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Correlation between Structure, Electrical, and Magnetic Properties of Some Alkali-Oxide Materials

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Amira Marzouki, Ameni Brahmia, Riadh Marzouki, Mosbah Jemmali, Ismat H. Ali and Mohamed Faouzi Zid

Submitted: 07 June 2021 Reviewed: 21 December 2021 Published: 10 February 2022

DOI: 10.5772/intechopen.102322

From the Edited Volume

Alkaline Chemistry and Applications

Edited by Riadh Marzouki

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In this chapter, the correlation between structure and electrical properties of Na2MP1.5As0.5O7 (MII = Co and Cu) are treated. The structural study shows that the cobalt and copper isotype materials can be crystallized in the tetragonal and monoclinic systems, respectively. The electrical study using impedance spectroscopy technique showed that these mixed diphosphate diarsenates are fast electrical conductors; however, the cobalt material exhibited more conductive property than the copper compound. In addition, the powder perovskite manganites La0.7M0.2M’0.1MnO3 (M = Sr, Ba and M’ = Na, Ag and K) have been prepared using the conventional solid-state reaction. The structural, magnetic, and magnetocaloric properties of these perovskite manganites compounds were studied extensively by means of X-ray powder diffraction (XRD) and magnetic measurements. These samples were crystallized in the distorted rhombohedral system with R3c space group. The variation of magnetization (M) vs. temperature (T) reveals that all compounds exhibit a second-order ferromagnetic to paramagnetic phase transition in the vicinity of the Curie temperature (TC). A maximum magnetic entropy change, ΔSMMax, of 4.07 J kg−1 K−1 around 345 K was obtained in La0.7Sr0.2Na0.1MnO3 sample upon a magnetic field change of 5 T. The ΔSMMax values of La0.7Ba0.2M’0.1MnO3 are smaller in magnitude compared to La0.7Sr0.2M’0.1MnO3 samples and occur at lower temperatures.


  • diphosphate-diarsenate
  • crystal structure
  • electrical properties
  • perovskite
  • magnetic materials
  • magnetocaloric effect

1. Introduction

The exploration of new alkali-based materials, especially Na-ion compounds, has become an area of intense activity [1, 2, 3]. In fact, these materials have the potential to replace lithium-based cathodes in the new generation of batteries. This trend can be explained by the global increase in demand for lithium and its toxicity compared to the low cost of sodium and its abundance in nature [4].

The two main methods of developing new cathodes, which are currently being explored, are either by researching new crystalline materials or by improving known materials by improving their electrical properties and electrochemical performance. In either case, crystallography remains the key to the development of these electrochemical systems as a determination of crystal structure and ion transport followed by electrochemical properties.

In this context, the exploration and investigation of phosphates, arsenates, and molybdates of transition metals and monovalent cations (Li, Na, K, Ag, etc.) have a promising field for various applications: electrical, piezoelectric processes, ferroelectric, magnetic, catalytic [5, 6]. Moreover, taking into account their remarkable structural richness, in particular the melilite structure [7], the olivine structure [8], and the sodium super ionic conductor (NaSICON) structure [9], these materials show several interesting physical properties, in particular, the ionic conduction and ion exchange [8, 9]. Many sodium-based materials have recently been prepared and tested for their electrical and/or electrochemical properties, including Na2CoP2O7 [10], LiCoAsO4 [11], Na1.86Fe3(PO4)3 [12], etc. These physicochemical properties are linked on the one hand to their structural wealth and on the other hand to the degree of openness of their anionic frameworks which can be dense, open, or microporous.

Thus, the investigation of this type of material requires a good correlation between crystal structure and electrical properties taking into account factors influencing the electrical conductivity such as porosity and the temperature range of stability of the crystal structure of the sample. In this chapter, the first part comprises a structural study of alkali metals (especially Na elements) transition metals (Co, Cu) phosphates-arsenates and their correlations with electrical properties.

