrogen storage properties under the action of a sinusoidal electromagnetic field by the LaNi3.6Al0.4Co0.7Mn0.3 alloy. J Pure Appl Math. 2023; 7(4):219-224.

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Abstract

The detection of the response of an intermetallic compound to a magnetic field consists of a precession on the spin displacement and the associated damping. The displacement of the magnetic spin results in a change in the crystallographic structure and subsequently a change in the properties of hydrogen storage. Thus, in order to improve the performance of hydrogen storage within the LaNi3.6Al0.4Co0.7Mn0.3 intermetallic, and aware of their significant effect on the storage of hydrogen, we propose firstly, to consider an experimental study of the magnetic properties of the LaNi3.6Al0.4Co0.7Mn0.3 intermetallic compound. For this, a sensitive Vibration Sample Magnetometer (VSM) is used. Then, the mass of hydrogen absorbed / desorbed under the effect of a sinusoidal electromagnetic excitation has been presented.

Key Words

Magnetic hysteresis cycle; Virgin magnetization curve; Rayleigh calculation; Electromagnetic field; Hydrogen absorption; Hydrogen desorption

Introduction

The depletion of fossil fuels and the growing demand for energy have led researchers to develop new energy storage techniques. Among which, the storage of hydrogen in the form of metal hydrides in Metal-Hydrogen Reactors is recommended. The LaNi₅ intermetallic and its derivatives are very attractive for the reversible storage of hydrogen since they are able to store hydrogen in moderate temperatures and pressures which gives them the safety advantage [1-10]. The study of the hydrogen storage properties in the LaNi₅ intermetallic and its derivatives remains the interest of several experimental and numerical recent researches [11-14]. To improve the reversible hydrogen storage properties in the LaNi₅ compound, researchers focused on the one hand on the study of the key operating and design parameters: initial experimental conditions, reactor configuration, heat exchanger [15-17]. In the recent years, the coupling of the hydrogen metal reactor with a Phase Change Material (PCM has been widely studied [18–20]. The found results showed that when the PCM is used the hydrogen storage process is faster and the reaction kinetics is improved. The effect of the incorporation of the natural graphite on the compacts LaNi5 hydrogen storage properties. The results showed that the heat transfer within the hydride bed and the hydrogen storage capacity are improved and the time reaction is reduced [21].

On the other hand, several researchers focused on the study of the effect of the controlled substitution on the enhancement of the reversible hydrogen storage by the LaNi₅ [22-26]. The effect of Sn on the stability of the LaNi_5-xSn_x (0<x<0.5) was studied [27]. They observed high stability of the sample, which contains the element Sn. On the other hand, the absorption time is not strongly influenced by the addition of Sn, but desorption is delayed when the content of Sn is greater than 0.4. A comparative study of the storage properties of the LaNi₅ compound and the LaNi_5-xSn_x compound showed that the parent compound has the higher hydrogen storage capacity [28]. The effect of Co doping on Ni sites on storage isotherms has been studied [29]. Results showed that the Co addition partially combines the phase β and γ and contributing to a higher cycle stability during long-term cycling. The substitution of Ni by Al and Co to combine their effects has been considered [30]. The results showed that the addition of Co renders the intermetallic resistant to decrepitation, while the addition of Al decreases the dislocation rate. The compound LaNi_3.95Co_0.75Al_0.25 combines the two effects. The combination between Co, Mn and Al has also been considered in the study of the hydrogen storage properties by the LaNi_3.6Al_0.4Co_0.7Mn_0.3 compound [31-33]. The results showed that the hydrogen storage reaction is improved marked by an enlargement of the interstitial sites and the isotherms equilibrium plateau is lowered.

In this paper we propose in the first part, a study of the physical properties (structural and magnetic) at room temperature of the LaNi_3.6Al_0.4Co_0.7Mn_0.3 compound. In the second part the hydrogen absorption and desorption reactions by the LaNi_3.6Al_0.4Co_0.7Mn_0.3 compound under the action of a sinusoidal variable electromagnetic field as a function of initial temperature are studied. In previous published works, we have studied the hydrogen desorption by the LaNi₅ compound under the action of an electromagnetic field and reversible hydrogen storage under the action of a magnetostatic field [34-35]. To our knowledge, the proposed work has not been done by considering these experimental conditions and the same doped compound.

Experimental Steps

Structural characterization

The X-ray technique is used to identify the crystalline phases present in the doped intermetallic compound and to determine its structural parameters. For this, an X’Pert diffractometer is used which uses a θ-θ arrangement in Bragg-Brentano geometry. All measurements are made by a copper anticathode. The acquisition of the diffracto-gram data is done in a step of 0.04.

