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A new challenge is obtaining and researching ceramic multifunctional materials containing phases with various properties, as well as Aurivillius phases, which determine their application. They show potential for use in electrochemical applications and ferroelectric and piezoelectric devices, sensors, and non-volatile memories. Presented are our studies of volumetric nonmonophasic ceramics from the RE-Ba-Cu-O (ReBCO, RE = rare-earth; Y, Dy) and Bi-Pb-Sr-Ca-Cu-O (B(Pb) SCCO) systems that are superconductors, obtained via solid phase synthesis. A bulk ceramic composite Y123/BaCuO2 was synthesized with starting stoichiometry of 1:3:4(Y:Ba:Cu) via a one-step procedure. It has superconducting and magnetic properties at low temperatures. DyBCO bulk ceramic with a nano-Fe3O4 additive was synthesized and characterized to identify the phase and elemental composition, the microstructure, and the superconducting transition temperature. The Aurivillius phases were synthesized via solid-phase synthesis and a melt-quench method. B(Pb)SCCO ceramics (2223, 2212, and 2201), with conductive properties, have been used as an addition to the active mass of a Zn electrode. The method of mixing the materials was also investigated. Their behavior in an alkaline environment and positive influence on the properties and longevity of the nickel-zinc battery has been studied. Part of the obtained ceramic systems was patented.
G. Nadjakov Institute of Solid State Physics, Bulgarian Academy of Sciences, Sofia, Bulgaria
Stanislav Slavov
Department of Mathematics, University of Chemical Technology and Metallurgy, Sofia, Bulgaria
*Address all correspondence to: angelina@issp.bas.bg
1. Introduction
In recent years, particular attention has been given to the synthesis and characterization of multifunctional materials, such as ceramics with various structures obtained through different methods, aiming at their practical applications. In the present paper, we present our previous results in the research of ceramic multifunctional materials which contain phases with various properties (ferromagnetic magnetic phases, superconductive ceramic phases, and others), as well as Aurivillius phases (which possess high-temperature dielectric properties). Conductive ceramics are a class of functional materials with high electrical conductivity and chemical stability [1, 2, 3, 4]. Ever since the discovery of high-temperature conductance in 1987 by Chu and Wu [5], there has been a special interest in cuprate ceramics, the methods of their preparation, and their application.
The properties of these ceramics make them suitable for applications in items such as magnetic bearings, permanent magnets, power cables, etc. “High-temperature superconductor” is a term that has been used interchangeably with “cuprate superconductor” for compounds like yttrium barium copper oxide (YBCO) and bismuth strontium calcium copper oxide (BSCCO), however, there are also other high-temperature superconductors. Research shows that Re123 (Re = rare earth element, such as Y, Eu, Gd, Dy, Nd, S, Ho, Er) materials are known as superconductors with a high Tc [6]. The crystal structure of the ReBCO materials is a multilayered perovskite structure [7]. Research over the years has been mainly focused on finding techniques that increase the transition temperature, Tc. Researchers have created many compounds from the YBCO family to obtain a Tc that is higher than that of Y123 (92 K), such as Y124 with a Tc = 80 K [8] and Y247 with a Tc that can vary from 30 K to 95 K, depending on the oxygen content [9, 10]. In 2009 Aliabadi, Farshchi and Akhavan [11] and Tavana [12] discovered a new Y-based high-temperature superconductor in the face of Y-Ba-Cu-O (Y-358), which becomes superconductive at over 100 K.
YBa2Cu3O7-x (Y123) and Bi2Sr2Ca2Cu3O7 (BSCCO) remain some of the most investigated superconductive systems. A reproducible and well-defined ceramic compound with nominal composition (Y123/BaCuO2) has been synthesized in a one-step reaction. It has been found that barium cuprate is one of the few copper oxides exhibiting ferromagnetic interactions, thus during Tc measurements, it can affect the transition width of the ρ-T curves [13, 14]. Studies have shown that, besides the superconducting properties, a composite ReBCO (Re = rare earth) compound that contains BaCuO2 exhibits magnetic properties as well. Thus, one can expect that such a diversity in the non-monophasic ReBCO ceramic’s property might be useful for future practical application [15, 16].
Using solid phase synthesis a bulk sample Dy-123 doped with nano-Fe3O was obtained. Inserting a low concentration of Fe3O4 into a Dy-Ba-Cu-O sample improves its superconductive properties. We assume that this occurs due to the presence of Fe3O4 nanoparticles and BaCuO2 and CuO phases at the boundaries of the grain which improves its connectivity [17].
The stability of these ceramics in a strong alkaline environment has been researched and its influence on their structure and properties has been traced. The magnetic properties of the resulting samples were measured, both before and after the electrochemical testing. The results show that the samples retain their superconductive properties after a stay in a strongly alkaline environment. They can be successfully used as an additive to the electrode in alkaline batteries, thus improving their cyclic operation capabilities [18].
Previous research conducted by us also demonstrates the potential of superconducting ceramics such as B(Pb)SCO 2201 and B(Pb)SCCO 2212 to be used as additives to the active mass of the zinc electrode in batteries and the effect on the electrochemical properties have been presented [19, 20, 21, 22, 23, 24, 25, 26, 27]. The influence of the different methods of obtaining a Zn active mass has been studied, as well as the content of the additive inside it [24, 25]. Using impedance spectroscopy the obtained Ni-Zn electrochemical alkaline systems (anode of nano-sized ZnO doped with differing content amounts of conducting ceramics) have been studied [26, 27]. The observed effect of adding them improves the battery’s properties and lifespan, which makes B(Pb)SCCO cuprate ceramics a promising doping material for the development of new electrochemical systems, as well as for use in different devices.