On the other hand, alkaline atoms have an electronic procession, composed of a set of inert internal layers, having the structure of a rare gas, and an additional electron, or valence electron, which orbiting an s-type orbital. The study of ionization potentials shows that this electron is easily torn off, the heavier the atom is the lesser the energy is required for ionization. The chemistry of alkali metals is essentially constituted by the study of the transition to the ionized state M+ and by the properties of this ion. Most alkaline compounds, therefore, have a purely ionic structure; this peculiarity, together with the fact that the most stable ionic edifices are constituted by ions of similar volume, makes it possible to predict that as a general rule hydrides, nitrides, carbides, and simple oxides, that is to say compounds possessing fairly small anions, will be all the more stable the lighter the alkali metal, while the salts corresponding to large anions, peroxides (O▬O)2−, superoxides (O▬O), oxacids, and halides will be more stable with heavy alkali metals.

The dangers of the impact of synthetic refrigerants on the environment are central to the global ecological scene. Global warming, by its complexity and magnitude, poses several challenges to the ecological future of the earth. One of the solutions proposed to slow down this process is to reduce the production of greenhouse gases. While demand is growing, the areas of refrigeration and air conditioning are trying to renew themselves to meet the new ecological requirements. Such developments will lead to new technologies applicable to domestic and industrial uses of microtechnologies, HVAC systems refrigerators, heat pumps and affecting the automotive, railway, aeronautical, and aerospace industries. Magnetocaloric cooling (MCE) is a possible solution and becomes a promising attempt. Magnetic refrigeration is a technology that relies on the magnetocaloric effect, similar to compressibility refrigerant for gas refrigeration.

The magnetocaloric effect being present in all magnetic substances gives a large field of research activity to find active materials suitable for every utility [13, 14]. Gadolinium is the reference material for magnetic cold at room temperature. This element also has the advantage of being an easy compound to obtain through its purity. It finds its technological development, thanks to the ease of implementation reflected by its high ductility and suitability. This is why it is used in most current magnetic refrigeration devices at room temperature. However, its prohibitive price (up to 3500 €/kg) and its limited reserves preclude it from possible magnetocooling materials for consumer applications. It is, therefore, important to find another magnetocaloric material. Manganese is an energetically clean alternative to address this problem and may be potential material for magnetic refrigeration.

The compounds LnMnO3, Ln2MnO4 (where Ln is a rare earth) are antiferromagnetic insulators. The partial substitution of Ln3+ by a divalent element A2+ (A2+ = Ca2+; Sr2+; Ba2+; Pb2+…), monovalent A+ (A+ = Ag+, Na+, K+…), trivalent A3+ (A3+ = Nd3+, Sm3+, Pr3+…), or a gap in Ln1−xAxMnO3 results in oxidation or partial reduction of Mn3+/Mn4+ ions, a structural transition (cubic ↔ rhombohedral ↔ orthorhombic) and an antiferromagnetic order change TN = 125 K in LaMnO3) ferromagnetic with Tc > 360 K depending on the composition [15, 16, 17, 18, 19, 20, 21, 22].

The manganese oxides, which we are interested in given the importance of their electrical and magnetic properties [23, 24], crystallize in a perovskite-like structure. For this structure, of general formula ABO3, the Bravais network of sites B (octahedral site), whose species are generally transition cations (Mn3+, Mn4+, Ti4+, Al3+…) occupying the eight vertices of the cube, is simple cubic. Oxygen ions occupy the midpoints of the ridges, and species A in coordination 12 (cuboctahedral site) occupying the center of the cube are alkaline ions (K+, Na+, Ag+…). Alkaline earth (Sr2+, Ca2+, Pb2+…) or rare earths (La3+, Pr3+, Nd3+…). Site B is, therefore, occupied by an ion of octahedral coordination, manganese in the case of manganites, thus forming the MnO6 octahedra (Figure 1(a) and (b)).

Figure 1.

Unit cell ABO3 (a), octahedral environment of species B and (b) cuboctahedral environment of species A.

It should be noted that the cations A and B must allow the electroneutrality of the compound; that is, the sum of the charges of the cations A and B must be equal to the total charge of the anions. Three types of ternary oxides can be found: cation A is monovalent (A+ B5+ O2−3), bivalent (A2+ B4+ O2−3), or trivalent (A3+ B3+ O2−3).


2. Structure, characterization, and electrical properties of Na2MP1.5As0.5O7 (MII = Co and Cu).

2.1 Structural characterizations

The X-ray powder diffractograms were recorded in the range 10–70° at 20°C with 0.02° step (Figures 2 and 3). GSAS software [25] using Rietveld method was used to confirm the crystallinity and purity of the obtained powders. The final reliability factors are Rp = 1.4%, Rwp = 1.9%, and Rp = 5.4%, Rwp = 6.9%, of the Co and Cu samples, respectively.

