Search results for: composite solid electrolyte

Authors: Yumei Wang, Xiaoyu Xu, Li Lu

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Solid-state battery adopts solid-state electrolyte such as oxide- and composite-based solid electrolytes. With the adaption of nonflammable or less flammable solid electrolytes, the safety of solid-state batteries can be largely increased. NASICON (Na₃Zr₂Si₂PO₁₂, NZSP) is one of the sodium ion conductors that possess relatively high ionic conductivity, wide electrochemical stable range and good chemical stability. Therefore, it has received increased attention. We report the development of high-density NZSP through liquid phase sintering and its organic-inorganic composite electrolyte. Through reactive liquid phase sintering, the grain boundary conductivity can be largely enhanced while using an organic-inorganic composite electrolyte, interfacial wetting and impedance can be largely reduced hence being possible to fabricate scalable solid-state batteries.

Keywords: solid-state electrolyte, composite electrolyte, electrochemical performance, conductivity

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Authors: Rafiuddin

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Composite solid electrolyte of the salt and oxide type is an effective approach to improve the ionic conductivity in low and intermediate temperature regions. The conductivity enhancement in the composites occurs via interfaces. Because of their high ionic conduction, composite electrolytes have wide applications in different electrochemical devices such as solid-state batteries, solid oxide fuel cells, and electrochemical cells. In this work, a series of novel (1‒x) (CdI2‒Ag2CrO4)‒xAl2O3 composite solid electrolytes has been synthesized. The prepared materials were characterized by X‒ray diffraction, differential thermal analysis, and AC impedance spectroscopy. The impedance spectra show single semicircle representing the simultaneous contribution of grain and grain boundary. The conductivity increased with the increase of Al2O3 content and shows the maximum conductivity (σ= 0.0012 S cm‒1) for 30% of Al2O3 content at 30 ℃.

Keywords: composite solid electrolyte, X-ray diffraction, Impedance spectroscopy, ionic conductivity

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Authors: M. Kotobuki, M. Koishi

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Li1.5Al0.5Ti1.5 (PO4)3(LATP) has received much attention as a solid electrolyte for lithium batteries. In this study, the LATP solid electrolyte is prepared by the co-precipitation method using Li3PO4 as a Li source. The LATP is successfully prepared and the Li ion conductivities of bulk (inner crystal) and total (inner crystal and grain boundary) are 1.1 × 10-3 and 1.1 × 10-4 S cm-1, respectively. These values are comparable to the reported values, in which Li2C2O4 is used as the Li source. It is conclude that the LATP solid electrolyte can be prepared by the co-precipitation method using Li3PO4 as the Li source and this procedure has an advantage in mass production over previous procedure using Li2C2O4 because Li3PO4 is lower price reagent compared with Li2C2O4.

Keywords: co-precipitation method, lithium battery, NASICON-type electrolyte, solid electrolyte

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state Lithium metal batteries (SSLMBs) that contain polymer and ceramic solid electrolytes have received considerable attention as an alternative to substitute liquid electrolytes in lithium metal batteries (LMBs) for highly safe, excellent energy storage performance and stability under elevated temperature situations. Here, a novel fast Li-ion conducting material, LiTa₂PO₈ (LTPO), was synthesized and electrochemical performance of as-prepared powder and LTPO-incorporated composite solid polymer electrolyte (LTPO-CPE) membrane were investigated. The as-prepared LTPO powder was homogeneously dispersed in polymer matrices, and a hybrid solid electrolyte membrane was synthesized via a simple solution-casting method. The room temperature total ionic conductivity (σt) of the LTPO pellet and LTPO-CPE membrane were 0.14 and 0.57 mS cm-1, respectively. A coin battery with NCM811 cathode is cycled under 1C between 2.8 to 4.5 V at room temperature, achieving a Coulombic efficiency of 99.3% with capacity retention of 74.1% after 300 cycles. Similarly, the LFP cathode also delivered an excellent performance at 0.5C with an average Coulombic efficiency of 100% without virtually capacity loss (the maximum specific capacity is at 27th: 138 mAh g−1 and 500th: 131.3 mAh g−1). These results demonstrates the feasibility of a high Li-ion conductor LTPO as a filler, and the developed polymer/ceramic hybrid electrolyte has potential to be a high-performance electrolyte for high-voltage cathodes, which may provide a fresh platform for developing more advanced solid-state electrolytes.

Keywords: li-ion conductor, lithium-metal batteries, composite solid electrolytes, liTa2PO8, high-voltage cathode

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Authors: Gregory Schmidt

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Solid-state lithium batteries are broadly accepted as promising candidates for application in the next generation of EVs as they should offer safer and higher-energy-density batteries. Nonetheless, their development is impeded by many challenges, including the resistive electrode–electrolyte interface originating from the removal of the liquid electrolyte that normally permeates through the porous cathode and ensures efficient ionic conductivity through the cell. One way to tackle this challenge is by formulating composite cathodes containing solid ionic conductors in their structure, but this approach will require the conductors to exhibit chemical stability, electrochemical stability, flexibility, and adhesion and is, therefore, limited to some materials. Recently, Arkema developed a technology called buffering layer which allows the transformation of any conventional porous electrode into a catholyte. This organic layer has a very high ionic conductivity at room temperature, is compatible with all active materials, and can be processed with conventional Gigafactory equipment. Moreover, this layer helps protect the solid ionic conductor from the cathode and anode materials. During this presentation, the manufacture and the electrochemical performance of this layer for different systems of cathode and anode will be discussed.

