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By constraining the charging–discharging to the alloying regime, Sb1.9Al0.1S3 nanorods deliver superior electrochemical performance for 1000 cycles at 5C rate, unlike poor cyclability observed when cycled in both conversion and alloying regimes.

Irradiation of materials by high energy (∼MeV) ions causes intense electronic excitations through inelastic transfer of energy that significantly modifies physicochemical properties. We report the effect of 100 MeV Ag ion irradiation and resultant localized (∼few nm) thermal spike on vertically oriented TiO2 nanorods (∼100 nm width) towards tailoring their structural and electronic properties. Rapid quenching of the thermal spike induced molten state within ∼0.5 picosecond results in a distortion in the crystalline structure that increases with increasing fluences (ions per cm2). Microstructural investigations reveal ion track formation along with a corrugated surface of the nanorods. The thermal spike simulation validates the experimental observation of the ion track dimension (∼10 nm diameter) and melting of the nanorods. The optical absorption study shows direct bandgap values of 3.11 eV (pristine) and 3.23 eV (5 × 1012 ions per cm2) and an indirect bandgap value of 3.10 eV for the highest fluence (5 × 1013 ions per cm2). First principles electronic structure calculations corroborate the direct-to-indirect transition that is attributed to the structural distortion at the highest fluence. This work presents a unique technique to selectively tune the properties of nanorods for versatile applications.

Since the inception of cobalt phthalocyanine for oxygen reduction reaction (ORR), non-platinum group metals have been the central focus in the area of fuel-cell electrocatalysts. Besides Fe-Nx active sites, a large variety of species are formed during the pyrolysis, but studies related to their ORR activity have been given less importance in the literature. Fe2O3 is one among them, and this study describes the role of Fe2O3 in the ORR. The Fe2O3 is carefully synthesized on various carbon supports and characterized using X-ray photoelectron spectroscopy (XPS) spectra, high-resolution transmission electron microscopy (HRTEM) images, and surface area analysis. The characterization techniques reveal that the Fe2O3 nanoparticles are present in the pores of the carbon supports, having a particle size ranging from 4 to 15 nm. The current density of the ORR on Fe2O3/C catalysts is increased compared with bare carbon supports, as discerned from the rotating ring-disk electrode (RRDE) voltammetry experiments, demonstrating the role of size-confined Fe2O3 nanoparticles. The overall number of electrons in the ORR is increased by the introduction of Fe2O3 on the carbon support. Based on the kinetic analysis, the ORR on Fe2O3/C follows a pseudo-4-electron or 2+2-electron ORR, where the first 2-electron ORR to H2O2 and second 2-electron H2O2 reduction reaction (HPRR) to H2O are assigned to the graphitic carbon (carbon defects) and Fe2O3 active sites, respectively. Theoretical studies indicate that the role of Fe2O3 is to decrease the free energy of O2 adsorption and reduce the energy barrier for the reduction of *OOH to OH-. The onset potential estimated from the free energy diagram is 0.42 V, matching with the HPRR activity demonstrated using the potential-dependent rate constants plot. Fe2O3/C shows higher stability by retaining 95% of the initial activity even after 20 000 cycles.

Semiconductor heterostructures such as TiO2/Sb2S3 and ZnO/Sb2S3 are promising for photoelectrochemical applications. In this work, we demonstrate the photoelectrochemical performance with enhanced current densities of Sb2S3 sensitized nanorods of TiO2 (TNR) and ZnO (ZNR) photoanodes. ZNR and TNR are synthesized by the hydrothermal method and annealed in the air (AA) and hydrogen (HA) ambient. Stoichiometric Sb2S3 are coated on ZNR and TNR by a facile one-step method using thermolysis of Sb-MPA precursor in air ambient. Structural, optical and microstructural studies are carried out to confirm the formation of phase pure Sb2S3 on ZnO and TiO2 oxide nanorods in the TiO2/Sb2S3 and ZnO/Sb2S3 heterojunction photoanodes. Photoelectrochemical studies show enhanced performance from the Sb2S3 sensitized photoanodes in comparison to the bare TNR or ZNR photoanodes. TNR-AA/Sb2S3(MPA) and TNR-HA/Sb2S3(MPA) heterostructures exhibit current densities of 1.79 mA/cm2 and 1.58 mA/cm2, respectively, which is six times higher than the uncoated photoanodes (0.38 mA/cm2 for TNR-AA and 0.20 mA/cm2 for TNR-HA). In the case of ZNR, we see a 10 to 15 fold increase in current density (~3.3 to 4 mA/cm2) upon sensitizing with Sb2S3 on photoanodes. Further hydrogen annealed ZNR sensitized with Sb2S3 (ZNR-HA/Sb2S3(MPA)) shows a slightly higher current density (3.9 mA/cm2) than the air annealed ZNR-AA/Sb2S3(MPA) (3.32 mA/cm2). Hydrogen annealing is beneficial for ZNR, whereas air-annealing is favored for TNR. Also, stability studies and photocurrent measurements are discussed for these photoanodes.

The influence of morphology and compositional mixing on the electrochemical performances of Li-rich layered oxides (LLOs), specifically to address the high rate capability, is investigated. LLOs of composition xLi₂MnO₃·(1 – x)LiMn₀.₂₅Ni₀.₃₈Co₀.₃₇O₂ (LMNC, x = 0, 0.2, 0.4, and 0.6), lying in the plane NMC(640)–LCO–LMO, are synthesized in nanoplatelet morphology, and the results are compared to the same compounds prepared by a conventional solid-state reaction (SSR). Hexagonal-shaped thin (∼50 nm) flakes of transition metal oxide–hydroxide [TMO(OH)], prepared by the hydrothermal process, are reacted with Li carbonate to derive nanoplatelet morphology of LMNC by topotactic conversion. Structural and compositional evolutions of LLOs are analyzed with Rietveld refinement. The composite nature of LMNC comprising of monoclinic Li₂MnO₃ and rhombohedral LiMO₂ phases is evidenced. High-resolution transmission electron microscopy studies show the existence of a monoclinic Li₂MnO₃ phase embedded within the rhombohedral layered oxide phase. A uniform compositional distribution of all elements is discerned from EDS mapping, strongly suggesting that metal cations in both TMO/OH and LMNC are highly intermixed. Electrochemical properties become better with the larger fraction of the Li₂MnO₃ phase in LiMO₂. Among four compositions examined, LMNC (x = 0.6) shows the best electrochemical performance, with a capacity of ∼240 mAh g–¹ (∼173 mAh g–¹) at 0.1 C (1 C) current rate. Cycling stability studies, carried out at 1 C rate for 100 cycles, show a high capacity retention of 86%. Capacity at 3 C (5 C) is ∼140 mAh g–¹ (∼80 mAh g–¹) in LMNC (x = 0.6). LMNC (x = 0 and 0.6) prepared by SSR show inferior properties, suggesting that morphology and thorough intermixing of monoclinic Li₂MnO₃ and rhombohedral LiMO₂ phases are shown to play a significant role. Although enhanced performance is generally attributed to the extra capacity contribution from the Li₂MnO₃ phase, this study unequivocally brings out the influence of morphology on the electrochemical properties.