Figure 2.

Rietveld refinement pattern of Na2CoP1.5As0.5O7 powder.

Figure 3.

Rietveld refinement pattern of Na2CuP1.5As0.5O7 powder.

In this case, the difference between the two diffractograms is noticeable. Indeed, the Na2CoP1.5As0.5O7 [26] material crystallizes in the tetragonal system of the space group P42/mnm with the unit cell parameters a = 7.764 (3) Å; c = 10.385 (3) Å. While the compound Na2CuP1.5As0.5O7 [27] crystallizes in the monoclinic system of the C2/c space group with the unit cell parameters a = 14.798 (2) Å; b = 5.729 (3) Å; c = 8.075 (2) Å; β = 115.00 (3)°.

In fact, the structural unit of the compound Na2CoP1.5As0.5O7 is formed by a site occupied by a cobalt atom, a site occupied by a phosphorus atom partially substituted by arsenic, two sites for the sodium atoms and three sites for the sodium atoms ten oxygen atoms. The asymmetric unit is shown in Figure 4.

Figure 4.

Structural unit of Na2CoP1.5As0.5O7 with atom labeling scheme.

(i) −y + 1/2, x − 1/2, −z + 1/2; (ii) −x + 1, −y, z; (iii) y + 1/2, −x + 1/2, −z + 1/2].

The projection of the structure in the b direction (Figure 5) illustrates the layered nature of the anionic framework with two alternating orientations of anion sheets [Co(P/As)2O7]2− per unit cell parallel to the ab plane where sodium cations are sandwiched between layers. Compared to Na2CoP2O7 [28] crystal structure, the substitution of the phosphorus ions by arsenic cations decreases the size of the interlayer space and decreases in binding Na▬O distance.

Figure 5.

Projection of the Na2CoP1.5As0.5O7 along b direction.

On the other hand, the structural unit of Na2CuP1.5As0.5O7 (Figure 6) contains two P2O7 units connected by the corner with two CuO4 with square plane geometry. The charge neutrality of the structural unit is ensured by four sodium ions.

Figure 6.

Structural unit projection of Na2CuP1.5As0.5O7.

The Cu2P4O15 groups of the structural unit are linked by oxygen peaks to give infinite chains, wavy sawtooth in the [001] direction (Figure 7). Na+ ions are located in the inter-chain space.

Figure 7.

Structure projection of Na2CuP1.5As0.5O7 in the ac plane showing the chain arrangement.

2.2 Electrical study of Na2CoP1.5As0.5O7

The electrical properties of the cobalt compound were studied using complex impedance spectroscopy [29] in the temperature range from 240 to 360°C after stabilization at each step of 30°C between 1 Hz and 13 MHz frequency range. The electrical parameters are concluded using the conventional electrical circuit: R//CPE-R//CPE, where Rest is a resistance and CPE is a constant phase element:

The electrical parameters are summarized in Table 1.

T (°C)Rtotal (105 Ω)σ (10−5 S cm−1)σd (10−4 S cm−1)

Table 1.

Results of electrical parameters of Na2CoP1.5As0.5O7.

The electrical measurements show that the electrical conductivity of Na2CoP1.5As0.5O7 increases from 4.0 × 10−6 S cm−1 at 240°C to 3.69 × 10−5 S cm−1 at 360°C. On the other hand, the activation energy which follows Arrhenius’ law is 0.56 eV.

2.3 Electrical study of Na2CuP1.5As0.5O7

The Na2CuP1.5As0.5O7 sample was sintered at 550°C for 2 h with 5°C/min of heating and cooling. The relative density of the obtained pellet is D = 88%. Electrical measurements in the temperature range of 260–380°C were performed using complex impedance spectroscopy. The recorded spectra are shown in Figure 8.

Figure 8.

Impedance spectra of Na2CuP1.5As0.5O7 recorded at 240–360°C.

The best refinements of impedance spectra were obtained when using a conventional electrical circuit Rg//CPEg-Rgb//CPEgb.

The values of the electrical parameters calculated at different temperatures are presented in Table 2.