Keywords: electrochemistry, all solid state battery, materials, interface

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Authors: Rainer Goetz, Zahra Ahaliabadeh, Princess S. Llanos, Aliaksandr S. Bandarenka, Tanja Kallio

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In order to understand the electrochemistry of all-solid-state batteries (ASSBs), the use of electrochemical equivalent circuits with a physical meaning is essential. A model battery is needed whose characterization is independent of the influence of the complex battery assembly. Lithium-Ion Conducting Glass-Ceramic (LICGC), a model solid electrolyte, is chosen for its stability in the air, but on the other hand, it is also well-known for its instability against metallic lithium upon direct contact. Hence, as a first step towards a model ASSB, the interface between lithium and the solid electrolyte (SE) is stabilized with thin (5 nm and 10 nm) coatings of titanium oxide (TO) and lithium titanium oxide (LTO). Impedance data shows that both materials are able to protect the SE surface from rapid degradation due to reducing lithium and, therefore, can serve as a protective interlayer on the anode side of a model ASSB.

Keywords: all-solid-state battery, lithium anode, solid electrolytes, interlayers

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Authors: Abdulrazzak Akroot, Lutfu Namli

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Solid oxide fuel cells (SOFCs) are one of the most promising technologies since they can produce electricity directly from fuel and generate a lot of waste heat that is generally used in the gas turbines to promote the general performance of the thermal power plant. In this study, the energy, and exergy analysis of a solid oxide fuel cell/gas turbine hybrid system was proceed in MATLAB to examine the performance characteristics of the hybrid system in two different configurations: anode-supported model and electrolyte-supported model. The obtained results indicate that if the fuel utilization factor reduces from 0.85 to 0.65, the overall efficiency decreases from 64.61 to 59.27% for the anode-supported model whereas it reduces from 58.3 to 56.4% for the electrolyte-supported model. Besides, the overall exergy reduces from 53.86 to 44.06% for the anode-supported model whereas it reduces from 39.96 to 33.94% for the electrolyte-supported model. Furthermore, increasing the air utilization factor has a negative impact on the electrical power output and the efficiencies of the overall system due to the reduction in the O₂ concentration at the cathode-electrolyte interface.

Keywords: solid oxide fuel cell, anode-supported model, electrolyte-supported model, energy analysis, exergy analysis

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Authors: Rida Batool, Faizah Altaf, Saba Nadeem, Afifa Aslam, Faisal Alamgir, Ghazanfar Abbas

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Today, the need of the hour is to find out alternative renewable energy resources in order to reduce the burden on fossil fuels and prevent alarming environmental degradation. Solid oxide fuel cell (SOFC) is considered a good alternative energy conversion device because it is environmentally benign and supplies energy on demand. The only drawback associated with SOFC is its high operating temperature. In order to reduce operating temperature, different types of composite material are prepared. In this work, titanium doped lanthanum gallium cerate (LGCT) composite is prepared through the co-precipitation method as electrolyte and examined for low temperature SOFCs (LTSOFCs). The structural properties are analyzed by X-Ray Diffractometry (XRD) and Fourier Transform Infrared (FTIR) Spectrometry. The surface properties are investigated by Scanning Electron Microscopy (SEM). The electrolyte LGCT has the formula LGCTO₃ because it showed two phases La.GaO and Ti.CeO₂. The average particle size is found to be (32 ± 0.9311) nm. The ionic conductivity is achieved to be 0.073S/cm at 650°C. Arrhenius plots are drawn to calculate activation energy and found 2.96 eV. The maximum power density and current density are achieved at 68.25mW/cm² and 357mA/cm², respectively, at 650°C with hydrogen. The prepared material shows excellent ionic conductivity at comparatively low temperature, that makes it a potentially good candidate for LTSOFCs.

Keywords: solid oxide fuel cell, LGCTO₃, cerium composite oxide, ionic conductivity, low temperature electrolyte

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Authors: Kumlachew Zelalem Walle, Chun-Chen Yang

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Solid-state lithium metal batteries (SSLMBs) are considered promising candidates for next-generation energy storage devices due to their superior energy density and excellent safety. However, recent findings have shown that the formation of lithium (Li) dendrites in SSLMBs still exhibits a terrible growth ability, which makes the development of SSLMBs have to face the challenges posed by the Li dendrite problem. In this work, an inorganic/organic mixture coating material (g-C3N4/ZIF-8/PVDF) was used to modify the surface of lithium metal anode (LMA). Then the modified LMA (denoted as g-C₃N₄@Li) was assembled with lithium nafion (LiNf) coated commercial NCM811 (LiNf@NCM811) using a bilayer hybrid solid electrolyte (Bi-HSE) that incorporated 20 wt.% (vs. polymer) LiNf coated Li6.05Ga0.25La3Zr2O11.8F0.2 ([email protected]) filler faced to the positive electrode and the other layer with 80 wt.% (vs. polymer) filler content faced to the g-C₃N₄@Li. The garnet-type Li6.05Ga0.25La3Zr2O11.8F0.2 (LG0.25LZOF) solid electrolyte was prepared via co-precipitation reaction process from Taylor flow reactor and modified using lithium nafion (LiNf), a Li-ion conducting polymer. The Bi-HSE exhibited high ionic conductivity of 6.8  10–4 S cm–1 at room temperature, and a wide electrochemical window (0–5.0 V vs. Li/Li+). The coin cell was charged between 2.8 to 4.5 V at 0.2C and delivered an initial specific discharge capacity of 194.3 mAh g–1 and after 100 cycles it maintained 81.8% of its initial capacity at room temperature. The presence of a nano-sheet g-C3N4/ZIF-8/PVDF as a composite coating material on the LMA surface suppress the dendrite growth and enhance the compatibility as well as the interfacial contact between anode/electrolyte membrane. The g-C3N4@Li symmetrical cells incorporating this hybrid electrolyte possessed excellent interfacial stability over 1000 h at 0.1 mA cm–2 and a high critical current density (1 mA cm–2). Moreover, the in-situ formation of Li3N on the solid electrolyte interface (SEI) layer as depicted from the XPS result also improves the ionic conductivity and interface contact during the charge/discharge process. Therefore, these novel multi-layered fabrication strategies of hybrid/composite solid electrolyte membranes and modification of the LMA surface using mixed coating materials have potential applications in the preparation of highly safe high-voltage cathodes for SSLMBs.