Magnetic measurement

The intermetallic compound was prepared from the high-purity elements (99.9%), in a sample holder is made in a glove box, under an argon atmosphere to avoid any surface passivation of the material with other gas. It was mechanically crushed out using a ball mill until obtaining particle sizes around 50 μm.

A Vibrating Sample Magnetometer (VSM) is used. The principle of measurement is the following: The sample is placed into a uniform magnetic field (H) where it acquires a magnetization M. It is moved inside coils. The magnetic flux passing through these coils is disturbed. In a superconductive loop, the flux must remain constant and quantified: an electric current is then induced in the circuit. This current creates a local flux variation in the coupling coil. This variation induces an alternating current in the SQUID. The output voltage of the amplifier is proportional to the variation in the number of initial flux quantum. The sample is moved in successive steps, each measurement of the flow variation form a point on the extraction curve. This curve is filtered to obtain the value of the magnetization.

Hydrogen storage measurement

The experimental devices as well as the hydrogen storage steps have been described in our previous published works [34-35]. 30 g of the intermetallic was prepared and placed into a copper reactor. The reactor is surrounded by a coil powered by a variable voltage generator (f = 50 Hz) and it is connected to a hydrogen tank by connecting tubes. A pressure sensor is installed between the reactor and the hydrogen tank to control the pressure variation during the reaction. The voltage delivered by the generator has been adjusted so as to reduce the effect of the electromagnetic induction heating. This is done by minimizing the energy dissipated by Joule effect. Thus, the reactor was crossed by a voltage of 0.9 volt. This voltage does not produce electromagnetic induction heating which allows us to focus only on the effect of the electromagnetic excitation on the hydrogen storage reaction by the intermetallic. An oscilloscope and a digital multi-meter were used to control the voltage delivered by the generator during the experiment. The reactor is immersed in a cylindrical aluminum heat exchanger which guarantees the cooling and heating of the hydride bed during absorption and desorption reactions by heat transfer water coming from the thermostatic bath. The water circulation in the heat exchanger is via a water inlet/outlet in Figure 1.

Figure 1: Electromagnetic field production

Results and Discussion

XRD analysis and Ritveld refinement

X-ray diffraction patterns of the LaNi3,6Al0.4 Mn0, 3 Co0,7 intermetalliccompounds is shown in Figure 2. The Rietveld refinement allows usto have a clear idea on the structure, the space group and theparameters of the parent and the doped intermetallic compounds(Table1). It is shown that the compound is a single phase with anorthorhombic crystal structure. The LaNi_3,6Al_0.4 Mn_{0, 3} Co_0,7 crystallizesin a Pnma space group.

Figure 2: The RX spectrum and the Rietveld refinement for the LaNi_3.6Al_0.4Co_0.7Mn_0.3 powder

Table 1 presents the values of the crystallographic axes and the unit cell volumes obtained from the XRD data.

TABLE 1 Results of the Rietveld refinement

Magnetic properties

Hysteresis cycle

Figure 3a represents the magnetic hysteresis cycle intermetallic compound at 25°C. It illustrates the relationship between the magnetization of the material and the applied magnetic field. The curve has three distinct zones:

• First zone: it is a linear zone. In fact, when the field increases the magnetization increases also. However, the increase due to magnetization is very slow compared to the increase in the field.

• Second zone: This zone is characterized by a remarkablevariation of the magnetization against zero fields.

• Third zone: it is a linear zone which shows that parentcompound reached saturation, however for the dopedmaterial it is not reached at the tested conditions.

Results found in Table 2 showed that intermetallic is magnetically soft presenting weak coercive field H_c (field at which M=f(H) change sign) and weak ramanant magnetization M_r (M at H=0). It has a paramagnetic character marked by a positive magnetic susceptibility χ.

TABLE 2 Experimental magnetic parameters from hysteresis cycles

Virgin magnetization curve

Figure 3b shows the virgin magnetization curves at room temperature (T=25°C). Starting from the demagnetized state (H=0, M=0) the magnetization increases with the applied H. In the virgin state H=0, the magnetic domains with positive magnetization combine with those with negative magnetization so that the total magnetization of the system is zero. As H increases, domains with magnetization oriented in the same direction of the exciting field increase in volume at the expense of domains with magnetization oriented opposite to the direction of the applied field. Finally, the magnetized domains in the opposite direction to the direction of H are eliminated, thus leading to saturation of magnetization. It is shown that the saturation of magnetization is not affected for the investigated compound.