T (°C)Rt (104 Ω)ρt (104 Ω cm)σ (10−5 S cm−1)σd (10−5 S cm−1)

Table 2.

Results of electrical parameters of Na2CuP1.5As0.5O7.

The conductivity of Na2CuP1.5As0.5O7 (Table 2) increase from 0.35 × 10−5 S cm−1 at 260°C to 3.13 × 10−5 S cm−1 at 380°C. On the other hand, the porosity of 12% of our sample prompted us to estimate the conductivity values of the fully dense sample of Na2CuP1.5As0.5O7 using the empirical formula proposed by Langlois and Couret [30].

Taking into account the porosity factor P = 0.12, the conductivity value of the dense material will be σd = (4σ/0.88). The conductivity values of a dense sample, calculated at different temperatures, are summarized in Table 2. In this case, the experimental conductivity of 3.5 × 10−6 S cm−1 corresponds to the corrected value of 1.59 × 10−5 S cm−1 to 260°C.

The activation energy calculated from the slope of the linear curve Ln(σ × T) = f(1000/T) is linear (Figure 9), with a slope that gives the value of Ea = 0.60 eV, satisfying Arrhenius law LnσT = Lnσ0 − Ea/kT (k = Boltzmann constant).

Figure 9.

Arrhenius plot of conductivity of the Na2CuP1.5As0.5O7 sample.

The electrical study shows that the activation energy decreases for Na2CuP1.5As0.5O7 compared to that of Na2CuP2O7 [27], i.e., 0.60 eV and 0.89 eV, respectively. Therefore, the effect of P/As substitution increases the electrical conductivity of the parent phase Na2CuP2O7 at a lower temperature [31]. Overall, a comparison of the conductivity values of the material studied Na2CuP1.5As0.5O7 (at T = 350°C, σd = 88% = 2.28 × 10–5 S cm−1; σd = 2.28 × 10−4 S cm−1 and Ea = 0.60 eV) with those found in the literature shows that our material can be classified as fast ionic conductors.


3. Structure, magnetic, and magnetocaloric of La0.7Sr0.2K0.1MnO3 and La0.7Ba0.2Na0.1MnO3 compounds

3.1 Structural characterization

Before proceeding with the magnetic study, it was necessary to ascertain the structure of the materials. Using the X-ray diffraction technique, it was possible to confirm that all the samples analyzed in this work have only one type of structure (single-phase) and that they corresponded to the given stoichiometry. The samples were reduced to powdered form, with a grinding time of 2 min, which was sufficient to obtain the random effect of orienting the structures without destroying them.

To check the nature and purity of the synthetic products, X-ray diffraction patterns were recorded at room temperature using the Panalytical X’Pert PRO diffractometer which is equipped with a copper anticathode (λKα1 = 1.54056 Å, λKα2 = 1.54439 Å) and provides good quality diffractograms.

Figure 10 presents the experimental X-ray diffraction spectra of La0.7Sr0.2Na0.1MnO3 compound refined via the WinPlotr graphical interface of FullProf_Suite which has been studied by W. Cheikh-Rouhou Koubaa et al. [32].

Figure 10.

X-ray diffraction patterns of La0.7Sr0.2Na0.1MnO3 sample.

The Rietveld analysis of X-ray diffraction patterns shows that the La0.7Sr0.2K0.1MnO3 and La0.7Ba0.2Na0.1MnO3 compounds are single-phase and crystallize in the rhombohedral Th2Zn17-type structure (space group, R_3m).

Figure 11 shows the evolution of the unit cell volume compared to ⟨rA⟩ for the two series. For La0.7Sr0.2M0.1MnO3 samples, an observed increase of ⟨rA⟩ occurred with a slight decrease in the volume of the unit cell from 352.5 Å for M = Na to 351.1 Å for M = K. While in the compounds La0.7Ba0.2M0.1MnO3, the evolution of unit cells is rather governed by ⟨rA⟩ than by σ2 observed increase in unit cell volume. It should be noted that, although the ionic radius of site A and the size of the mismatch are similar for both samples, La0.7Sr0.2K0.1MnO3 and La0.7Ba0.2Na0.1MnO3, the unit cell volume has different values. This behavior highlights the effects of the difference in electronegativity between the A-site ions in our compounds [33]. With increasing ⟨rA⟩, the Mn▬O▬Mn binding angle decreases from 166.7° for sample La0.7Sr0.2Na0.1MnO3 to 165.9° for the sample La0.7Ba0.2Na0.1MnO3. However, the Mn▬O bond length increases from 1.957 Å to 1.968 Å, which influences the dual force of exchange. Effects of monovalent doping on the structural, magnetic, and magnetocaloric properties in La0.7M0.2M0.1MnO3 manganese oxides (M = Sr, Ba and M’ = Na, Ag, K) has been studied to control the value evaluation of magnetic entropy and cooling capacity.