The development of new materials with ferroelectric or hybrid properties, the following application directions can be defined as storage devices such as FERAM and DRAM and semiconductor elements [28], capacitors, sensors; high-temperature piezoelectric materials, namely the class of layered bismuth-containing compounds with additives, such as SrBi4Ti4O15 with a Curie temperature of about 530°C [29] and K0.5Bi4.5Ti4O15 [30] with Curie temperature 555°C and d33 about 21.2 pC/N, Saito at al [31], Takenaka at al [32], Zhang et al. [33] with equivalent properties to piezoelectric bismuth-based materials, such as similar strain rate at room temperature, better thermal resistance up to the Curie temperature; electro-optical ceramic materials and their application — transparent thin films, usually the compounds LiNbO3 and Li(Nb, Ta)O3, and with an amorphous matrix with included ferroelectric crystals such as (Na, K)NbO3, BaTiO3 [34, 35], LiNbO3 [36], Bi2VO5.5 [37], Bi2GeO [38]. The presented results regarding multifunctional ceramic materials show great potential for use in a wide spectrum of applications.
The cuprate superconductors, also called cuprate ceramics, have been obtained via solid-phase synthesis. For the preparation of the composite material, a mixture of yttrium-barium-copper-oxide (YBCO) is obtained with an initial nominal stoichiometric composition of 1:2:3 and 1:3:4. Y2O3, BaCO3, and CuO are mixed and homogenized to form a homogeneous mixture. This mixture is then subjected to a three-step thermal treatment in an oxygen-rich environment [15, 16]. Following the same scheme, samples of the Dy-Ba-Cu-O system, which has been doped with nano-Fe3O4 [17, 39].
B(Pb)SCO 2201 and B(Pb)SCCO 2212 ceramics were prepared using a two-step solid-state synthesis. Starting materials including Bi2O3, PbO, CuO, SrCO3, and CaCO3 are dried, weighed in the required stoichiometric ratios, and homogenized. They are then heated at 780°C for 24 hours, crushed again, and pressed into tablets at 5–6 MPa. The tablets are subsequently fired: B(Pb)SCO 2201 at 830°C for 24 hours, and B(Pb)SCCO 2212 at 830°C for 48 hours under ambient air atmosphere [19].
To prepare the Zn electrode, an active mass is used, which is prepared from nanosized ZnO, carboxymethylcellulose (CMC 3% solution), polytetrafluoroethylene (PTFE 60% suspension) in a weight ratio of 81:14:5, and an additive B(Pb)SCO 2201 or B(Pb)SCCO 2212) with a different content [19, 20, 21, 22, 23, 24, 25, 26, 27]. CMC and PTFE serve as plasticizers. The mixing is done either through mechanical mixing, ultrasonic mixing, or ball milling. The prepared paste is applied onto a current collector made of modified copper foam. The obtained electrodes are dried at 70°C for one hour and pressed at a pressure of 30 MPa. The studied electrode package consists of electrodes measuring 5.0 × 3.0 cm with a thickness of 0.15 cm, separated by a microporous separator, and immersed in an alkaline electrolyte.
Polyphase samples were synthesized in the system Bi2O3–TiO2–Nd2O3 using the method of melt quenching, and developed a methodology for the control of the constituent material Auriuvilius and pyrochlore crystalline phases. The method is used to control the high-frequency dielectric characteristics [40]. Additionally, the glass-crystal materials for sensors in the system SiO2-Bi2O3-TiO2 have been synthesized by a method of melt quenching and controlled crystallization of the glass and subsequent synthesis of thin layers by ink-screen-printing technique [41]. The materials in the system La2O3-Gd2O3-PbO-MnO-B2O3, demonstrate the synthesis of a monophasic material with a content of perovskite crystalline phase (La1-xGdx)0.6 Pb0.4MnO3 which has been shown to be promising for ferroelectric applications [42].
2.2 Methods
The following contemporary methods were used to analyze the structure and morphology of the synthesized and alkaline-treated samples: standard X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive X-ray spectroscopy (EDX). The non-stoichiometric oxygen coefficient (δ) and the total oxygen content (y) were determined by a spectrophotometric method [43]. To establish the superconductive properties, magnetic measurements (AC/DC) were used.
For the electrochemical characterization of the initial ceramics and the obtained electrodes, the following techniques were employed: cyclic voltammetry (CV), chrono-potentiometry (CP), and potentiostatic electrochemical impedance spectroscopy (PEIS) using a Biologic potentiostat/galvanostat SP200 instrument.
A bulk ceramic composite Y123/BaCuO2 was synthesized by a solid-state reaction with starting stoichiometry of 1:3:4(Y:Ba:Cu) [15]. The ceramic composite Y123/BaCuO2 obtained in a one-step procedure was studied and appears to lead to a material possessing both superconducting and magnetic properties at low temperatures. We have shown that if the nominal starting composition is 1:3:4 (Y:Ba:Cu) one can obtain a two-phase composite with 62 wt% of superconducting YBCO with high critical temperature equal to 92.6 K and 38 wt% of magnetic BaCuO2. It was also proven that the stability of obtained composite in alkaline solution is superior over pure Y123 material which is important for practical application.