Li-intercalation and -deintercalation effects on the magnetic properties of defect-rich (DR) and defect-suppressed (DS) MoS2 nanosheets are investigated. Active defect sites take large Li (x ≈ 2 in...

Designing solid-state perovskite oxide solar cells with large short circuit current (JSC) and open circuit voltage (VOC) has been a challenging problem. Epitaxial BiFeO3 (BFO) films are known to exhibit large VOC (>50 V). However, they exhibit low JSC (≪μA/cm2) under 1 Sun illumination. In this work, taking polycrystalline BiFeO3 thin films, we demonstrate that oxygen vacancies (VO) present within the lattice and at grain boundary (GB) can explicitly be controlled to achieve high JSC and VOC simultaneously. While aliovalent substitution (Ca2+ at Bi3+ site) is used to control the lattice VO, Ca and Ti cosubstitution is used to bring out only GB-VO. Fluorine-doped tin oxide (FTO)/Bi1-xCaxFe1-yTiyO3-δ/Au devices are tested for photovoltaic characteristics. Introducing VO increases the photocurrent by four orders (JSC ∼ 3 mA/cm2). On the contrary, VOC is found to be

Since the inception of cobalt phthalocyanine for oxygen reduction reaction (ORR), non-platinum group metals have been the central focus in the area of fuel-cell electrocatalysts. Besides Fe-N

Irradiation of materials by high energy (∼MeV) ions causes intense electronic excitations through inelastic transfer of energy that significantly modifies physicochemical properties. We report the effect of 100 MeV Ag ion irradiation and resultant localized (∼few nm) thermal spike on vertically oriented TiO

Single crystalline perovskite solar cells (PSC) are promising for their inherent stability due to the absence of grain boundaries. While the development of single crystals of perovskite with enhanced optoelectronic properties is known, studies on the growth, device performance and understanding of the intrinsic stability of single crystalline perovskite thin film solar cell devices fabricated on electron selective contacts are scarcely explored. In this work, we examine the impact of mesoporous TiO2 (m-TiO2) and planar TiO2 (p-TiO2) on the growth of single crystalline-methyl ammonium lead iodide (SC-MAPbI3) film, PSC device performance and film stability under harsh weather conditions (T ∼ 85 °C and RH ∼ 85%). Self-grown SC-MAPbI3 films are developed on m-TiO2 and p-TiO2 by inverse temperature crystallization under ambient conditions without the need for sophisticated glove-box processing. The best device with m-TiO2 as an electron transport layer showed a promising power conversion efficiency of 3.2% on an active area of 0.3 cm2 in hole transport material free configuration, whereas, only 0.7% was achieved for the films developed on p-TiO2. Complete conversion of precursor to perovskite phase and better surface coverage of the film leading to enhanced absorption and reduced defects of single crystalline perovskite on m-TiO2 compared to its p-TiO2 leads to this large difference in efficiency. Mesoporous device retained more than 70% of its initial performance when stored at 30 °C under dark for more than 5000 h at 50% RH; while the planar device degraded after 1500 h. Thermal and moisture endurance of SC-MAPbI3 films are investigated by subjecting them to temperatures ranging from 35 °C to 85 °C at a constant relative humidity (RH) of 85%. X-ray diffraction studies show that the SC-MAPbI3 films are stable even at 85 °C and 85% RH, with only slight detection (30–35%) of PbI2 at these conditions. This study highlights the superior stability of SC-MAPbI3 films which paves way for further studies on improving the stability and performance of the ambient processed PSCs.

We show that it is possible to tune the magnetic properties in MoS2 without any intentional magnetic dopants but by simply controlling the magnetically active defect sites. The layer thickness and ...

Rutile TiO2 (TiO2-NR) and ZnO (ZnO-NR) in nanorod microstructural forms are synthesized by hydrothermal route. The oxides are grown directly on fluorine doped SnO2 coated glass, and annealed in air (AA) and hydrogen (HA) atmosphere for 3 h at 450 °C. A detailed structural, optical, and microstructural study confirms the phase formation in the AA and stability in HA samples. EPR signal with g-values of ~1.99 and ~1.95 from TiO2-NR and ZnO-NR photoanodes respectively confirms the presence of oxygen vacancy (OV) related defects. The EPR signals are stronger in TiO2-NR-HA compared to TiO2-NR-AA and is absent in ZnO-NR-AA suggesting increased defect concentration on hydrogenation. Further this leads to two order increase in photoconductivity for hydrogenated TiO2-NR-HA and ZnO-NR-HA photoanodes when measured under 1 Sun illumination compared to AA photoanodes. Photovoltaic power conversion efficiency for both dye and Sb2S3 sensitized solar cells are found to increase by 2 to 3 times in hydrogenated ZnO-NR. In contrast, TiO2-NR show two-fold decrease in efficiency on hydrogenation. The efficiency change is consistent with the change in interface impedance, which increases for dye or Sb2S3 sensitized TiO2-NR-HA photoanode, whereas, decreases for sensitized ZnO-NR-HA photoanode. These studies show that despite of one to two to three order increase in photoconductivity, the sensitizer/photoanode interface impedance play a significant role in deciding the efficiency.

Semiconductor quantum dot (QD)–graphene composites are promising materials for photovoltaics and photocatalysis because of efficient charge extraction and transport property of graphene. Analysis o...