Figure 11.

Unit cell volume versus ⟨rA⟩ for La0.7M0.2M’0.1MnO3 (M = Sr, Ba and M’ = Na, Ag and K) samples.

3.2 Study of magnetic properties

The magnetic behaviors are subjected to two variables, which are the temperature and the applied magnetic field. It is possible to control these two factors experimentally and, thus, to keep one constant while studying the influence of the other on the magnetization M. The magnetic measurements were carried out on the two magnetometers BS2 and BS1 of the NEEL Institute used in the low/high-temperature configuration. The evolution of the magnetization as a function of the temperature and of the M(H, T) field was carried out on either side of the Curie temperature for each compound. The temperature of transition from the ferromagnetic state to the paramagnetic state was determined from the thermomagnetic curve M(T). TC corresponds to the minimum value of (dM/dT). The change in magnetic entropy was evaluated from the M(H, T) matrix based on the corresponding Maxwell equation.

Magnetic measurements of these compounds La0.7Sr0.2K0.1MnO3 and La0.7Ba0.2Na0.1MnO3 as a function of temperature in the temperature range 20–350 K under an applied magnetic field of 50mT show that all substituted samples show a magnetic transition from paramagnetic to ferromagnetic with decreasing temperature, as shown in Figure 12.

Figure 12.

Temperature dependence of the magnetization under an applied magnetic field 50 mT.

Figure 13 shows that the Curie temperature varies according to the ionic rays. It goes to lower values with ⟨rA⟩ and varies from 340 K for ⟨rA⟩ = 1.182 Å to 311.5 K for ⟨rA⟩ = 1.247.

Figure 13.

Curie temperature versus ⟨rA⟩ for La0.7M0.2M’0.1MnO3 (M = Sr, Ba and M’ = Na, Ag and K) samples.

3.3 Study of magnetic properties under an applied magnetic field

In manganites, magnetism is essential of the localized type. A simple way to check, at low temperature, the ferromagnetic state, the fixed spin state, or the coexistence of a ferromagnetic and antiferromagnetic state of a sample, is to compare the value of the saturation magnetization with its calculated value assuming full alignment of the manganese spins of this compound. This procedure gives an estimate of the degree of alignment of the moments. For this, we present the study of the magnetic properties of these samples under an applied magnetic field up to the value of 7 tesla. As the study of the thermal variations of the magnetization under weak magnetic field (0.05 T) showed that the samples Pr0.6−xEuxSr0.4MnO3 (0.0 ≤ x ≤ 0.2) present a magnetic transition as a function of the temperature, it is then interesting to specify the nature of the magnetic order at low temperatures. M’nassri et al. [34] performed magnetization measurements as a function of the magnetic field applied at various temperatures.

The difference observed between the compounds La0.7Sr0.2K0.1MnO3 and La0.7Ba0.2Na0.1MnO3 is fully explained by the effects of the difference in electronegativity between the ions at site A for the two samples. The magnetization measurements as a function of the applied magnetic field up to 7 T at several temperatures confirmed the ferromagnetic behavior of these samples at low temperature, and the results are shown in Figure 14.

Figure 14.

(a) Isotherm magnetization curves M(H, T). (b) Temperature dependence of the spontaneous magnetization Msp and 1/χ for La0.7Sr0.2Na0.1MnO3 sample.