The composite material was obtained which consists of a Y123 phase with oxygen content of 6.88 to 6.99 and a BaCuO2 phase in a 2:1 ratio [15, 16]. This composite material and the method of obtaining it have been patented [16]. On Figure 1 the x-ray diffraction spectra are presented: YBCO material with a superconductive Y123 phase (specter a), the obtained composite material containing a superconductive Y123 phase and a BaCuO2 phase before (specter b) and after alkaline treatment (specter c), while Figure 2 represents its magnetic hysteresis before (curve a) and after alkaline treatment (curve b). It is superconductive at a temperature higher than that of liquid nitrogen, possesses magnetic properties, and is resistant to alkaline environments. The presence of superconductive and magnetic properties and its resistance to alkaline environments increase the possibilities of application in all areas of technology.
Figure 1.
X-ray diffraction spectra of, respectively: YBCO material with a superconductive Y123 phase (spectrum (a)), the obtained composite material containing superconductive Y123 phase and BaCuO2 phase before (spectrum (b)) and after its alkaline treatment (spectrum (c)) [16].
Figure 2.
Magnetic hysteresis loops (magnetization curves) of the obtained composite material before (curve (a)) and after alkaline treatment [16].
Another composite material with multifunctional properties from the Dy-Ba-Cu-O (with a nominal composition of 123) system was also obtained by solid-phase synthesis. It was doped with Fe3O4 nanopowder, which is imported after the second stage of synthesis. The obtained results show that additions of Fe3O4 nanopowder at low concentrations to the Re(Y;Dy)-Ba-Cu-O systems improve the superconducting properties by increasing the critical temperature and critical current density of the obtained polycrystalline bulk ceramics with inhomogeneous composition. Homogeneous distribution of iron is observed on their surface, respectively [17].
The multiphase structure is observed in the SEM micrographs of the sample Dy123 with Fe3O4 shown in Figure 3. The main Dy123 phase has a typical surface with elongated grains and an average grain size of ~3.74 μm. The EDX confirms the non-monophasic composition of the ceramic sample as seen in Table 1.
Figure 3.
SEM of Dy123 with Fe3O4 [17].
Spectrum element
Series
1 Atom. C. [at. %]
2 Atom. C. [at. %]
3 Atom. C. [at. %]
4 Atom. C. [at. %]
5 Atom. C. [at. %]
6 Atom. C. [at. %]
Dysprosium
L
11.65
0.28
0
4.68
4.71
4.30
Barium
L
9.04
0.26
12.59
9.34
9.39
8.52
Copper
K
11.13
44.99
17.70
13.25
13.22
14.61
Oxygen
K
68.19
54.47
57.07
71.57
71.40
71.13
Chlorine
K
0
0
12.33
0
0
0.42
Iron
K
0
0
0.32
1.16
1.29
1.02
Phase
DyBaCu
CuO
BaCuO2+ Fe
Dy123+ Fe
Dy123+ Fe
Dy123+ Fe
Table 1.
Elemental composition of the Dy123 + Fe3O4 sample obtained by EDX analysis [17].
In Figure 4 the EDX mapping of Dy123 with Fe3O4 sample is shown. Whole crystals of CuO and BaCuO2 are visible on the surface, with small quantities of Fe also detected scattered around the Dy123, CuO and BaCuO2 crystals. We believe that Fe does not react with the other elements and does not form phases of its own.
Figure 4.
EDX mapping analysis of Dy123 with Fe3O4 [17].
The significant benefits that the rechargeable alkaline Ni-Zn battery system can provide, including its high specific energy and power density, affordable electrode materials, ecologically benign chemistry, and straightforward metal recycling procedure, are what have sparked interest in these batteries [44, 45, 46, 47, 48]. The durability of a Ni-Zn battery’s Zn anode, which is typically a paste-type composite electrode with a main component of electrochemically active ZnO powder and various additives to enhance the electrode’s electrochemical properties, is a major factor in the battery’s life cycle. The electrochemical heterogeneity of the anode mass and active surface loss during charge/discharge cycling, which results in progressive changes to the electrode shape and capacity loss, are mostly caused by ZnO’s poor electrical conductivity [44, 49]. A powder additive, such as acetylene black, is added to the zinc electrode mass to increase conductivity, although this could cause a rise in hydrogen gas evolution during the charging process. Next, we will go over the study of superconducting BSCCO ceramics as an additive to the Zn electrode mass. It improves the electrode’s properties, conductivity, and structural stability, making it a suitable additive to a Zn electrode in alkaline battery systems.
For the first time, structural and morphological changes in B(Pb)SCCO 2212 and B(Pb)SCCO 2201 ceramics were investigated before and after their electrochemical treatment (CV and CP measurements) in a Ni-Zn battery-like medium (7 M KOH, 25°C) [21]. This is the first step toward understanding the observed improvements in the characteristics of the Zn electrode when using ceramic additives. After CV (Figure 5), various reduction products are found, such as CuO, Bi2O3, Bi2CuO4, Ca(OH)2, and Sr.(OH)2, and the CV curves show that at higher negative potentials the Cu and Bi compounds are further reduced to metallic Cu and Bi (1). This can lead to the formation of metal particles that improve the overall conductivity of the electrode as well as the contact between the particles of the active ZnO. On the other hand, the Ca- and Sr- products in the case of the B(Pb)SCCO 2212 modification do not participate in the redox processes.
Figure 5.
CV curves of B(Pb)SCCO 2212 (a) and B(Pb)SCCO 2201 (b) in 7M KOH solution. Scan rate: 5 mV s−1 [21].