One step electrodeposition method has been used to realize highly porous ZnO pin hole (ZP) and ZnO rosette sheets (ZS) nanostructure based photo-anodes for efficient photoelectrochemical (PEC) splitting of water. Electrodeposited ZP and ZS based photo-anodes exhibit enhanced photocurrent density of 0.62 mA/cm2 and 0.76 mA/cm2 respectively (at a bias of 0.75 V). Further on hydrothermal amination (A), these electrodeposited ZP and ZS (A-ZP and A-ZS) nanostructure based photo-anodes had shown enhanced photocurrent density of 1.02 mA/cm2 and 1.27 mA/cm2, respectively. Surface morphology, evolution and elemental study were done using FESEM and EDX. Raman spectra of aminated photo-anodes have peaks at ∼270 cm−1 and ∼511 cm−1 related to stretching vibration mode between Zn N and Zn O. The peaks at wave number ∼558 cm−1 and ∼571 cm−1 is due to formation of Zn C bonds and because of complex defects respectively. ZnO exhibits low PEC activity, but on nano-structuring in the form of ZP and ZS improves its light absorption capacity. Hydrothermal amination red shifts (∼25 nm) the absorption band at ∼ 425 nm. The N and C act as electron reservoirs in A-ZP and A-ZS photo-anodes and efficiently separate the photo-generated electron/hole pairs and restrain charge recombination to generate photo-reactive sites. Electrochemical impedance spectroscopy (EIS) revealed that A-ZP and A-ZS had low charge transfer resistance compared to their bare counterparts. This lead to considerably improved PEC performance. An unprecedented increase in IPCE values in A-ZP and A-ZS can be assigned to the decrease in band gap and thereby significant enhancement in photocurrent density. These result in to proper charge segregation and improved charge transportation. The maximum value of IPCE is 9.6% for A-ZS sample and it is also clear that ZP and ZS nanostructured film have higher IPCE values at ∼400 nm than traditional ZnO thin film. A-ZP and A-ZS based photo-anodes have exhibited enhanced PEC performance as evident from IPCE measurements and thus can be a prospective candidate for PEC and optoelectronic applications.

Bi-rich Bi2Te3 thin films are prepared at 300 K using e-beam evaporation technique. A source power of 45 W for e-beam is used. Post deposition, these as-deposited Bi-rich Bi2Te3 (Bi-BT-AD) films are annealed at 100 °C (Bi-BT-100), 200 °C (Bi-BT-200) and 300 °C (Bi-BT-300) for 1 h under a pressure of 3 × 10−4 Pa. X-ray diffraction measurements reveal the presence of Bi phase together with crystalline Bi2Te3 indicating the possible presence of Bi-rich Bi2Te3 phase in the Bi-BT-AD film. The broad peaks from Bi2Te3 (015) plane indicate nanocrystalline nature of particles. With annealing, no change in diffraction pattern is observed for Bi-BT-100. However, Bi-BT-200 and Bi-BT-300 films show the emergence of x-ray reflection from unknown phases around 2θ ~ 20° and 47°. This indicates Bi related secondary phase segregation and the thermodynamic instability for the presence of Bi in Bi2Te3 lattice. From Raman studies it is discerned that Bi secondary phase coexists along with the Bi-rich Bi2Te3 nanocrystalline grains. On vacuum annealing Bi-rich Bi2Te3 phase in thin films prevails as evidenced from the p-type electrical characteristics, while excess Bi disappears and converts into an unknown minor phase. The resistivity of all the annealed films are ~ 0.9 × 10−4 Ωcm. The Seebeck coefficients also do not show any change and remain around 33 to 36 μV/K. Thermoelectric properties of Bi-BT-100 exhibit high power factors when measured at different ΔT with a maximum of ~ 17.5 × 10−4 W/K2 m for ΔT = 100 °C. Thus, unlike the near-stoichiometric thin films, Bi-rich thin films require low temperature annealing (~100 °C) to achieve optimized parameters. Bi-rich Bi2Te3 thin films also show higher power factor compared to the near-stoichiometric thin films. Thus, favourable thermoelectric properties can be achieved at 300 K for temperature sensitive device fabrication using Bi-rich Bi 2Te3 thin films.

Magnetodielectric (MD) properties of as-prepared (AP) and air-annealed ${\mathrm{Bi}}_{1\ensuremath{-}x}{\mathrm{Ca}}_{x}{\mathrm{Fe}}_{1\ensuremath{-}y}{\mathrm{Ti}}_{y}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ nanoparticle ceramics made by spark plasma sintering process are investigated as a function of temperature. Aliovalent ${\mathrm{Ca}}^{2+}$ substitution at ${\mathrm{Bi}}^{3+}$ site creates oxygen vacancies (${\mathrm{V}}_{\mathrm{O}}$) in the lattice disrupting the intrinsic spin cycloid of ${\mathrm{BiFeO}}_{3}$, which are suppressed when the charge compensating ${\mathrm{Ti}}^{4+}$ is co-substituted. In addition, cation substitution reduces the grain size and increases surface oxygen vacancies. These lattice and surface ${\mathrm{V}}_{\mathrm{O}}$ defects play a significant role in enhancing the magnetic properties. Zero-field-cooled magnetization curves of all AP samples show a sharp Verwey-like transition at \ensuremath{\sim}120 K, which weakens on air-annealing. A coexistence of positive and negative MD [MD = $\frac{\mathrm{\ensuremath{\Delta}}\ensuremath{\varepsilon}(H)}{\ensuremath{\varepsilon}(H=0)}$; $\mathrm{\ensuremath{\Delta}}\ensuremath{\varepsilon}(H)=\ensuremath{\varepsilon}(H)\ensuremath{-}\ensuremath{\varepsilon}(H=0)$] response is observed, with the former dominating at 300 K and the latter at 10 K. As-prepared 5 at.% (10 at.%) Ca and Ca-Ti substituted ${\mathrm{BiFeO}}_{3}$ ceramics exhibit a maximum MD response of --10% (\ensuremath{\sim}+3%) at 10 K (300 K). Negative MD response diminishes for air-annealed ${\mathrm{Bi}}_{1\ensuremath{-}x}{\mathrm{Ca}}_{x}{\mathrm{Fe}}_{1\ensuremath{-}y}{\mathrm{Ti}}_{y}{\mathrm{O}}_{3\ensuremath{-}\ensuremath{\delta}}$ ceramics due to the reduction in ${\mathrm{V}}_{\mathrm{O}}$ concentration. Samples exhibiting dominant positive MD response show a similar trend for MD $vs$ H and ${M}^{2}$ vs H plots. This agreement between ${M}^{2}$ and $\mathrm{\ensuremath{\Delta}}\ensuremath{\varepsilon}(H)$ demonstrates a strong inherent MD coupling. On the contrary, negative MD does not follow this trend yet shows a linear relationship of MD vs ${M}^{2}$, suggesting a strong coupling between the magnetic and dielectric properties. Temperature-dependent MD studies carried out at 5 T show a gradual change from negative to positive values. Negative MD at low temperatures could be activated by the spin-lattice coupling, which dominates even at high frequency (1 MHz) under the applied field. Other contributions, including Verwey-like transition, magnetoresistance, and Maxwell-Wagner effects, do not influence the observed MD response. A prominent role of oxygen vacancies in altering the MD behavior of ${\mathrm{BiFeO}}_{3}$ is discussed in detail.