Figure 3: Magnetic hysteresis cycle (a) and virgin magnetization curve (b) at room

Mathematical Rayleigh calculation

Rayleigh region is the first part of the initial magnetization curve, where low magnetizing fields are acting on the material. In this region, initial magnetization curve is a parabolic curve described by second order polynomial equation called Rayleigh law [36, 37]:

Where B is the magnetic flux density, H is the magnetizing field, μ₀ is the magnetic permeability of free space, μi is the initial relative magnetic permeability, α_R is called Rayleigh coefficient and M is the magnetization.

Linear dependence between relative magnetic permeability μ and magnetizing field is given [38]:

The magnetization can be expressed as a function of the applied field H according to the Raleigh law [37-38]:

Where M is the magnetization, H is the internal field, χ₀ is the initial susceptibility and α is the Rayleigh constant. The initial magnetic susceptibility and Rayleigh constant are the parameters which depending on the properties of the materials (Table 3).

TABLE 3 Experimental magnetic parameters from the virgin curve

Figure 4 show the magnetization fitted curve according to the Raleigh law. The fitting parameters for the LaNi_3.6Al_0.3Mn_0.4Co_0.7 are summarized in Table 4. The value of the susceptibilities found from fitting is in good agreement with the experimental value.

Figure 4: Raleigh fitting

TABLE 4 Calculated parameters from fitting of the LaNi₅ and LaNi_3.6Al_0.4Co_0.7Mn_0.3 intermetallic compounds according to the Raleiyh law

In the present case, the value of the susceptibility of the intermetallic compound confirms that the intermetallic is paramagnetic.

The Rayleigh constant is negative at low temperatures. The negative value confirms that the two materials are magnetically soft [39]. This means that in each particle when the magnetization is reversed, there are no potential barriers for the motion of the domain walls of the initial multi-domain state of the particle [40].

Hydrogen storage reaction under the action of the electromagnetic field

The pressure sensor installed between the reactor bed and the hydrogen tank measures a voltage difference. This pressure difference is converted to a pressure using equation 5:

• Hydrogen absorbed / desorbed mass calculation

It is assumed that hydrogen behaves like an ideal gas in the temperature ranges (0°C-100°C) and at pressures below 15 bars.

A gram atom of hydrogen at temperature T (°K) and pressure P (atm) occupies the volume:

With T₀=273°K, P_atm=1.0133 bar, V_a is the total volume of the buffer tank, pipes and free space in the reactor, V_a is estimated equal to 11207 cm³.

The number of atoms gram of hydrogen in a volume V at a temperature T and a pressure P is given by:

During absorption, the number of gram atoms of hydrogen at time t = 0 s is given by:

At a time t, the number of gram atoms of hydrogen in the two free volumes of the tank and the reactor is given by:

Where T₀ is the initial temperature used in K, P (t) is the applied pressure in the tank.

The number of gram atoms of hydrogen absorbed and desorbed is given by:

The absorbed and desorbed hydrogen concentrations are then given by:

Finally, the mass of absorbed and desorbed hydrogen are given by:

• Absorption reaction

The hydrogen absorbed mass is calculated according to eq.14. Figure 5(a-c) represent the hydrogen mass variationduring absorption reaction as a function of initialtemperature and magnetic field. Results show that theapplied electromagnetic field does not promote theabsorption reaction. It is observed that in the case of lowtemperature (T=5°C), the mass of hydrogen absorbed isconsiderably affected by the applied field. The increase intemperature suppresses the electromagnetic effect. This isexplained by the fact that at low temperature, the magneticfield applied causes a disorder which blocks the reaction.

Figure 5: Hydrogen absorption at different temperatures

• Desorption reaction

The desorbed hydrogen mass is calculated using eq. 15.Figure 6(a-c) represent the hydrogen mass variation duringdesorption reaction. It is observed that the appliedmagnetic field does not affect the desorption reaction at40°C and 50°C. However, it promote the reaction at 60°C.

Figure 6: Hydrogen desorption at different temperatures

Conclusion

The magnetic properties of the LaNi_3.6Al_0.4Mn_0.3Co_0.7 at room temperature have been determinate and the magnetic parameters have been calculated. The hydrogen storage properties under the action of an electromagnetic field have been considered. Results showed that the compound is a paramagnetic compound. It is classified as magnetically soft. The applied magnetic field disfavor the absorption hydrogen reaction and promote the desorption reaction.

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