Keywords: high-voltage cathodes, hybrid solid electrolytes, garnet, graphitic-carbon nitride (g-C3N4), ZIF-8 MOF

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Authors: Rafiuddin

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Solid polymer electrolytes have emerged as an area of interest in the field of solid state chemistry owing to their facile and cost-effective synthesis and number of applications in different areas of chemistry, extending over a wide range of temperatures. In the present work, polymer composite solid electrolyte comprising of Polyaniline (PANI) as polymer and potassium silver iodide (KAg4I5) using alumina (Al2O3) of different compositions having the formula (1-x) PANI- KAg4I5. x Al2O3 with x ranging from 0.0 to 0.5 was prepared by solid state reaction method. The structural elucidation and characterization was done by X- Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric- Differential Thermal Analysis (TG-DTA) and Impedance Spectroscopy. The thermal analysis shows a phase transition at 147°C attributed to β-α phase transition of AgI due to the disproportionation of KAg4I5 to AgI and KAg2I3 at temperatures higher than 36°C. The X Ray diffraction analysis also confirms the presence of both AgI and KAg2I3 in the samples. The conductivities recorded over a temperature range of 40-250° C lie in the range of 10-1 to 10-3 S cm-1. Maximum conductivity was seen in the compositon x = 0.4 i.e. 1.84 × 10-2 Scm-1 at 313 K and 1.38 × 10-1 Scm-1 at 513 K, with a minimum activation energy of 0.14 eV.

Keywords: polymer solid electrolytes, XRD, DTA, electrical conductivity, impedance spectroscopy

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Authors: Benjamin Orimolade, Emily Draper

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The interest in all solid electrochromic devices (ECD) is ongoing. This is because these devices offer realistic applications of electrochromic materials in products such as sensors, windows and energy storage devices. The use of quasi-solid (gel) electrolytes for the construction of these ECDs is attractive because of their ease of preparation, availability, low cost, improved electrochromic performance, good ionic conductivity and prevention of leakages in ECDs. Herein, we developed a gel electrolyte consisting of polyacrylamide modified with succinonitrile for an ECD containing leucine-modified naphthalene diimide (NDI-L) as electrochromic material. The amount of succinonitrile in the gel was optimized, and the structure, surface morphology, and ionic conductivity of the electrolytes were assessed using microscopic techniques and electrochemical methods. The ECD fabricated with the gel electrolyte displayed good electrochromic performance with a fast switching response of up to 10 s and outstanding stability. These results add significant insight into understanding the inter- and intra-molecular interaction in succinonitrile gel electrolytes and provide a typical practicable high-performance gel electrolyte material for solid electrochromic devices.

Keywords: electrochromic device, gel electrolytes, naphthalene diimide, succinonitrile

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Authors: Fernando G. Torres, Omar P. Troncoso

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A wide range of bacteria synthesizes and secretes polymeric substances composed of a mixture of high-molecular-mass heteropolysaccharides. Nostoc commune cyanobacteria grow in colonial spherules of 10-20 mm in diameter. These spherules are filled with an internal gel made from a variety of polysaccharides known as Nostoc commune exopolysaccharides (NCE). In this paper, we report the use of these exopolysaccharides as a raw material for the preparation of a solid polymer electrolyte. Ammonium iodide and 1-butyl-3-methylimidazolium chloride ([Bmim]Cl) salts were used to provide NCE films with ionic conductivity. In addition, a carboxymethylation treatment was used to further increase the conductivity of NCE films. The structural characterization of the NCE films was assessed by FTIR, XRD, and DSC tests. Broadband dielectric spectroscopy (BDS) and dielectric thermal analysis (DETA) were used to evaluate the ionic conductivity of the samples. The results showed that NCE can be used to prepare solid polymer electrolyte films and that carboxymethylation improves their ionic conductivity. These NCE films can be used in the development of novel energy storage devices such as flat batteries or supercapacitors.

Keywords: polymer electrolyte, Nostoc commune, cyanobacteria, exopolysaccharides

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Authors: Yong-Jie Lin, Yi-Feng Lin

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In this study, scandium-doped yttria-stabilized zirconia (ScYSZ) and In2O3 nanoparticles (NPs) with cubic crystalline structures were successfully prepared using a facile hydrothermal process. ScYSZ films were prepared by the pressing of ScYSZ NPs and were further used for the electrolyte of solid oxide fuel cells (SOFCs). To increase the ionic conductivity of the ScYSZ electrolyte, different amounts of In2O3 NPs [0 wt% (X(In2O3)=0), 0.21 wt% (X(In2O3)=0.001) and 1.13 wt% (X(In2O3)=0.005)] were doped in the ScYSZ films to increase their oxygen vacancy. The result shows In2O3 NP/ScYSZ films with 1.13 wt% (X(In2O3 )=0.005) In2O3 NPs doping are with largest ionic conductivity of 0.057Ω-1 cm-1 at 900oC, which is 1.6 and 1.8 times higher than YSZ and In2O3 NP/ScYSZ films with 0.21 wt% (X(In2O3)=0.001) In2O3 NPs doping, respectively.