A Li-rich layered oxide (LLO) cathode with morphology-dependent electrochemical performance with the composition Li1.23Mn0.538Ni0.117Co0.114O2 in three different microstructural forms, namely, randomly shaped particles, platelets, and nanofibers, is synthesized through the solid-state reaction (SSR-LLO), hydrothermal method (HT-LLO), and electrospinning process (ES-LLO), respectively. Even though the cathodes possess different morphologies, structurally they are identical. The elemental dispersion studies using energy-dispersive X-ray spectroscopy mapping in scanning transmission electron microscopy show uniform distribution of elements. However, SSR-LLO and ES-LLO nanofibers show slight Co-rich regions. The electrochemical studies of LLO cathodes are evaluated in terms of charging/discharging, C-rate capability, and cyclic stability performances. A high reversible capacity of 275 mA h g-1 is achieved in the fibrous LLO cathode which also demonstrates good high-rate capability (80 mA h g-1 at 10 C-rate). These capacities and rate capabilities are superior to those of SSR-LLO [210.5 mA h g-1 (0.1 C-rate) and 4 mA h g-1 (3 C-rate)] and HT-LLO [242 mA h g-1 (0.1 C-rate) and 22 mA h g-1 (10 C-rate)] cathodes. The ES-LLO cathode exhibits 88% capacity retention after 100 cycles at 1 C-rate. A decrease in voltage on cycling is found to be common in all three cathodes; however, minimal voltage decay and capacity loss are observed in ES-LLO upon cycling. Well-connected small LLO particles constituting fibrous microstructural forms in ES-LLO provide an enhanced electrolyte/cathode interfacial area and reduced diffusion path length for Li+. This, in turn, facilitates superior electrochemical performance of the electrospun Co-low LLO cathode suitable for quick charge battery applications.

(i) Edge and planar defect-rich and (ii) defect-suppressed MoS2 nanosheets are fabricated by controlled annealing of wet-chemically processed precursors. Wrinkles, folds, bends, and tears lead to the introduction of severe defects in MoS2 nanosheets. These defects are suppressed and highly crystalline MoS2 nanosheets are obtained upon high-temperature annealing. The influence of defects on the electrochemical properties, particularly rate capability and cycling stability, in the Li intercalation regime (1 V to 3 V vs. Li/Li+) and conversion regime (10 mV to 3 V vs. Li/Li+) are investigated. In the intercalation regime, the initial Li intake (x in LixMoS2) for defect-rich nanosheets is larger (x ≈ 1.6) as compared to that in defect-suppressed MoS2 (x ≈ 1.2). Although the reversible initial capacity of all the anodes is nearly the same (x ≈ 0.9) at 0.05C rate, defect-rich MoS2 exhibits high rate capability (>40 mA h g-1 at 40C or 26.8 A g-1). When cycled at 10C (6.7 A g-1) for 1000 cycles, 75% capacity retention is observed. High rate capability can be attributed to the defect-rich nature of MoS2, providing faster access to lithium intercalation by a shortened diffusion length facilitated by Li adsorption at the defect sites. The defect-rich nanosheets exhibit a power density of ∼20% more than that of defect-suppressed nanosheets. For the first time, MoS2/Li cells with a high power density of 10-40 kW kg-1 in the intercalation regime have been realized. In the conversion regime, defect-rich and defect-suppressed MoS2 exhibit initial lithiation capacities of ∼1000 and ∼840 mA h g-1, respectively. Defect-rich MoS2 had a capacity of ∼800 mA h g-1 at 0.1C (67 mA g-1), whereas defect-suppressed MoS2 had a capacity of only ∼80 mA h g-1 at the same current rate. Capacity retention of 78% was observed for defect-rich MoS2 with a reversible capacity of 591 mA h g-1 when cycled at 0.1C (67 mA g-1) for 100 cycles. Despite having a lower energy density in the intercalation regime, the power density of defect-rich MoS2 in the intercalation regime is significantly larger (by three orders of magnitude) as compared to that of defect-suppressed MoS2 in the conversion regime. Defect-rich MoS2 nanosheets are promising for high-rate-capability applications when operated in the intercalation regime.

Nano-porous nano-silicon (npn-Si) anode for Li-ion battery is a great promise to mitigate problems associated with large volume expansion and pulverization during the charging-discharging cycle. Here we report the synthesis of highly porous Si from MCM-41, through a magnesiothermic reduction ((MR) method. Structural studies confirm the complete conversion of MCM-41 to crystalline silicon from the particle core to the surface. Morphological studies reveal the retention of porous network in the parent compound after reduction. The silicon anode is fabricated using two types of aqueous binders viz Na salt of carboxymethyl cellulose (Na-CMC), alginate (Na-Alg) demonstrates good cycling stability and rate performance. Among these, porous silicon with former binder shows a higher initial charge capacity of 2767 mAhg−1 even at a current rate of C/2 and retains 705 mAhg−1 capacity after 500 cycles. While, alginate binder showed much higher initial capacity of 3000 mAhg−1 and retained almost the same capacity as Na-CMC after 10 cycles and beyond. High capacity and reasonably good retention of nano-porous nano-silicon is attributed to (i) the accommodation of the drastic volume change in porous Si to effectively mitigate the mechanical stress, (ii) enhanced electrochemical kinetics and (iii) high Li flux in the porous structure.

Composite photoanode comprising mesoporous microspheres with a smooth spherical morphology exhibiting high light scattering due to optical whispering gallery modes (WGMs) is used to fabricate whisperonic solar cell (WSC) devices. The photoanode is sensitized with CdS–CuInS2 thin films (CdS–CIS-TF) of ∼5 nm thickness. CdS–CIS-TF-sensitized photoanodes exhibit strong coupling with WGM. These WSC devices show an average (ηavg) efficiency (η) of ≈3.2% in comparison with ηavg ≈ 1.9% for the nanoparticulate-based photoanode. The observed efficiency is the highest for CdS–CIS-TF-sensitized solar cells made using I–/I3– electrolyte. This remarkable increase in ηavg (∼60%) is attributed to increased photon absorption by the sensitizer films because of the presence of WGM scattering prevailing in smooth microspheres. Thus, WSC photoanode configuration is a promising approach to enhance the efficiency of TF-sensitized solar cells.