The authors show that below TC, the magnetization M increases strongly with the magnetic field applied for H < 0.5 T then saturates above 1 T. The saturation magnet changes to higher values as the temperature decreases. This result confirms the ferromagnetic behavior of our sample at low temperature. Figure 14b shows the temperature dependence of the spontaneous magnetization Msp and 1/χ for the sample La0.7Sr0.2Na0.1MnO3. The experimental value of the spontaneous magnetization Msp(exp), deduced from the M(H) curves is 3.48 μB/Mn. The amplitude of the Msp(exp) is comparable to the theoretical value of 3.6 μB/mole calculated for full spin alignment. The critical exponent defined by.


and deduced from the fit of the curve Msp(T) is 0.31, which confirms the ferromagnetic behavior of the samples from the group Cheikh-Rouhou team at low temperature

3.4 Magnetocaloric effect

Entropy is a measure of order in the magneto-thermodynamic system. High order is related to low entropy and vice versa. Dipoles, that is, electron spins, can take on different orientations. If these entities are oriented in the same direction in a paramagnetic material, a ferromagnetic or a diamagnetic material, the order and the magnetization are high. It is obvious that applying a magnetic field aligns the electronic spins and lowering the temperature (releasing energy from the system) also results in a more ordered arrangement. So the external magnetic field generates the stress parameter, while the magnetization determines the order parameter of such magnetic materials.

In order to obtain a maximum of information on the thermodynamic behavior and to observe the magnetocaloric effect in the manganites in the vicinity from their magnetic transition temperature, we have studied the magnetocaloric behavior of the whole range of composition x.

After having studied magnetic measurements of magnetization as a function of temperature M(T) as well as magnetization as a function of the magnetic field at various temperature M(μ0H, T), we have calculated, the magnetic entropy change ΔSM of all our synthesized compounds as a function of temperature T and magnetic field H.

Based on the thermodynamic theory, magnetic entropy change is determined through the numerical integration of the magnetization isotherms, according to Maxwell’s thermodynamic relation given by the following equation [34, 35]:


where Mi and Mi + 1 are the magnetization values measured at the Hi field and at temperatures Ti and Ti + 1, respectively [35].

We have shown in Figure 15, the variations in entropy (−ΔSM) as a function of temperature for different magnetic fields applied for these La0.7Sr0.2Na0.1MnO3 and La0.7M0.2M0.1MnO3 sample (M = Sr, Ba and M’ = Na, Ag and K) system. These curves show that the entropy value (−ΔSM) varies with temperature and has a peak around the transition temperature TC. The sample La0.7Sr0.2Na0.1MnO3 shows the highest value of ΔSMMax, 4.07 J kg−1 K−1, around 345 K. For the sample La0.7Ba0.2Na0.1MnO3, we observed an asymmetric broadening of the peak ΔSM, which could be explained by a structural inhomogeneity. We can also notice that the magnetic and negative entropy for all our samples was due to the ferromagnetism encountered in these samples. The value of the entropy (−ΔSMMax) was also observed to increase when the applied magnetic field increased. Although these ΔSMMax values in these samples are lower than those observed in Gd or Gd-based compounds, the ΔSMMax curves as a function of temperature are significantly wider. This wider temperature range with a large change in magnetic entropy is useful for an ideal Ericsson refrigeration cycle. In addition, our samples are interesting in application as potential candidates in magnetic refrigeration because they are inexpensive, easier to manufacture, possess tunable TC, and have high chemical resistance stability.

Figure 15.

Magnetic entropy change −ΔSM evolution versus temperature at (a) Several magnetic applied fields for La0.7Sr0.2Na0.1MnO3 sample (b) At 5 T for La0.7M0.2M0.1MnO3 samples (M = Sr, Ba and M’ = Na, Ag and K).


4. Conclusion

During our research on the investigation of new phosphates, arsenates of metals (Co, Cu) and alkali cations, we were able to isolate 2 crystalline phases. These compounds have shown remarkable structural diversity, even though they are isoformular. The synthesis method adopted was dry synthesis. In addition, P/As substitution showed conservation of structure in each material with variation in cation-oxygen distances. On the other hand, the effect of substitution is remarkable on the electrical properties. In fact, the sodium Co and Cu diphosphates-diarsenates are more conductive than the pure diphosphates. Alkaline atoms have an electronic procession, composed of a set of inert internal layers, having the structure of a rare gas, and an additional electron, or valence electron, which orbiting an s-type orbital. The magnetic and magnetocaloric study on the La0.7M0.2M’0.1MnO3 family shows that there is a Curie temperature in the vicinity of the room temperature and very high magnetic entropy values. We can conclude that these compounds are good candidates for magnetic refrigeration.