Keywords: indium oxide/scandium doping Yttria-stabilized zirconia, solid oxide fuel cells, scandium-doped yttria-stabilized zirconia, indium oxide

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Authors: Hyun-Jong Choi, Minjun Kwak, Doo-Won Seo, Sang-Kuk Woo, Sun-Dong Kim

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Solid Oxide Cell(SOC) systems can contribute to the transition to the hydrogen society by utilized as a power and hydrogen generator by the electrochemical reaction with high efficiency at high operation temperature (>750 ℃). La1-xSrxCo1-yFeyO3, which is an air electrode, is occurred stability degradations due to reaction and delamination with yittria stabilized zirconia(YSZ) electrolyte in a water electrolysis mode. To complement this phenomenon SOCs need gadolinium doped ceria(GDC) buffer layer between electrolyte and air electrode. However, GDC buffer layer requires a high sintering temperature and it causes a reaction with YSZ electrolyte. This study carried out low temperature sintering of GDC layer by applying Cu-oxide as a sintering aid. The effect of a copper additive as a sintering aid to lower the sintering temperature for the construction of solid oxide fuel cells (SOFCs) was investigated. GDC buffer layer with 0.25-10 mol% CuO sintering aid was prepared by reacting GDC power and copper nitrate solution followed by heating at 600 ℃. The sintering of CuO-added GDC powder was optimized by investigating linear shrinkage, microstructure, grain size, ionic conductivity, and activation energy of CuO-GDC electrolytes at temperatures ranging from 1100 to 1400 ℃. The sintering temperature of the CuO-GDC electrolyte decreases from 1400 ℃ to 1100 ℃ by adding the CuO sintering aid. The ionic conductivity of the CuO-GDC electrolyte shows a maximum value at 0.5 mol% of CuO. However, the addition of CuO has no significant effects on the activation energy of GDC electrolyte. GDC-LSCF layers were co-sintering at 1050 and 1100 ℃ and button cell tests were carried out at 750 ℃.

Keywords: Co-Sintering, GDC-LSCF, Sintering Aid, solid Oxide Cells

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Authors: Siddhant Srivastav, Shilpa Singh, Sumanta Kumar Meher

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Innovative renewable energy sources for energy storage/conversion is the demand of the current scenario in electrochemical machinery. In this context, choosing suitable organic precipitants for tuning the crystal characteristics and microstructures is a challenge. On the same note, herein we report broccoli flower-like porous Mn3O4/NiSe2−MnSe2 composite synthesized using a simple two step hydrothermal synthesis procedure assisted by sluggish precipitating agent and an effective cappant followed by intermediated anion exchange. The as-synthesized material was exposed to physical and chemical measurements depicting poly-crystallinity, stronger bonding and broccoli flower-like porous arrangement. The material was assessed electrochemically by cyclic voltammetry (CV), chronopotentiometry (CP) and electrochemical impedance spectroscopy (EIS) measurements. The Electrochemical studies reveal redox behavior, supercapacitive charge-discharge shape and extremely low charge transfer resistance. Further, the fabricated Mn3O4/NiSe2−MnSe2 composite based solid-state hybrid supercapacitor (Mn3O4/NiSe2−MnSe2 ||N-rGO) delivers excellent rate specific capacity, very low internal resistance, with energy density (~34 W h kg–1) of a typical rechargeable battery and power density (11995 W kg–1) of an ultra-supercapacitor. Consequently, it can be a favorable contender for supercapacitor applications for high performance energy storage utilizations. A definitive exhibition of the supercapacitor device is credited to electrolyte-ion buffering reservior alike behavior of broccoli flower like Mn3O4/NiSe2−MnSe2, enhanced by upgraded electronic and ionic conductivities of N- doped rGO (negative electrode) and PVA/KOH gel (electrolyte separator), respectively

Keywords: electrolyte-ion buffering reservoir, intermediated-anion exchange, solid-state hybrid supercapacitor, supercapacitive charge-dischargesupercapacitive charge-discharge

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Authors: Boor Singh Lalia, Yarjan Abdul Samad, Raed Hashaikeh

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Three different kinds of solid polymer electrolytes were prepared using polyethylene oxide (PEO) as a base polymer, networked cellulose (NC) as a physical support and LiClO4 as a conductive salt for the electrolytes. Networked cellulose, a modified form of cellulose, is a biodegradable and environmentally friendly additive which provides a strong fibrous networked support for structural stability of the electrolytes. Although the PEO/NC/LiClO4 electrolyte retains its structural integrity and mechanical properties at 100oC as compared to pristine PEO-based polymer electrolytes, it suffers from poor ionic conductivity. To improve the room temperature conductivity of the electrolyte, PEO is replaced by the polyethylene glycol (PEG) which is a liquid phase that provides high mobility for Li+ ions transport in the electrolyte. PEG/NC/LiClO4 shows improvement in ionic conductivity compared to PEO/NC/LiClO4 at room temperature, but it is brittle and tends to form cracks during processing. An advanced solid polymer electrolyte with optimum ionic conductivity and mechanical properties is developed by using a ternary system: TEGDME/PEO/NC+LiClO4. At room temperature, this electrolyte exhibits an ionic conductivity to the order of 10-5 S/cm, which is very high compared to that of the PEO/LiClO4 electrolyte. Pristine PEO electrolytes start melting at 65 °C and completely lose its mechanical strength. Dynamic mechanical analysis of TEGDME: PEO: NC (70:20:10 wt%) showed an improvement of storage modulus as compared to the pristine PEO in the 60–120 °C temperature range. Also, with an addition of NC, the electrolyte retains its mechanical integrity at 100 oC which is beneficial for Li-ion battery operation at high temperatures. Differential scanning calorimetry (DSC) and thermal gravimetry analysis (TGA) studies revealed that the ternary polymer electrolyte is thermally stable in the lithium ion battery operational temperature range. As-prepared polymer electrolyte was used to assemble LiFePO4/ TEGDME/PEO/NC+LiClO4/Li half cells and their electrochemical performance was studied via cyclic voltammetry and charge-discharge cycling.