Carbon-coated single crystalline nanotubular (NT) and nanoparticular (NP) LiFe1-xMnxPO4 (x = 0, 0.2, and 0.5) cathodes are fabricated to study the effect of compositional and microstructural changes on Li+ diffusion and electrochemical properties. Insight in to the compositional effect on Li+ diffusion is obtained from DFT facilitated climbing image nudged elastic band (CI-NEB) simulations. NT cathodes exhibit exceptionally good discharge capacities ∼60 (∼165) mAhg−1, ∼32 (∼110) mAhg−1 and ∼22 (∼82) mAhg−1 at 25C (1C) rate for x = 0, 0.2, 0.5, respectively. NP cathodes show capacity

A synergetic approach of employing smooth mesoporous TiO2 microsphere (SμS-TiO2)–nanoparticulate TiO2 (np-TiO2) composite photoanode, and size and defect controlled CdSe quantum dots (QD) to achieve high efficiency (η) in a modified Grätzel solar cell, quantum dot sensitized whisperonic solar cells (QDSWSC), is reported. SμS-TiO2 exhibits whispering gallery modes (WGM) and assists in enhancing the light scattering. SμS-TiO2 and np-TiO2 provide conductive path for efficient photocurrent charge transport and sensitizer loading. The sensitizer strongly couples with the WGM and significantly enhances the photon absorption to electron conversion. The efficiency of QDSWSC is shown to strongly depend on the size and defect characteristics of CdSe QD. Detailed structural, optical, microstructural and Raman spectral studies on CdSe QD suggest that surface defects are prominent for size ~2.5 nm, while the QD with size > 4.5 nm are well crystalline with lower surface defects. QDSWSC devices exhibit an increase in η from ≈0.46% to η ≈ 2.74% with increasing CdSe QD size. The reported efficiency (2.74%) is the highest compared to other CdSe based QDSSC made using TiO2 photoanode and I−/I3− liquid electrolyte. The concept of using whispering gallery for enhanced scattering is very promising for sensitized whisperonic solar cells.

CuInS2 (CIS) based solar cell devices are fabricated by sensitizing TiO2 photoanodes with CIS quantum dots (CIS-QDs). Morphologically different TiO2, viz. Degussa P25 nanoparticles, smooth and fibrous microspheres (SμS and FμS respectively) are used to fabricate photoanodes. CIS-QDs are synthesized using dodecanethiol (DDT), CuI and In(OAc)3 precursors by solvothermal method. DDT surfactant present on the CIS QDs surface is replaced with 3-mercaptopropionic acid in a single phase one step procedure to enable efficient loading of QDs onto photoanode and as linker molecule for charge carrier extraction. The CIS QDs sensitized on SμS and FμS microsphere photoanode layers exhibit a photoconversion efficiency (η) of 3.2% and 1.6%, respectively, in comparison to η ≈ 2.1% for nanoparticulate TiO2 (Degussa P25). Further increase in efficiency is obtained (3.8% for SμS and 2.5% for FμS) when composite photoanode films made of porous microspheres filled with nanoparticulate P25 are used. A maximum efficiency of 3.8% (with JSC ≈ 6.2 mA, VOC ≈ 926 mV and FF ≈ 66 for cell area ≈ 0.25 cm2 and thickness ≈ 20 µm) is realized when 4.6 nm CIS QDs sensitized on composite photoanode (consisting of 80 wt. % SμS and 20 wt. % P25) is used. High VOC observed is unprecedented and is possible due to combined effect of SμS+P25 composite photoanode properties such as fewer defects, good connectivity between particles, effective light scattering, minimum recombination, and effective electron transport and size optimized CuInS2 QDs. Electrochemical impedance spectroscopy studies reveal a low interfacial resistance and longer electron life time in SμS+P25 composite photoanodes.

We investigate the structural and ferromagnetic properties of Mo1-xMnxS2 and Mo1-xCoxS2 (x = 0, 0.025, 0.05, 0.075, 0.1 and 0.25) nanosheets synthesized by a wet chemical process. X-ray diffraction (XRD) patterns confirm the 2H polytype of MoS2 for both pristine and doped nanosheets. From X-ray absorption near-edge spectral (XANES) studies, Mn doping in MoS2 is found to be very ineffective even for x up to 0.25 and is found to be in Mn4+ oxidation state. Cobalt doping in MoS2 is very effective and found in a mixed oxidation state of 2+/3+. For x > 0.05, Co9S8 secondary phase is discerned in XRD. XANES and extended X-ray absorption fine structure study further confirm the absence of Co, Mn clusters. All the MoS2 nanosheets are multi-layered (~10 to 20 layers) as discerned from Raman and high-resolution transmission electron microscopy (HRTEM) studies. HRTEM images also show the presence of planar and edge defects in MoS2 nanosheets. These defects arise from the bends, tears, folds and edges of the nanosheets. In addition to these defects, sulphur vacancy point defects are predominant as evidenced from electron paramagnetic resonance signal at g = 2.03. Pristine MoS2 nanosheets exhibit weak ferromagnetism [magnetization (MS) = 19 × 10−3 emu/g and 1.3 × 10−3 emu/g at T = 5 K and 300 K] mostly arising from the planar defects. While the magnetization increases roughly 6 (3) times higher for Mn-doped MoS2 compared to the pristine MoS2 nanosheets at 300 K (5 K). For Co-doped MoS2 nanosheets 7 times increase in MS is found at 300 K, however, the changes are minimal at 5 K. A small change in MS for Mo1-xMnxS2 nanosheets is due to ineffective Mn substitution at Mo sites. On the contrary, Co doped samples exhibit strong paramagnetic contribution at 5 K. Despite effective substitution of Co in MoS2, the saturation magnetization values obtained after subtracting the paramagnetic component are slightly less compared to Mn doped samples. This is most probably due to the dominant antiferromagnetic interaction and the Co9S8 phase segregation. Thus, our experiments show that controlled Mn and Co doping in the low concentration (x

Mesoporous TiO2 nanoparticles are excellent photoanodes for sensitized solar cells (SSC). However, a significant loss in the photoconversion efficiency (PCE) occurs due to the inefficient light absorption. Large Mie scattering from mesoporous micron-sized spheres could be used to enhance the absorption and hence the PCE. Here, we show that a composite comprising a TiO2 mesoporous microsphere with smooth surface (SμS-TiO2) exhibiting whispering gallery modes (WGM) and a commercial TiO2 mesoporous nanoparticle (Degussa P25) with an optimum ratio (80:20 wt %) shows significant enhancement in PCE of DSSC and QDSSC devices. SμS-TiO2 exhibits strong WGM as evidenced from the photoluminescence studies carried out using a laser with an excitation wavelength λexc = 325 nm. These microspheres sensitized with N719 dye or CdSe/CuInS2 QDs are shown to exhibit emission characteristics strongly coupled to WGM resulting in an enhanced PCE in SSC. Increases in PCE of ∼24% in DSSC devices and 80–95% in QDSSC devices of 0.2...