The structural and morphological changes occurring in B(Pb)SCCO 2212 and B(Pb)BSCCO 2201 conducting ceramics in an alkaline environment have been investigated, providing additional insights into the mechanisms of the ongoing processes. Electron microscopy reveals that after electrochemical treatment, B(Pb)SCCO 2212 becomes smoother and forms higher and larger facets, while the surface of B(Pb)SCCO 2201 becomes grain-covered [21].
Comparing the X-ray diffraction patterns of B(Pb)SCCO 2212 and B(Pb)SCCO 2201 ceramics before and after their chrono-potentiometric study shows that the primary phases are preserved with reduced intensity after electrochemical treatment, and the appearance of Bi2O3 is observed [21].
The potential of B(Pb)SCCO 2201 and B(Pb)SCCO 2212 undergoes a sharp change when current is applied, indicating an initial breakdown reaction of the ceramic additive before the reduction reactions. The electrode potential remains relatively constant, which suggests that the breakdown is unaffected by the reduction products. The process may continue until the complex structure of B(Pb)SCCO ceramics is completely reduced, leading to the formation of simpler oxides such as CuO, Bi2O3, Bi2CuO4, Ca(OH)2, and Sr(OH)2 [21].
These results demonstrate that when the ceramics are treated in an alkaline environment, they undergo partial reduction to oxides and hydroxides, leading to the formation of insoluble Zn compounds, which reduce the solubility of ZnO in the electrolyte and suppress the shape change of the electrode, thereby improving conductivity. In the case of B(Pb)SCCO 2212, the presence of Ca and Sr. products contributes to the stabilization of the electrode, reducing its solubility in the alkaline electrolyte, suppressing dendrite formation, and mitigating gas evolution during operation [21]. These positive effects are believed to be the cause of the observed up to 30% extension in battery life when using a conducting ceramic as an additive in the zinc electrode of the nickel-zinc system [19].
Ultrasound was also used to mix the additives in the preparation of the electrode mass [24]. The micrographs of ZnO with carbon additive, ZnO with carbon and B(Pb)SCCO 2201 additive, and ZnO with carbon and B(Pb)SCCO 2212 additive obtained by the ultrasound-assisted mixing are shown (Figure 6). The ultrasound-assisted mixing of the active mass leads to superior particle distribution, as seen on the SEM images. This is most noticeable in Figure 6b. The SEM micrographs of the electrodes provided evidence for their better homogenization, while the impedance measurements confirmed the better conductivity of the zinc mass obtained through ultrasonic irradiation [24, 25]. In Table 2, the average values of EDX results are presented. It is seen that the composition did not change during the ultrasound mixing.
Figure 6.
SEM images of ZnO with carbon additive (a), ZnO with carbon and B(Pb)SCCO 2201 additive (b), and ZnO with carbon and B(Pb)SCCO 2212 additive (c) with EDX analysis [24].
Samples
Elemental content, [at. %]
Zn
C
Bi
Pb
Sr
Ca
Cu
O
Sample a)
18.27
21.81
59.91
Sample b)
Spectrum 1
4.25
6.57
1.34
7.04
3.74
77.07
Spectrum 2
25.33
0.36
74.31
Sample c)
Spectrum 3
5.2
6.41
0.76
6.19
5.35
7.57
68.52
Spectrum 4
46.76
53.24
Table 2.
EDX analysis results for ZnO with carbon additive (Sample a), ZnO with carbon and 2201 additive, and ZnO (Sample b) with carbon and 2212 additive (Sample c) [24].
During the ultrasound treatment, the composition of the active mass is preserved. Physically mixing the B(Pb)SCCO additives with active zinc mass for Ni-Zn battery has already been proven to have an influence in our past investigations. The PEIS measurements show that the overall resistance of the electrode and that of the charge transfer in the electric double layer is reduced by the BSCCO additives and thus the electrochemical reaction is facilitated. These effects are strengthened due to the ultrasonic treatments, although to a very low degree. Due to that, we believe that better homogenization through ultrasonic irradiation of the additives with the ZnO may enhance the conductivity, the stability and increase the life of the battery even more. This study gives us a basis for future investigation of the newly prepared Zn electrodes in a Ni-Zn electrochemical cell [25].
In more detail, the structural, morphological, and electrochemical changes that might occur in the active mass and the electrodes, due to the different methods of preparation, have been examined: ball-milling treatment, ultrasound, and mechanical (by hand) mixing [25]. This study has proven useful in explaining how the different methods of preparation might improve or worsen the homogenization of the zinc mass content and the overall performance of the Zn-electrode. The results show that the method of grinding in a ball-mill does not contribute to better homogenization of the ceramic additives in the active zinc mass. The ultrasound treatment for ½ hour leads to better homogenization of the active mass with B(Pb)SCCO 2212 and B(Pb)SCO 2201 ceramic and respectively the reduction of the electrode resistance. The reason for the observed results can be explained on one hand by the processes that take place during ultrasonic treatment and on the other hand by the presence of calcium carbonate in B(Pb)SCCO 2212, which probably favors faster processes at the micro level. In the absence of B(Pb)SCCO 2212 more time is needed for the manifestation of the desired effect [25].