Keywords: solid polymer electrolyte, ionic conductivity, mechanical properties, lithium ion batteries, cyclic voltammetry

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Authors: Umran Kurtan, Hamide Aydin, Sevim Unugur Celik, Ayhan Bozkurt

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In the present work, novel hBN/polyacrylonitrile composite nanofibers were produced via electrospinning approach and loaded with the electrolyte for rechargeable lithium-ion battery applications. The electrospun nanofibers comprising various hBN contents were characterized by using Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The influence of hBN/PAN ratios onto the properties of the porous composite system, such as fiber diameter, porosity, and the liquid electrolyte uptake capability were systematically studied. Ionic conductivities and electrochemical characterizations were evaluated after loading electrospun hBN/PAN composite nanofiber with liquid electrolyte, i.e., 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (1:1 vol). The electrolyte loaded nanofiber has a highest ionic conductivity of 10−3 S cm⁻¹ at room temperature. According to cyclic voltammetry (CV) results it exhibited a high electrochemical stability window up to 4.7 V versus Li+/Li. Li//10 wt% hBN/PAN//LiCO₂ cell was produced which delivered high discharge capacity of 144 mAhg⁻¹ and capacity retention of 92.4%. Considering high safety and low cost properties of the resulting hBN/PAN fiber electrolytes, these materials can be suggested as potential separator materials for lithium-ion batteries.

Keywords: hexagonal boron nitride, polyacrylonitrile, electrospinning, lithium ion battery

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Authors: Jinliang Yuan, Jong-Sung Yu, Bengt Sundén

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A computational fluid dynamics (CFD) model is developed for rechargeable non-aqueous electrolyte lithium-air batteries with a partial opening for oxygen supply to the cathode. Multi-phase transport phenomena occurred in the battery are considered, including dissolved lithium ions and oxygen gas in the liquid electrolyte, solid-phase electron transfer in the porous functional materials and liquid-phase charge transport in the electrolyte. These transport processes are coupled with the electrochemical reactions at the active surfaces, and effects of discharge reaction-generated solid Li2O2 on the transport properties and the electrochemical reaction rate are evaluated and implemented in the model. The predicted results are discussed and analyzed in terms of the spatial and transient distribution of various parameters, such as local oxygen concentration, reaction rate, variable solid Li2O2 volume fraction and porosity, as well as the effective diffusion coefficients. It is found that the effect of the solid Li2O2 product deposited at the solid active surfaces is significant on the transport phenomena and the overall battery performance.

Keywords: Computational Fluid Dynamics (CFD), modeling, multi-phase, transport phenomena, lithium-air battery

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Authors: Kwangwon Seo, Haksoo Han

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Al-Si was synthesized and introduced in poly 2,2’-m-(phenylene)-5,5’-bibenzimidazole (PBI). As a result, a series of five Al-Si/PBI composite (ASPBI) membranes (0, 3, 6, 9, and 12 wt.%) were developed and characterized for application in high temperature polymer electrolyte membrane fuel cells (HT-PEMFCs). The chemical and morphological structure of ASPBI membranes were analyzed by Fourier transform infrared spectroscopy, X-ray diffractometer and scanning electron microscopy. According to the doping level test and thermogravimetric analysis, as the concentration of Al-Si increased, the doping level increased up to 475%. Moreover, the proton conductivity, current density at 0.6V, and maximum power density of ASPBI membranes increased up to 0.31 Scm-1, 0.320 Acm-2, and 0.370 Wcm-2, respectively, because the increased concentration of Al-Si allows the membranes to hold more PA. Alternatively, as the amount of Al-Si increased, the tensile strength of PA-doped and -undoped membranes decreased. This was resulted by both excess PA and aggregation, which can cause serious degradation of the membrane and induce cracks. Moreover, the PA-doped and -undoped ASPBI12 had the lowest tensile strength. The improved performances of ASPBI membranes imply that ASPBI membranes are possible candidates for HT-PEMFC applications. However, further studies searching to improve the compatibility between PBI matrix and inorganic and optimize the loading of Al-Si should be performed.

Keywords: composite membrane, high temperature polymer electrolyte membrane fuel cell, membrane electrode assembly, polybenzimidazole, polymer electrolyte membrane, proton conductivity

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Authors: Y. Mateyshina, A.Ulihin, N.Uvarov