We present a detailed study on the photovoltaic performance of dye and quantum dot (QD) sensitized solar cells fabricated using nanoporous TiO2 photoanodes prepared by a template approach. Nanoporous TiO2 particles (TNPO) are prepared by sol-gel method using dextran (TNPO-D) and glucose (TNPO-G) as templates. The decomposition of templating agents during calcination introduces nanopores (∼10 nm) in TiO2 nanoparticles as evidenced from the HRTEM studies. Oxygen vacancies are also introduced in TiO2 nanoparticles due to prevailing reducing ambient during decomposition. Oxygen vacancy (VO) related defects are evidenced from EPR spectra from a strong absorption signal observed at g-value of 1.994 related to Ti3+-VO-Ti3+ defect sites. The defect concentration estimated from EPR spectra is found to be ∼5 to 15 times larger for nanoporous TiO2 particles compared to Degussa P25-TiO2. TNPO samples also show enhanced defect level photoluminescence emission. The photovoltaic efficiency (η) and the IPCE of DSSC and QDSSC are strongly influenced by the defect concentration and seen to decrease with increasing VO in TiO2 nanoparticles. Twofold lower η is found in both DSSC (∼6.38% to 3.66%) and QDSSC (∼1.69% to 0.46%) devices made using nanoporous TiO2 compared to P25-TiO2 photoanode solar cells. P25-TiO2 also shows significant decrease in η when oxygen vacancies are introduced by hydrogen annealing process, which reveal detrimental effect of VO on the photovoltaic properties. EIS studies suggest increased interfacial resistance in solar cells made from nanoporous TiO2 photoanodes.

Enhanced rate capability of interconnected LiNi1/3Mn1/3Co1/3O2 (NMC) nanoparticles fabricated via electrospinning method is presented. Interconnected NMC nanoparticles have a discharge capacity of 175 mAh g−1 at 0.1C and 94 mAh g−1 at 1C. Similar nanoparticular NMC cathode without interconnections, fabricated by co-precipitation method, has a capacity of 22 mAh g−1 at 1C. Interconnected NMC nanoparticles have good cycling stability after 500 cycles at 1C with a capacity of ~17 mAh g−1. Though the rate capability of Interconnected NMC nanoparticles is superior, cycling stability is similar across cathodes, indicating that capacity fading is intrinsic to the cathode.

We report a facile and low-cost solution-based approach to synthesize various binary, ternary and quaternary metal chalcogenide thin films. Homogeneous metal chalcogenides single precursor is prepared by dissolving metal salt (metal chloride/acetate) in ethanolic/methanolic solution of 3-Mercaptopropionic acid (MPA) at room temperature. High-quality CdS, ZnS, Sb2S3, CuInS2 (CIS) and Cu2ZnSnS4 (CZTS) metal sulfide thin films are successfully synthesized by thermalizing these metal-MPA precursor solution at 350 °C in air for 15 min. The mechanism of metal sulfide formation is analyzed by FTIR and thermogravimetry coupled with mass spectrometry. This study highlights the formation of intermediate metal-MPA complex as a single precursor, which eventually decomposes into metal sulfide upon heating at 350 °C. The film thickness, morphology and composition of metal sulfide can be controlled by the concentration of reactants, deposition cycles and the choice of solvent. XRD, Raman, UV–vis spectroscopy, diffuse reflectance spectroscopy and energy dispersive analyses ascertain the phase purity of the films. Bandgap estimates, morphology, narrow Urbach width with low defect densities in the bandgap region, uniform thickness discerned from cross-section SEM, uniformity in the elemental maps and the photoconductivity studies further confirm high-quality of the films. Attaining molecular-level homogeneous precursor solution and inertness to the air ambient enables precise control on the stoichiometry and the enhanced uniformity of deposited films. This facile method will have potential application in large scale synthesis of different metal chalcogenide thin films by a thermolysis process and is highly suitable for controlling stoichiometry and spatial uniformity of deposited films sought in solar cell, optoelectronic and catalysis applications.

The recent surge of interest in using all-inorganic materials like CsPbI3 for photovoltaic devices has brought significant interest in exploring the properties of BiFeO3 (BFO) by substituting Cs+ and K+ at the Bi3+ site. The aim of the present work is to study the parameters like controlling the lattice and surface oxygen vacancy (VO) defects which can significantly improve the photovoltaic device performances. Monovalent substituted and aliovalent co-substituted Bi1−xM'xFe1−yM"yO3−δ (M′ = K+ and Cs+; M" = Ti4+; x = y = 0 and 0.1) are grown on fluorine-doped tin oxide (FTO)/glass substrates by metal-organic chemical solution deposition method. Photoconductivity and photovoltaic properties of these films are studied in FTO/Bi1−xM'xFe1−yM"yO3−δ/Au capacitor configuration. Aliovalent substitution (for M' = K+ and Cs+, BK10FO and BCs10FO, respectively) at Bi3+ sites create VO in BFO thin films. Further, grain size reduction from 100 nm to 30 nm also results in the creation of surface VO defects. Tauc plot shows a reduction in the bandgap (Eg) values from 2.32 eV to 2.26 eV due to the formation of mid-bandgap VO defect states. Consequently, ferroelectric properties also get diminished. Aliovalent K+-Ti4+ co-substitution in BFO thin films brings back the Eg values to 2.3 eV, i.e., similar to pristine BFO thin films suggesting suppression of VO. This results in the revival of ferroelectric nature in aliovalent co-substituted thin films. Photoconductivity studies show two order enhancement in conductivity for BK10FO thin film devices compared to pure BFO. This enhancement is attributed to the mid-bandgap VO defect states due to aliovalent substitution. On the other hand, photoconductivity observed in BCs10FO devices is comparable with pristine BFO devices. Contrary to this, aliovalent co-substituted thin films show a decreasing trend of photoconductivity compared to M'+ substituted BFO suggesting that VO defects get suppressed due to charge compensation. Photoconductivity and photovoltaic device studies show similar behavior. BK10FO devices exhibit short circuit current density (JSC) ~0.45 µA/cm2, which is larger than that observed in BFO devices (JSC ~0.3 µA/cm2). But, BCs10FO devices show lesser JSC 0.07 µA/cm2. Open circuit voltage (VOC) observed in BFO devices is around 3 V which decreases to 0.1 V and 0.06 V for BK10FO and BCs10FO devices, respectively. This decrease in VOC is attributed to the reduction of the ferroelectric nature of the films. BFO, BK10FO, and BCs10FO devices show photovoltaic switching upon poling the films. Co-substituted thin films show a reduction in the JSC and betterment in the VOC compared to the monovalent substituted BFO thin films. This happens due to the suppression of VO defects by partial charge compensation in aliovalent co-substituted BFO films. This study explicitly brings out the role of VO on the photovoltaic and photoconductivity properties of BFO thin films.