The impedance characteristics of electrochemical systems (ECSs) were also investigated, in which the anodes are obtained from nanosized ZnO material doped with high-temperature superconducting ceramic Bi1.7Pb0.3Sr2Ca2Cu3Oy (B(Pb)SCCO 2212) at a concentration of 5, 7 or 10 wt .% for the purpose of electrochemical applications (such as Ni-Zn batteries) [26]. The electrically conductive properties of such alkaline electrolyte ECSs were characterized at ambient temperature by electrochemical impedance spectroscopy measurements. The frequency spectra of Z* of the produced ECSs were recorded by electrical impedance-meter Bio-Logic SP–200, in the range 0.1 Hz – 100 kHz, at room temperature (in our case 25°C). By this technique [50, 51], both real (ReZ) and imaginary (ImZ) parts of the complex electrical impedance Z* = ReZ + i ImZ are simultaneously measured as a function of the frequency f of the alternating-current (AC) electric field applied. The amplitude of the AC voltage applied between the electrodes of ECSs was 10 mVRMS (sine function). The dimensions of the electrodes were 5.0 cm × 3.0 cm, their thicknesses were 0.15 cm, and the distance between them was 36 mm. They were separated by a microporous separator in an alkaline electrolyte (liquid KOH). For the sake of comparison, reference ECSs with identical geometry were designed with copper (Cu) (99.99% pure) or undoped ZnO anodes [26].
The effect of ceramic additives on the complex electrical impedance and electrical conductivity of the studied ECSs was evaluated. It was demonstrated that the incorporation of B(Pb)SCCO 2212 HTSC ceramics at a concentration of 7 wt% into the ZnO anode material of ECSs leads to an increase in their static (DC) electrical conductivity. In addition, the AC conductivity of the ECSs is also improved and approaches the values corresponding to ECSs with undoped ZnO anode through identical ECSs geometrical configurations. The Nyquist plots in Figure 7a clearly show the higher electrical conductivity of the studied ECSs having ZnO anode doped with BPSCCO ceramics, as compared to the undoped ZnO anode.
Figure 7.
(a) Nyquist plots for complex impedances measured for the studied ECSs. The designations are as in Figure 1. The insert: Enlarged view; (b) fitted data for ECSs with BPSCCO-doped ZnO anodes (data from (a)) to the equivalent circuit scheme shown at the top of (b). The lines represent the fitting results [26].
Also, it is apparent in Figure 7a that RB of the active volume of the studied ECSs is decreased when the BPSCCO percentage in the ZnO mass of the anode of the ECSs was increased from 5 wt% to 7 wt%. By further increase of the BPSCCO concentration up to 10 wt%, RB slightly diminishes, and practically there is no difference in resistance between identically constructed ECSs with the anode of ZnO doped with the BPSCCO at either 7 wt% or 10 wt% (Figure 7a). The same applies for the corresponding values of the electrical conductivity σ = d/(RB A). Note also that at these two concentrations (7 wt% and 10 wt%) of BPSCCO, ImZ < ReZ/2 for the maximum ImZ value of the circles in the Nyquist plots, i.e., the dispersive character of capacity is evident, in contrast to the case for 5 wt% BPSCCO. Accordingly, the ECS scheme needs to be modified by adding new elements, as drawn in Figure 7b. Such an ECS model gives satisfying fit results that agree very well with the experimental data points (Figure 7b).
The electrical properties of the alkaline systems whose Zn electrodes (anodes) contain active mass produced from composites of ZnO and B(Pb)SCCO 2212 conductive cuprate ceramics (5, 7 and 10 wt%) were investigated in terms of complex impedance (Z*) and tangent loss spectra [27]. The aim was to trace the effect of the ceramics as additives on the impedimetric response and tangent loss spectra of the electrochemical cells. The analysis of the electric impedance spectra of such electrochemical systems indicated that the redox processes in them are enhanced by the increase of the concentration of the B(Pb)SCCO 2212 ceramic additives (in the range 5–10 wt.%). Significantly, at a lower concentration of B(Pb)SCCO 2212, for example, 5 wt.%, a lower electric loss was established for the examined cells (related to the better surface properties of the layer deposited on the anode). Thus, such composite material (Zn active mass) with included B(Pb)SCCO 2212 conductive ceramics can be proper for producing electrodes in Ni-Zn electrochemical alkaline systems with enhanced performance.
For the first time, copper-based superconducting ceramics have been proposed as additives to the negative electrode of nickel/zinc batteries. The addition of copper-based superconducting ceramics such as BSCCO (2201, 2212, 2223) or YBCO (123) improves the bulk conductivity and structure of the zinc electrode, reduces gas evolution during electrode charging, which has a favorable effect on capacity retention and extends the electrode’s lifespan (Figure 8) [19].
Figure 8.
Dependency of capacity on the number of cycles for a nickel-zinc alkaline battery cell with zinc electrodes containing additives of BSCCO 2212 copper-based superconducting ceramics (curve a), YBCO 123 copper-based superconducting ceramics (curve b), and carbon material - acetylene black (curve c) [19].
These positive effects of the B(Pb)SCCO ceramic, observed from the tested electrochemical systems, make it a promising doping material for the development of new electrochemical systems as well as for use in different devices.
The dielectric properties of the samples in the system Bi2O3-TiO2-Nd2O3 have been studied in frequency 2.7 GHz and control of dielectric parameters is realized by precise control of the percentage of initial oxides and synthesis temperatures [40]. Depending on the controlled melting conditions and additional heat treatment of the supercooled compositions, different polyphase glass-ceramic materials with different microstructures in the systems Bi2O3-TiO2-SiO2 and Bi2O3-TiO2-Nd2O3 controlled microstructural features and dielectric properties were obtained [52].
The obtained results are the built and patented systems of new materials based on ferroelectric ceramics, with application for capacitor batteries with specific thermal parameters [53, 54]. In addition to that, a new sequence of technological procedures has been created, which relates to the production of conductive composite ceramic materials for industrial use [53]. Furthermore, conductive ceramics have been made for use in hydrogen generators [54].