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Electrolytes with different type of charge carrier can find widely application in different using, e.g. sensors, electrochemical equipments, batteries and others. One of important components ensuring stable functioning of the equipment is electrolyte. Electrolyte has to be characterized by high conductivity, thermal stability, and wide electrochemical window. In addition to many advantageous characteristic for liquid electrolytes, the solid state electrolytes have good mechanical stability, wide working range of temperature range. Thus search of new system of solid electrolytes with high conductivity is an actual task of solid state chemistry. Families of alkali perchlorates and nitrates have been investigated by us earlier. In literature data about transport properties of alkali nitrites are absent. Nevertheless, alkali nitrites MeNO2 (Me= Li+, Na+, K+, Rb+ and Cs+), except for the lithium salt, have high-temperature phases with crystal structure of the NaCl-type. High-temperature phases of nitrites are orientationally disordered, i.e. non-spherical anions are reoriented over several equivalents directions in the crystal lattice. Pure lithium nitrite LiNO2 is characterized by ionic conductivity near 10-4 S/cm at 180°C and more stable as compared with lithium nitrate and can be used as a component for synthesis of composite electrolytes. In this work composite solid electrolytes in the binary system LiNO2 - A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) were synthesized and their structural, thermodynamic and electrical properties investigated. Alkali nitrite was obtained by exchange reaction from water solutions of barium nitrite and alkali sulfate. The synthesized salt was characterized by X-ray powder diffraction technique using D8 Advance X-Ray Diffractometer with Cu K radiation. Using thermal analysis, the temperatures of dehydration and thermal decomposition of salt were determined.. The conductivity was measured using a two electrode scheme in a forevacuum (6.7 Pa) with an HP 4284A (Precision LCR meter) in a frequency range 20 Hz < ν < 1 MHz. Solid composite electrolytes LiNO2 - A A (A= MgO, -Al2O3, Fe2O3, CeO2, SnO2, SiO2) have been synthesized by mixing of preliminary dehydrated components followed by sintering at 250°C. In the series of nitrite of alkaline metals Li+-Cs+, the conductivity varies not monotonically with increasing radius of cation. The minimum conductivity is observed for KNO2; however, with further increase in the radius of cation in the series, the conductivity tends to increase. The work was supported by the Russian Foundation for Basic research, grant #14-03-31442.

Keywords: conductivity, alkali nitrites, composite electrolytes, transport properties

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Authors: Dimitra Sygkridou, Dimitrios Karageorgopoulos, Elias Stathatos, Evangelos Vitoratos

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Transparent nickel doped cobalt sulfide was fabricated on a SnO2:F electrode and tested as an efficient electrocatalyst and as an alternative to the expensive platinum counter electrode. In order to investigate how this electrode could affect the electrical characteristics of a dye-sensitized solar cell, we manufactured cells with the same TiO2 photoanode sensitized with dye (N719) and employing the same quasi-solid electrolyte, altering only the counter electrode used. The cells were electrically and electrochemically characterized and it was observed that the ones with the Ni doped CoS2 outperformed the efficiency of the cells with the Pt counter electrode (3.76% and 3.44% respectively). Particularly, the higher efficiency of the cells with the Ni doped CoS2 counter electrode (CE) is mainly because of the enhanced photocurrent density which is attributed to the enhanced electrocatalytic ability of the CE and the low charge transfer resistance at the CE/electrolyte interface.

Keywords: nickel doped cobalt sulfide, counter electrodes, dye-sensitized solar cells, quasi-solid state electrolyte, hybrid organic-inorganic materials

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Authors: U. Farooq, A. Samson, V. Thangadurai, R. Edwards

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In recent years, an impressive research has been conducted to introduce the solid-state electrolytes for the future energy storage devices like Li-ion batteries more specifically. In this work we tried to prepare a ceramic electrolyte (Li6.5 La2.5 Ba0.5 Nb Zr O12(LLBNZO)) and sintered the pallets of as-prepared material at elevated temperature like 1050, 1100, 1150 and 1200 °C. The objective to carry out this research was to observe the effect of temperature on porosity, density and transport properties of materials. Preliminary results suggest that the material sintered at higher temperature could show enhanced performance in terms of fast ionic transport. This enhancement in performance can be attributed to low porosity of materials which is result of high temperature sintering.

Keywords: solid state battery, electrolyte, garnet structures, Li-ion battery

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Authors: Hu-Cheng Weng, Jhen-Ting Huang, Chia-Chia Chang, An-Ya Lo

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In this study, carbon mesoporous material, CMK-3, was adopted as supporting material for electroactive polymerspolyaniline (PANI), polyaniline, for supercapacitor application, where hydroquinone (HQ) was integrated to enhance the redox reaction of PANI. The results show that the addition of PANI improves the capacitance of electrode from 89 F/g (CMK-3) to 337 F/g (PANI/CMK-3), the addition of HQ furtherly improves the capacitance to 463 F/g (PANI/CMK-3/HQ). The PANI provides higher energy density and also acts as binder of the electrode; the CMK-3 provides higher electron double layer capacitance EDLC and stabilize the polyaniline by its highly porosity. With the addition of HQ, the capacitance of PANI/CMK-3 was further enhanced. In-situ analyses including cyclic voltammetry (CV), chronopotentiometry (CP), electron impedance spectrum (EIS) analyses were applied for electrode performance examination. For materials characterization, the crystal structure, morphology, microstructure, and porosity were examined by X-ray diffraction (XRD), scanning electron microscope (SEM), and transmission electron microscopy (TEM), and 77K N2 adsorption/desorption analyses, respectively. The effects of electrolyte pH value, PANI polymerization time, HQ concentration, and PANI/CMK-3 ratio on capacitance were discussed. The durability was also studied by long-term operation test. The results show that PANI/CMK-3/HQ with great potential for supercapacitor application. Finally, the potential of all-solid PANI/CMK-3/HQ based supercapacitor was successfully demonstrated.