Anatase TiO2 microspheres with smooth and fibrous morphology (SμS and FμS) resembling laddu and dandelion are synthesized by solvothermal and hydrothermal methods, respectively. A detailed analysis of these two microstructures using XRD, UV–vis spectroscopy, electron microscopy and surface area measurement techniques are presented. Photoanodes fabricated using these microspheres and their composites with nanoparticles (Degussa P25) are tested for photovoltaic (PV) performance using a standard Gratzel-type dye-sensitized solar cell (DSSC) configuration. The DSSC made up of SμS and FμS microspheres exhibit an efficiency (η) of 8.4% and 6.4% respectively, in comparison to η≈7.1% for nanoparticulate P25. Further enhancement in η is realized in the composite photoanode films made of porous SμS/FμS microspheres filled with nanoparticulate P25 TiO2. High power conversion efficiency of 8.9% (for cell area of 0.5 cm2 and thickness of ~25 µm) was achieved in composite photoanode film consisting of 80 wt% SμS and 20 wt% P25. Electrochemical impedance spectroscopy studies reveal a low interfacial resistance in composite photoanodes, which is desired for efficient electron generation and transport. Composite microspheres filled with P25 nanoparticles in their voids show enhanced efficiency than the mesoporous TiO2 microspheres. Thus, SμS-nanoparticle composite TiO2 film possesses essential attributes necessary for an efficient photoanode viz. large surface area for dye adsorption, good connectivity between nanocrystallites for the efficient electron transport, and higher scattering properties for better light harvesting efficiency.

The influence of Ag plasmons and reduced graphene oxide (RGO) on ZnO nanorods (Z-NRs)-based photoanodes for photoelectrochemical splitting of water is the main focus of the present experimental study. Plasmonic layer of Ag is incorporated either as a base (Ag-Z-NRs) layer or as a top layer (Z-NRs-Ag) in an electrochemically deposited Z-NRs-based photoanodes. Z-NRs-Ag photoanodes exhibited better optical absorption as plasmonic layer stimulates charge transfer and restrain charge recombination. It had shown the photocurrent density of ~0.79 mA cm−2, at a bias of 1.4 V/RHE. A mediator layer of RGO when introduced in Z-NRs-Ag photoanodes synergistically with Ag plasmons enhances the photocurrent density to ~1.3 mA cm−2 at a bias of 1.4 V/RHE. Structure and surface morphology of the synthesized photoanodes was studied using x-ray diffraction and field emission scanning electron microscopy. Elemental analysis and optical characterization was done using energy-dispersive x-ray analysis, UV–Visible absorption spectroscopy and Raman spectroscopy. The current–voltage characteristics, electrochemical impedance spectroscopy, Mott–Schottky analysis, photoconversion efficiency and incident photon to current conversion efficiency measurements have been used to substantiate our observations of synthesized photoanodes.

Nanocrystalline thin films of a V-VI compound Bi 2 Te 3 are fabricated with uniform thickness by e-beam evaporation at room temperature. The as-deposited films are stoichiometric, monophasic, highly strained and polycrystalline. We studied the effect of vacuum annealing (at a pressure of ~ 3 × 10 − 6 mbar) on composition, structure, optical and electrical properties of these films. It is observed that, as the annealing temperature increases (from 100 °C to 300 °C), the crystallites grow with a preferential orientation along (110) planes with slight increase in the crystallite size from ~ 14 nm to 30 nm. This is associated with the breaking of quintuple layers and rearrangement of crystallographic planes in the crystallites with Te rich surface emerging on vacuum annealing as evidenced from the XRD, Raman and high-resolution TEM studies. The direct bandgap (0.116 eV) of as-deposited Bi 2 Te 3 changes from 0.092 eV to 0.113 eV on annealing at 100 °C to 300 °C, respectively. Interestingly, we observe a gradual change from a semiconductor to metallic behavior on annealing the samples from 100 °C to 300 °C. Such a transition from negative temperature coefficient (NTC) to positive temperature coefficient (PTC) is seen mainly due to the percolation of Te - rich crystallite surfaces, which evolve as the annealing temperature increases. While the films annealed at 200 °C and 250 °C shows a broad semiconductor to metallic transition at ~ 150 K and 200 K respectively, the thin films annealed at 300 °C are found to exhibit complete metallic behavior below room temperature. The electrical property and Seebeck coefficient studies with power factors in the range of ~ 4 to 12 × 10 − 4 W/K 2 m for films annealed above 200 °C suggest that the vacuum annealed Bi 2 Te 3 thin films are favorable for thermoelectric applications.

Environmental deterioration and depletion in conventional energy resources greatly demand the need for photovoltaic devices, which use solar radiation to meet future energy demands. Efficient light management plays a pivotal role in improving the performance of photovoltaic devices. Various avenues have been explored to address light management in solar cells. Employing whispering gallery mode (WGM) microresonators in solar cell device is one such strategy. Using resonating structures for light scattering is recently gaining momentum as they exhibit great potential to enhance the efficiency through light trapping. Functional material based microresonators further provide added advantage as they combine inherent optical resonance with the material properties suitable for photovoltaics like efficient charge separation and transport in one platform. “Whisperonic solar cell” is a broadly classified device in which resonating cavities are used in the cell architecture to effectively scatter the light, resulting in enhanced light absorption and thus efficiency. Recent studies reveal that WGM enabled optical microcavities can effectively get coupled to the light absorber in a sensitized solar cell (SSC) and improve the performance of SSC significantly. In this short review, we briefly present the idea of enhancing the efficiency of solar cell using whispering gallery modes. Several case studies available from the literature for realizing the concept of WGM for light trapping are highlighted. Particular focus is given to the quantum dot sensitized whisperonic solar cells. The concept is much more universal and will be useful both in thin film and sensitizer solar cells.