In summary, the scientific and applied contributions can be clarified as:
Creation of new composite materials from natural raw materials and methods for their industrial production.
A composite material has been obtained, consisting of the Y123 phase and the BaCuO2 phase in a ratio of 2:1. It exhibits superconductivity at temperatures higher than that of liquid nitrogen, displays magnetic properties, and is resistant in alkaline environments. It finds applications in the field of electrical industry, computer technology, space technology, medicine, alkaline rechargeable batteries used as power sources, and more.
New constructions and materials for ceramic capacitor batteries.
The composition of the active mass of the negative zinc electrode, consisting of powdered zinc and/or zinc oxide and binders with high hydrogen evolution overpotential, also includes an additive of copper superconductive ceramic. It improves the volumetric conductivity and structure of the zinc electrode, reduces gas evolution during electrode charging, which has a favorable effect on capacity stability and extends the electrode’s lifespan, and can find application as a negative electrode in alkaline rechargeable batteries, particularly nickel-zinc batteries.
The works presented in this chapter are developed as part of contract №: BG-RRP-2.004-0002-C01, project name: BiOrgaMCT, Procedure BG-RRP-2.004 “Establishing of a network of research higher education institutions in Bulgaria”, funded by BULGARIAN NATIONAL RECOVERY AND RESILIENCE PLAN and is part of an inter-academic collaboration project between the Bulgarian Academy of Sciences, the Estonian Academy of Sciences, Tallinn University of Technology and the Institute of Low Temperature and Structure Research, Polish Academy of Sciences.
Dedicated to our teacher prof. Yanko Dimitriev.
We express our gratitude to our colleagues, who participated in the realization of these scientific developments, and to academician Alexander Petrov for his invaluable advice and support.
References
1.Liu HJ, Luo MQ , Yang LX, Zeng CL, Fu C. A high strength and conductivity bulk MAGNÉLI phase Ti4O7 with superior electrochemical performance. Ceramics International. 2022;48(17):25538-25546. DOI: 10.1016/j.ceramint.2022.05.233
2.Chen M, Liu Q , Zhu J, Cao W, Chen J, Su J. The influence of ZrO2 doping on microstructure and electrical properties of zno-based conductive ceramics. Ceramics International. 2021;47(17):24959-24965. DOI: 10.1016/j.ceramint.2021.05.223
3.Bondarchuk AN, Corrales-Mendoza I, Tomás SA, Marken F. A hematite photoelectrode grown on porous and conductive SNO2 ceramics for solar-driven water splitting. International Journal of Hydrogen Energy. 2019;44(36):19667-19675. DOI: 10.1016/j.ijhydene.2019.06.055
4.Wang G, Liu Y, Duan Y, Ye J, Lin Z. Effects of porosity on the electrochemical oxidation performance of Ti4O7 electrode materials. Ceramics International. 2023;49(10):15357-15364. DOI: 10.1016/j.ceramint.2023.01.120
5.Wu MK, Ashburn JR, Torng CJ, Hor PH, Meng RL, Gao L, et al. Superconductivity at 93 K in a new mixed-phase Y-ba-cu-O compound system at ambient pressure. Physical Review Letters. 1987;58(9):908-910. DOI: 10.1103/physrevlett.58.908
6.Andreouli C, Tsetsekou A. Processing effect on microstructure and superconducting properties of sintered ReBa2Cu3Oy ceramics — The role of ionic radius. Journal of the European Ceramic Society. 2000;20(12):2101-2114. DOI: 10.1016/s0955-2219(00)00074-1
7.Karppinen M, Yamauchi H. Hole-doping routes for understanding the relationship between atomic arrangements and superconductivity properties in multi-layered copper oxides. International Journal of Inorganic Materials. 2000;2(6):589-599. DOI: 10.1016/s1466-6049(00)00085-4
8.Marsh P, Fleming RM, Mandich ML, DeSantolo AM, Kwo J, Hong M, et al. Crystal structure of the 80 K superconductor YBa2Cu4O8. Nature. 1988;334(6178):141-143. DOI: 10.1038/334141a0
9.Karpinski J, Rusiecki S, Bucher B, Kaldis E, Jilek E. The nonstoichiometry of the high-Tc superconductor Y2Ba4Cu7O15±x (14 K⩽Tc⩽68 K). Physica C: Superconductivity. 1989;161(5-6):618-625. DOI: 10.1016/0921-4534(89)90398-5
10.Genoud J-Y, Graf T, Triscone G, Junod A, Muller J. Variation of the superconducting and structural properties of Y2Ba4Cu7Oz with oxygen content (14.1 < z < 15.3, 30 K ⩽ Tc ⩾ 95 K). Physica C: Superconductivity. 1992;192(1-2):137-146. DOI: 10.1016/0921-4534(92)90753-y
11.Aliabadi A, Akhavan Farshchi Y, Akhavan M. A new Y-based HTSC with Tc above 100K. Physica C: Superconductivity and Its Applications. 2009;469(22):2012-2014. DOI: 10.1016/j.physc.2009.09.003