Keywords: CMK3, PANI, redox electrolyte, solid supercapacitor

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Authors: Jen-Yuan Wang, Min-Chuan Wang, Der-Jun Jan

Abstract:

Polymer electrolytes can be classified into four major categories, solid polymer electrolytes (SPEs), gel polymer electrolytes (GPEs), polyelectrolytes and composite polymer electrolytes. SPEs suffer from low ionic conductivity at room temperature. The main problems for GPEs are the poor thermal stability and mechanical properties. In this study, a GPE containing PMMA and succinonitrile is prepared to solve the problems mentioned above, and applied to the assembly of a quasi-solid-state electrochromic device (ECD). In the polymer electrolyte, poly(methyl methacrylate) (PMMA) is the polymer matrix and propylene carbonate (PC) is used as the plasticizer. To enhance the mechanical properties of this GPE, succinonitrile (SN) is introduced as the additive. For the electrochromic materials, tungsten oxide (WO3) is used as the cathodic coloring film, which is fabricated by pulsed dc magnetron reactive sputtering. For the anodic coloring material, Prussian blue nanoparticles (PBNPs) are synthesized and coated on the transparent Sn-doped indium oxide (ITO) glass. The thickness of ITO, WO3 and PB film is 110, 170 and 200 nm, respectively. The size of the ECD is 5×5 cm2. The effect of the introduction of SN into the GPEs is discussed by observing the electrochromic behaviors of the WO3-PB ECD. Besides, the composition ratio of PC to SN is also investigated by measuring the ionic conductivity. The optimized ratio of PC to SN is 4:1, and the ionic conductivity under this condition is 6.34x10-5 S∙cm-1, which is higher than that of PMMA/PC (1.35x10-6 S∙cm-1) and PMMA/EC/PC (4.52x10-6 S∙cm-1). This quasi-solid-state ECD fabricated with the PMMA/SN based GPE shows an optical contrast of ca. 53% at 690 nm. The optical transmittance of the ECD can be reversibly modulated from 72% (bleached) to 19% (darkened), by applying potentials of 1.5 and -2.2 V, respectively. During the durability test, the optical contrast of this ECD remains 44.5% after 2400 cycles, which is 83% of the original one.

Keywords: electrochromism, tungsten oxide, prussian blue, poly(methyl methacrylate), succinonitrile

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Authors: Maria V. Morozova, Yulia V. Emelyanova, Anastasia A. Levina, Elena S. Buyanova, Zoya A. Mikhaylovskaya, Sofia A. Petrova

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The solid solutions of lanthanum niobates substituted by yttrium, bismuth and tungsten were synthesized. The structure of the solid solutions is either LaNbO4-based monoclinic or BiNbO4-based triclinic. The series where niobium is substituted by tungsten on B site reveals phase-modulated structure. The values of cell parameters decrease with increasing the dopant concentration for all samples except the tungsten series although the latter show higher total conductivity.

Keywords: impedance spectroscopy, LaNbO4, lanthanum ortho-niobates, solid electrolyte

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Authors: Wei Quan, Liu Chao, Mohammed N. Afsar

Abstract:

The dielectric properties and ionic conductivity of novel "ceramic state" polymer electrolytes for high capacity lithium battery are characterized by radio-frequency and Microwave methods in two broad frequency ranges from 50 Hz to 20 KHz and 4 GHz to 40 GHz. This innovative solid polymer electrolyte which is highly ionic conductive (10-3 S/cm at room temperature) from -40 oC to +150 oC and can be used in any battery application. Such polymer exhibits properties more like a ceramic rather than polymer. The various applied measurement methods produced accurate dielectric results for comprehensive analysis of electrochemical properties and ion transportation mechanism of this newly invented polymer electrolyte. Two techniques and instruments employing air gap measurement by capacitance bridge and inwave guide measurement by vector network analyzer are applied to measure the complex dielectric spectra. The complex dielectric spectra are used to determine the complex alternating current electrical conductivity and thus the ionic conductivity.

Keywords: polymer electrolyte, dielectric permittivity, lithium battery, ionic relaxation, microwave measurement

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Authors: Hatem I. Mokhtar, Randa A. Abd-El-Salam, Ghada M. Hadad

Abstract:

An improved nano-composite of self-doped polyaniline nanofibers and silica-coated magnetite nanoparticles were prepared and evaluated for suitability to magnetic dispersive micro solid-phase extraction. The work focused on optimization of the composite capacity to extract four fluoroquinolones (FQs) antibiotics, ciprofloxacin, enrofloxacin, danofloxacin, and difloxacin from water and improvement of composite stability towards acid and atmospheric degradation. Self-doped polyaniline nanofibers were prepared by oxidative co-polymerization of aniline with anthranilic acid. Magnetite nanopariticles were prepared by alkaline co-precipitation and coated with silica by silicate hydrolysis on magnetite nanoparticles surface at pH 6.5. The composite was formed by self-assembly by mixing self-doped polyaniline nanofibers with silica-coated magnetite nanoparticles dispersions in ethanol. The composite structure was confirmed by transmission electron microscopy (TEM). Self-doped polyaniline nanofibers and magnetite chemical structures were confirmed by FT-IR while silica coating of the magnetite was confirmed by Energy Dispersion X-ray Spectroscopy (EDS). Improved stability of the composite magnetic component was evidenced by resistance to degrade in 2N HCl solution. The adsorption capacity of self-doped polyaniline nanofibers based composite was higher than previously reported corresponding composite prepared from polyaniline nanofibers instead of self-doped polyaniline nanofibers. Adsorption-pH profile for the studied FQs on the prepared composite revealed that the best pH for adsorption was in range of 6.5 to 7. Best extraction recovery values were obtained at pH 7 using phosphate buffer. The best solvent for FQs desorption was found to be 0.1N HCl in methanol:water (8:2; v/v) mixture. 20 mL of Spiked water sample with studied FQs were preconcentrated using 4.8 mg of composite and resulting extracts were analysed by HPLC-UV method. The prepared composite represented a suitable adsorbent phase for magnetic dispersive micro-solid phase application.