  1. 1. Brian LE, Nazar F. Sodium and sodium-ion energy storage batteries. Current Opinion in Solid State & Materials Science. 2012;16:168-177
  2. 2. Shakoor RA, Seo DH, Kim H, Park YU, Kim J, Kim SW, et al. A combined first principles and experimental study on Na3V2(PO4)2F3 for rechargeable Na batteries. Journal of Materials Chemistry. 2012;22:20535
  3. 3. Kim H, Shakoor RA, Park C, Yeon Lim S, Kim JS, Jo YN, et al. Na2FeP2O7 as a positive electrode material for rechargeable aqueous sodium-ion batteries. Advanced Functional Materials. 2013;23:1147
  4. 4. Peng Y, Yang L, Ju X, Liao B, Ye K, Li L, et al. A comprehensive investigation on the thermal and toxic hazards of large format lithium-ion batteries with LiFePO4 cathode. Journal of Hazardous Materials. 2020;381:120916
  5. 5. Goodenough JB, Hong HY-P, Kafalas JA. Fast Na+ -ion transport in skeleton structures. Materials Research Bulletin. 1976;11:203-220
  6. 6. Kanazawa T. Inorganic Phosphate Materials, Materials Science Monographs. Vol. 52. Amsterdam: Elsevier; 1989
  7. 7. Erragh F, Boukhari A, Elouadi B, Holt EM. Crystal structures of two allotropic forms of Na2CoP2O7. Journal of Crystallographic and Spectroscopic Research. 1991;21:321-326
  8. 8. Padhi AK, Nanjundaswamy K, Goodenough JB. Phospho‐olivines as positive‐electrode materials for rechargeable lithium batteries. Journal of the Electrochemical Society. 1997;144(4):1188-1194
  9. 9. Durif A. Crystal Chemistry of Condensed Phosphates. US: Springer; 1995
  10. 10. Barpanda P, Lu J, Ye T, Kajiyama M, Chung S-C, Yabuuchi N, et al. A layerstructured Na2CoP2O7 pyrophosphate cathode for sodium-ion batteries. RSC Advances. 2013;3:3857-3860. DOI: 10.1039/C3RA23026K
  11. 11. Satya Kishore MVVM, Varadaraju UV. Synthesis, characterization and electrochemical studies on LiCoAsO4. Materials Research Bulletin. 2006;41:601-607
  12. 12. Essehli R, Ben Yahia H, Maher K, Sougrati MT, Abouimrane A, Park J-B, et al. Unveiling the sodium intercalation properties in Na1.860.14Fe3(PO4)3. Journal of Power Sources. 2016;324:657-664
  13. 13. Tishin AM, Spichkin YI. The Magnetocaloric Effect and Its Applications. Bristol: Institute of Physics Publishing; 2003
  14. 14. Tegus O, Brück E, Buschow KHJ, de Boer FR. Transition-metal-based magnetic refrigerants for room-temperature applications. Nature. 2002;415:150
  15. 15. Cherif K, Dhahri J, Dhahri E, Oumezzine M, Vincent H. Effect of indium substitution on structural, magnetic and magnetocaloric properties of La0.5Sm0.1Sr0.4Mn1−xInxO3 (0 ≤ x ≤ 0.1) manganites. Journal of Solid State Chemistry. 2002;163:466
  16. 16. Tlili MT, Chihaoui N, Bejar M, Dhahri E, Valente MA, Hlil EK. Charge ordering analysis by electrical and dielectric measurements in Ca2−xPrxMnO4 (x = 0–0.2) compounds. Journal of Alloys and Compounds. 2011;509:6447
  17. 17. Daoudi A, Le Flem G. Sur une série de solutions solides de formule Ca2−xLnxMnO4 (Ln = Pr, Nd, Sm, Eu, Gd). Journal of Solid State Chemistry. 1972;5:57
  18. 18. Takahashi J, Kamegashira N. Low-temperature structural phase transitions in rare earths substituted calcium manganese oxides [Ca2−xLnxMnO4, where Ln=Nd, Sm-Lu and Y]. Materials Research Bulletin. 1993;28:451