12.Superconductors. Superconductors. Available from: http://www.superconductors.org/
13.Sreedhar K, Ganguly P. Magnetic susceptibility studies on ternary oxides of copper(II). Inorganic Chemistry. 1988;27(13):2261-2269. DOI: 10.1021/ic00286a011
14.Ganguly P, Sreedhar K, Raju AR, Demazeau G, Hagenmuller P. Electron paramagnetic resonance studies of some ternary oxides of copper (II). Journal of Physics: Condensed Matter. 1989;1(1):213-226. DOI: 10.1088/0953-8984/1/1/018
15.Stoyanova-Ivanova A, Terzieva S, Georgieva S, Blagoev B, Kovacheva D, Zaleski A, et al. Superconductivity and magnetic studies of bulk Y123/BaCuO2 composite. Romanian Journal of Physics. 2018;61:1-2
16.Stoyanova-Ivanova A, Terzieva S, Blagoev B, Georgieva-Kiskinova S, Kovacheva D. Composite material and method of obtaining it. 2020. Patent #67066
17.Stoyanova-Ivanova A, Kolev S, Petrova V, Petkov O, Tran L, Babij M, et al. Physicochemical study of bulk Dy-123 doped with nano-Fe3O4. Bulgarian Chemical Communications. 2022;54(Special Issue B1):71-76. DOI: 10.34049/bcc.54.B1.0404
18.Stoyanova-Ivanova A, Terzieva DS, Ivanova DG, Mladenov AM, Kovacheva GD, Raicheff GR, et al. The use of high-temperature superconducting cuprate as a dopant to the negative electrode in Ni-Zn batteries. Bulgarian Chemical Communications. 2015;47(1):221-228
19.Mladenov M, Raicheff R, Stoyanov L, Stoyanova-Ivanova A, Terzieva S, Kovacheva D. Electrode mass for zinc electrode of alkaline rechargeable batteries. 2018. Patent #66730
20.Lilov PA, Vasilev AY, Stoyanova AE, Marinov YG, Stoyanova-Ivanova AK. Electrochemical impedance study of HTSC ceramics YBCO and BSCCO in presence of electrolyte. Bulgarian Chemical Communications. 2018;50(Special issue A):153-157
21.Stoyanova-Ivanova A, Lilov P, Vasev A, Stoyanova A, Ivanova G, Karashanova D, et al. Studies of structural and morphological properties of cuprate conductive ceramics after electrochemical treatment in alkaline electrolyte. Materials Chemistry and Physics. 2020;239:121934. DOI: 10.1016/j.matchemphys.2019.121934
22.Stoyanova-Ivanova A, Vasev A, Lilov P, Petrova V, Marinov Y, Stoyanova A, et al. Conductive ceramic based on the Bi-Sr-Ca-Cu-O HTSC system as an additive to the zinc electrode mass in the rechargeable Ni-Zn batteries – Electrochemical impedance study. Proceedings of the Bulgarian Academy of Sciences. 2019;72(2):174-171. DOI: 10.7546/crabs.2019.02.05
23.Ivanova G, Stoyanova-Ivanova A, Kovacheva D, Stoyanova A. Improvement of the electrochemical properties of Ni-Zn rechargeable batteries by adding B(Pb)SrCaCuO conducting ceramics. Bulgarian Chemical Communications. 2019;51(1):66-72
24.Petrova V, Stoyanova-Ivanova A, Lilov P, Petkov O, Ivanova G, Karamanova B, et al. Ultrasound assisted mixing of zinc active mass with conductive ceramic additives for Ni-Zn battery. ECS Transactions. 2019;95(1):227-234. DOI: 10.1149/09501.0227ecst
25.Stoyanova-Ivanova A, Ivanova G, Leffterova E, Petrova V, Petkov O, Stoyanova A. Influence of various preparation methods on the electrochemical properties of the active Zn mass with conductive cuprate ceramics as additives. Current Topics in Electrochemistry. 2021;23:25-32
26.Stoyanova-Ivanova A, Lefterova E, Ivanova G, Marinov Y, Hadjichristov G, Stoyanova A. Impedance spectroscopy study of Ni-Zn electrochemical alkaline systems with anode of nano-sized zno doped with conducting ceramics b(pb)scco 2212. Proceedings of the Bulgarian Academy of Sciences. 2022;75(3):358-366. DOI: 10.7546/crabs.2022.03.05
27.Angelina, Lefterova E, Marinov Y, Ivanova G, Stoyanova A, Hadjichristov G. Electrochemical cells with anodes performed with Zn active mass with added B(Pb)SCCO 2212 conductive ceramics. Comptes rendus de l’Académie bulgare des Sciences. 2023;76(6):871-880
28.Buhay H, Sinharoy S, Kasner WH, Francombe MH, Lampe DR, Stepke E. Pulsed laser deposition and ferroelectric characterization of bismuth titanate films. Applied Physics Letters. 1991;58(14):1470-1472. DOI: 10.1063/1.105200
29.Maeder MD, Damjanovic D, Voisard C, Setter N. Piezoelectric properties of Srbi4ti4O15 ferroelectric ceramics. Journal of Materials Research. 2002;17(6):1376-1384. DOI: 10.1557/jmr.2002.0205
30.Wang C-M, Wang J-F. Aurivillius phase potassium bismuth titanate: K0.5Bi4.5Ti4O15. Journal of the American Ceramic Society. 2008;91(3):918-923. DOI: 10.1111/j.1551-2916.2007.02211.x
31.Saito Y, Takao H, Tani T, Nonoyama T, Takatori K, Homma T, et al. Lead-free piezoceramics. Nature. 2004;432(7013):84-87. DOI: 10.1038/nature03028