Keywords: fluoroquinolones, magnetic dispersive micro extraction, nano-composite, self-doped polyaniline nanofibers

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Authors: Shari Ann S. Botin, Ruziel Larmae T. Gimpaya, Rembrant Rockwell Gamboa, Rinlee Butch M. Cervera

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In recent years, demand for the use of solid electrolytes as alternatives to liquid electrolytes has increased due to recurring battery safety and stability issues, in addition to an increase in energy density requirement which can be made possible by using solid electrolytes. Among the solid electrolyte systems, Li7La3Zr2O12 (LLZ) is one of the most promising as it exhibits good chemical stability against Li metal and has a relatively high ionic conductivity. In this study, pure and doped LLZ were synthesized via conventional solid state reaction. The precursor chemicals (such as LiOH, La2O3, Ga2O3 and ZrO2) were ground and then calcined at 900 °C, pressed into pellets and finally sintered at 1000 °C to 1200 °C. The microstructure and ionic conductivity of the obtained samples have been investigated. Results show that for pure LLZ, sintering at lower temperature (1000 °C) produced tetragonal LLZ while sintering at higher temperatures (≥ 1150 °C) produced cubic LLZ based from the XRD results. However, doping with Ga produces an easier formation of LLZ with cubic structure at lower sintering duration. On the other hand, the lithium conductivity of the samples was investigated using electrochemical impedance spectroscopy at room temperature. Among the obtained samples, Ga-doped LLZ sintered at 1150 °C obtained the highest ionic conductivity reaching to about 1x10⁻⁴ S/cm at room temperature. In addition, fabrication and initial investigation of an all-solid state Lithium Battery using the synthesized LLZ sample with the use of commercial cathode materials have been investigated.

Keywords: doped LLZ, lithium-ion battery, pure LLZ, solid electrolytes

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Authors: C. S. Wong, K. H. Badri, N. Ataollahi, K. P. Law, M. S. Su’ait, N. I. Hassan

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Novel bio-based polymer electrolyte was synthesized with LiClO4 as the main source of charge carrier. Initially, polyurethane-LiClO4 polymer electrolytes were synthesized via polymerization method with different NCO/OH ratios and labelled as PU1, PU2, PU3, and PU4. Subsequently, the chemical, thermal properties and ionic conductivity of the films produced were determined. Fourier transform infrared (FTIR) analysis indicates the co-ordination between Li+ ion and polyurethane in PU1 due to the greatest amount of hard segment of polyurethane in PU1 as proven by soxhlet analysis. The structures of polyurethanes were confirmed by 13 nuclear magnetic resonance spectroscopy (13C NMR) and FTIR spectroscopy. Differential scanning calorimetry (DSC) analysis indicates PU 1 has the highest glass transition temperature (Tg) corresponds to the most abundant urethane group which is the hard segment in PU1. Scanning electron microscopy (SEM) of the PU-LiClO4 shows the good miscibility between lithium salt and the polymer. The study found that PU1 possessed the greatest ionic conductivity (1.19 × 10-7 S.cm-1 at 298 K and 5.01 × 10-5 S.cm-1 at 373 K) and the lowest activation energy, Ea (0.32 eV) due to the greatest amount of hard segment formed in PU 1 induces the coordination between lithium ion and oxygen atom of carbonyl group in polyurethane. All the polyurethanes exhibited linear Arrhenius variations indicating ion transport via simple lithium ion hopping in polyurethane. This research proves the NCO content in polyurethane plays an important role in affecting the ionic conductivity of this polymer electrolyte.

Keywords: ionic conductivity, palm kernel oil-based monoester-OH, polyurethane, solid polymer electrolyte

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Authors: Yasin Polat, Yılmaz Dağdemir, Mehmet Arı

Abstract:

Samarium (III) oxide and Ytterbium (III) oxide doped Bismuth trioxide solid solutions, the nano ceramic (Bi2O3)1-x-y(Sm2O3)x(Yb2O3)y ternary system were obtained with x=5, 20 mol %, and y=5, 20 mol % dopant concentrations have been synthesized in air atmosphere with solid state reaction. Temperature dependent electrical conductivity of the samples have been investigated by 4-point probe technique by heating and cooling process. Doped-Bi2O3 materials of solid electrolyte systems are good oxygen anions O2-conductors which have collected much attention as potential solid ceramic electrolytes for solid oxide fuel cells (SOFCs) because of their relatively high oxygen ionic conductivity at lower temperatures.(Bi2O3)-based electrolytes have also wide other technological applications in devices with high economical interest such as oxygen sensors, ceramic membranes for oxygen separation, oxygen pumps, catalyzing of some heterogeneous reactions, partial oxidation of the hydrocarbons, and additive material in paints. In recent years, many experimental researches have mostly focused on improving of the Bi-based electrolytes which have high oxide ionic conductivity at low temperatures and better performance as alternatives to traditional stabilized zirconia has taken place. Generally, these systems are much better solid electrolytes than well-known stabilized zirconia, because some of the bismuth trioxide phases exhibit higher ion conductivity than other oxide ionic conductors. Crystal structure of the Nano ceramic (Bi2O3)1-x-y(Sm2O3)x(Yb2O3)y has been determined by X-Ray powder diffractions (XRD) measurements before and after electrical conductivity measurements of the samples. Surface and grain structure properties of the samples were determined by SEM analysis. The samples which synthesized in this study can be used in industrial applications such as electrolytes of the solid oxide fuel cells (SOFC).

Keywords: 4-point probe technique, bismuth trioxide, solid state reaction, solid oxide fuel cell

Procedia PDF Downloads 255