  19. 19. Takahashi J, Kikuchi T, Satoh H, Kamegashira N. Phase transition of Ca2-xSmxMnO4 (x < 0.5). Journal of Alloys and Compounds. 1993;192:96
  20. 20. Dhahri E, Guidara K, Cheikhrouhou A, Joubert JC, Pierre J. Monovalent effects on structural, magnetic and magnetoresistance properties in doped manganite oxides. Phase Transitions. 1998;66:99
  21. 21. Teresa JMDE, Ibarra MR, Garcia J, Blasco J, Ritter C, Algarabel PA, et al. Spin-glass insulator state in (Tb-La)2/3Ca1/3MnO3 perovskite. Physical Review Letters. 1996;76:3392
  22. 22. Ju HL, Kwon C, Li Q, Greene RL, Venkatesan T. Magnetic anisotropy and strain states of (001) and (110) colossal magnetoresistance thin films. Applied Physics Letters. 1994;65:2108
  23. 23. Ziese M. Extrinsic magnetotransport phenomena in ferromagnetic oxides. Reports on Progress in Physics. 2002;65:143
  24. 24. Shankar KS, Kar S, Raychaudhuri AK, Subbanna GN. Fabrication of ordered array of nanowires of La0.67Ca0.33MnO3La0.67Ca0.33MnO3 (x=0.33)(x=0.33) in alumina templates with enhanced ferromagnetic transition temperature. Applied Physics Letters. 2003;84(6):993
  25. 25. Larson AC, Von Dreele RB. General Structure Analysis System (GSAS). Report LAUR 86–748. Los Alamos, NM: Los Alamos National Laboratory; 2000
  26. 26. Marzouki R, Ben Smida Y, Sonni M, Avdeev M, Zid MF. Synthesis, structure, electrical properties and Na+ migration pathways of Na2CoP1.5As0.5O7. Journal of Solid State Chemistry. 2020;285:121058
  27. 27. ALQarni OSA, Marzouki R, Smida YB, Avdeev M, Alghamdi MM, Zid MF. Synthesis, electrical properties and Na+ migration pathways of Na2CuP1.5As0.5O7. PRO. 2020;8:305
  28. 28. MacDonald JR. Impedance Spectroscopy. New York: Wiley; 1987
  29. 29. Sanz F, Parada C, Rojo JM, Ruiz-Valero C, Saez-Puche R. Studies on tetragonal Na2CoP2O7, a novel ionic conductor. Journal of Solid State Chemistry. 1999;145(2):604-611. DOI: 10.1006/jssc.1999.8249
  30. 30. Langlois S, Couret F. Electrochemical measurements of mass transfer coefficients in a cell simulating tooth canals. Journal of Applied Electrochemistry. 1989;19:43
  31. 31. Hafidi E, El Omari M, El Omari M, Bentayeb A, Bennazha J, El Maadi A, et al. Conductivity studies of some diphosphates with the general formula AI2BIIP2O7 by impedance spectroscopy. Arabian Journal of Chemistry. 2013;6:253-263
  32. 32. Cheikh-Rouhou Koubaaa W, Koubaaa M, Cheikhrouhou A. Effect of monovalent doping on the structural, magnetic and magnetocaloric properties in La0.7M0.2M′0.1MnO3 manganese oxides (M=Sr, Ba and M′=Na, Ag, K). Physics Procedia. 2009;2:989-996
  33. 33. Koubaa WC, Koubaa M, Cheikhrouhou A. Structural, magnetotransport, and magnetocaloric properties of La0.7Sr0.3−xAgxMnO3 perovskite manganites. Journal of Alloys and Compounds. 2008;453:42
  34. 34. M’nassri R, Cheikhrouhou-Koubaa W, Koubaa M, Boudjada N, Cheikhrouhou A. Magnetic and magnetocaloric properties of Pr0.6-xEuxSr0.4MnO3 manganese oxides. Solid State Communications. 2011;151:1579
  35. 35. Mc Michael RD, Ritter JJ, Shull RD. Enhanced magnetocaloric effect in Gd3Ga5−xFexO12. Journal of Applied Physics. 1993;73:6946

Written By

Amira Marzouki, Ameni Brahmia, Riadh Marzouki, Mosbah Jemmali, Ismat H. Ali and Mohamed Faouzi Zid

Submitted: 07 June 2021 Reviewed: 21 December 2021 Published: 10 February 2022