32.Takenaka T, Nagata H, Hiruma Y. Current developments and prospective of lead-free piezoelectric ceramics. Japanese Journal of Applied Physics. 2008;47(5):3787-3801. DOI: 10.1143/jjap.47.3787
33.Zhang S-T, Kounga AB, Aulbach E, Ehrenberg H, Rödel J. Giant strain in lead-free piezoceramics Bi0.5Na0.5TiO3–BaTiO3–K0.5Na0.5NbO3 system. Applied Physics Letters. 2007;91(11):112906. DOI: 10.1063/1.2783200
34.N. F. Borrelli, Andrew Herczog, R. D. Maurer, Electro-optic effect of ferroelectric microcrystals in a glass matrix, Applied Physics Letters 7, 117-118 (1965), doi.org/10.1063/1.1754333
35.Bell AJ. Ferroelectrics: The role of ceramic science and engineering. Journal of the European Ceramic Society. 2008;28(7):1307-1317. DOI: 10.1016/j.jeurceramsoc.2007.12.014
36.Graça MP, Ferreira da Silva MG, Valente MA. Structural and electrical properties of SiO2–Li2O–NB2O5 glass and glass-ceramics obtained by thermoelectric treatments. Journal of Materials Science. 2007;42(8):2543-2550. DOI: 10.1007/s10853-006-1208-z
37.Shankar MV, Varma KBR. Crystallization of ferroelectric bismuth vanadate in Bi2O3–V2O5–SRB4O7 glasses. Journal of Non-Crystalline Solids. 1998;226(1-2):145-154. DOI: 10.1016/s0022-3093(97)00490-0
38.Pengpat K, Holland D. Glass-ceramics containing ferroelectric bismuth germanate (BI2GEO5). Journal of the European Ceramic Society. 2003;23(10):1599-1607. DOI: 10.1016/s0955-2219(02)00410-7
39.Koutzarova T, Nedkov I, Ausloos M, Cloots R, Midlarz T, Nogues M. The influence of the polycrystalline state and partial Dy substitution on the superconducting properties of YBCO. Physica Status Solidi (A). 2002;191(1):235-242. DOI: 10.1002/1521-396x
40.Slavov SS, Soreto Teixeira S, Graça MP, Costa LC, Popova V, Dimitriev YB. Bi2O3-TiO2-Nd2O3lead-free material for microwave device applications. International Journal of Applied Glass Science. 2018;10(2):202-207. DOI: 10.1111/ijag.12976
41.Afify A, Slavov S, Mahmoud A, Hassan M, Ataalla M, Staneva A, et al. Determination of the sensing characteristics of SiO2-Bi2O3-TiO2 system toward relative humidity. Journal of Chemical Technology and Metallurgy. 2018;53(6):1073-1080
42.Raykov R, Staneva A, Dimitriev Y, Slavov S, Soreto Teixeira S, Prezas PR, et al. Dielectric relaxation in glass and glass-ceramic materials of the system La2O3-Gd2O3-pbo-mno-B2O3. International Journal of Applied Glass Science. 2018;10(1):75-82. DOI: 10.1111/ijag.12553
43.Nedeltcheva T, Georgieva S, Vladimirova L, Stoyanova-Ivanova A. Increasing the sensitivity of the spectrophotometric determinations of the oxygen content in YBCO superconducting samples using the I3−-starch compound. Talanta. 2009;77(5):1745-1747. DOI: 10.1016/j.talanta.2008.10.019
44.Linden D, Reddy TB. Chapter 31: Nickel-zinc batteries. In: Handbook of Batteries. 3rd ed. New York, New York, USA: McGraw Hill; 2004
45.Shukla A. Nickel-based rechargeable batteries. Journal of Power Sources. 2001;100(1-2):125-148. DOI: 10.1016/s0378-7753(01)00890-4
46.McLarnon FR, Cairns EJ. The secondary alkaline zinc electrode. Journal of the Electrochemical Society. 1991;138(2):645-656. DOI: 10.1149/1.2085653
47.Geng M. Development of advanced rechargeable Ni/MH and Ni/Zn batteries. International Journal of Hydrogen Energy. 2003;28(6):633-636. DOI: 10.1016/s0360-3199(02)00137-4
48.Phillips J, Mohanta S, Geng M, Barton J, McKinney B, Wu J. Environmentally friendly nickel-zinc battery for high rate application with higher specific energy. ECS Transactions. 2009;16(16):11-17. DOI: 10.1149/1.3087437
49.Yuan YF, Yu LQ , Wu HM, Yang JL, Chen YB, Guo SY, et al. Electrochemical performances of Bi based compound film-coated ZnO as anodic materials of Ni–Zn secondary batteries. Electrochimica Acta. 2011;56(11):4378-4383. DOI: 10.1016/j.electacta.2011.01.006
50.Barsoukov E, Macdonald JR, editors. Impedance Spectroscopy: Theory, Experiment, and Applications. Hoboken, NJ, USA: John Wiley & Sons; 2005. DOI: 10.1604/9780471647492
51.Lvovich VF. Impedance Spectroscopy: Applications to Electrochemical and Dielectric Phenomena. Hoboken, NJ, USA: John Wiley & Sons; 2012
52.Slavov S, Krapchanska M, Kashchieva E, Parvanov S, Dimitriev Y. Synthesis of doped bismuth titanate ceramics with Nd2O3 and SiO2 and their electrical properties. Journal of Chemical Technology and Metallurgy. 2013;48(2):174-178
53.Petar NG, Venetka SP, Stanislav SS, Andrei ID. Composition of electrically conductive composite ceramic material and method for its preparation. Pending patent №RO1358. U/00020/26.05/2020. 2020.
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