(i) Edge and planar defect-rich and (ii) defect-suppressed MoS2 nanosheets are fabricated by controlled annealing of wet-chemically processed precursors. Wrinkles, folds, bends, and tears lead to the introduction of severe defects in MoS2 nanosheets. These defects are suppressed and highly crystalline MoS2 nanosheets are obtained upon high-temperature annealing. The influence of defects on the electrochemical properties, particularly rate capability and cycling stability, in the Li intercalation regime (1 V to 3 V vs. Li/Li+) and conversion regime (10 mV to 3 V vs. Li/Li+) are investigated. In the intercalation regime, the initial Li intake (x in LixMoS2) for defect-rich nanosheets is larger (x ≈ 1.6) as compared to that in defect-suppressed MoS2 (x ≈ 1.2). Although the reversible initial capacity of all the anodes is nearly the same (x ≈ 0.9) at 0.05C rate, defect-rich MoS2 exhibits high rate capability (40 mA h g-1 at 40C or 26.8 A g-1). When cycled at 10C (6.7 A g-1) for 1000 cycles, 75% capacity retention is observed. High rate capability can be attributed to the defect-rich nature of MoS2, providing faster access to lithium intercalation by a shortened diffusion length facilitated by Li adsorption at the defect sites. The defect-rich nanosheets exhibit a power density of ∼20% more than that of defect-suppressed nanosheets. For the first time, MoS2/Li cells with a high power density of 10-40 kW kg-1 in the intercalation regime have been realized. In the conversion regime, defect-rich and defect-suppressed MoS2 exhibit initial lithiation capacities of ∼1000 and ∼840 mA h g-1, respectively. Defect-rich MoS2 had a capacity of ∼800 mA h g-1 at 0.1C (67 mA g-1), whereas defect-suppressed MoS2 had a capacity of only ∼80 mA h g-1 at the same current rate. Capacity retention of 78% was observed for defect-rich MoS2 with a reversible capacity of 591 mA h g-1 when cycled at 0.1C (67 mA g-1) for 100 cycles. Despite having a lower energy density in the intercalation regime, the power density of defect-rich MoS2 in the intercalation regime is significantly larger (by three orders of magnitude) as compared to that of defect-suppressed MoS2 in the conversion regime. Defect-rich MoS2 nanosheets are promising for high-rate-capability applications when operated in the intercalation regime.

LiVPO4F (LVPF) is a promising high voltage (4.2 V vs. Li/Li+) and high energy density (655 Wh kg−1) cathode material for lithium ion batteries. The challenge is to prepare phase pure and conducting material suitable for battery application. In this work carbon coated LiVPO4F (LVPF/C) is synthesized by sol-gel method, and the effect of carbon coating and control on F content on the structure, morphology, electrochemical properties of LVPF/C are studied comprehensively. Li3V2(PO4)3 and Li9V3(P2O7)3(PO4)2 form as minor secondary phases when LVPF is prepared without carbon source. In contrast Li3V2(PO4)3 and V2O3 are found when lauric acid is used as carbon source. Using optimal concentration of polytetrafluoroethylene (35 wt. % PTFE) and lauric acid (27 wt. % LA) in the synthesis yields carbon coated LVPF (LVPF/C-35) with best electrochemical performance. Lattice parameters of LiVPO4F are consistent with the reported values. Electrochemical properties of the LVPF/C-X cathodes (X = 25, 35 and 45 wt. % PTFE) show the discharge capacities of ∼ 85.4 (∼ 7), ∼ 114.7 (∼ 84.1), ∼ 102.7 (∼ 14.2) mA h g−1 at 0.1C (10C) rates, when scanned in the voltage range of 3.0–4.5 V vs. Li/Li+. A flat potential profile at ∼ 4.2 V vs. Li/Li+ is seen during charging-discharging profiles of the LVPF/C-X samples. From CV studies, the diffusion coefficient is found to be of the order of 10−16 cm2s−1 during oxidation and reduction. BET surface area is more (∼ 75.95 m2 g−1) for LVPF/C-35 compared to other two samples. From Electrochemical impedance spectroscopy, the influence of charge-transfer resistance resulting from the cathode electrolyte interface layer on electrochemical properties is studied.

Phase pure carbon-coated high voltage cathode material LiVPO4F (LVPF/C) is synthesized by a facile sol-gel method and reacting the precursor powder with PTFE. Secondary phases such as Li3V2(PO4)3, Li9V3(P2O7)3(PO4)2, V2O3 and LiVP2O7 are shown to get mitigated by the addition of lauric acid, which also acts as carbon source. Phase pure LiVPO4F with good conducting properties are produced under the optimum use of oleic acid (OA; 1.31 mg, 0.84 wt. %) and lauric acid (LA; 0.25 mg, 0.16 wt. %) which are used to control particle size and carbon coating reagent, respectively. Polytetrafluoroethylene (PTFE, 35 wt.%) is reacted with the precursor during annealing to control fluorine loss. Rietveld refinement indicates the formation of phase pure LiVPO4F. The optimized cathode, LVPF/C (0.25 g LA), exhibit flat potential during the lithiation and dilithiation process with plateaus ~ 4.21 V and ~4.17 V at 0.1C-rate. Discharge capacities of 96.3 mAh g−1 (44.6 mAh g−1) are obtained at 0.1C(10C)-rate. Diffusion coefficient ~10−15 cm2s−1 is estimated from cyclic voltammetry studies. Carbon additive decreases the internal resistance and enables easy charge transfer resistance through the electrode-electrolyte interface. The cumulative effect of synthesizing phase pure compound, carbon coating, with optimum diffusion coefficient and charge transfer resistance provide the better electrochemical performance of the LVPF/C cathode.

Bandgap engineering in lead-free Cs2Ag1-xNaxBiCl6 (x = 0 to 1) double perovskite alloys synthesized through solution-based approach is investigated. The bandgap is shown to vary from 2.64 eV to 3.01 eV as Ag+ at B′ site gets replaced with Na+ cation. Despite a linear change in the lattice parameter according to Vegard's law, bandgap (Eg) changes in a nonlinear fashion for x = 0 to 1 with much lower Eg values observed than predicted by Vegard's rule. Further, we show the bandgap bowing effect in Cs2Ag1-xNaxBiCl6. Raman spectroscopic studies reveal that the changes in the vibrational mode positions arise due to the systematic variations in local distortions of [BiCl6]3– and [AgCl6]5– octahedra. The bandgap change, Raman mode frequency shift, Raman peak width, and the ratio of intensities of Raman modes all show a similar trend as a function of Na substitution concentration (x). The changes are minimal and linear for x from 0 to ∼0.6 and deviate sharply for higher Na concentration (x > 0.6). These observations strongly suggest that the sublattice distortion in the A2B′B″X6 lattice arises due to a mismatch in the octahedra. This imparts a nonlinear change in the bandgap. Thus, a strong interplay between the [Ag(Na)Cl6]5− and [BiCl6]3– octahedra is shown to have a significant influence on the deviation of bandgap from Vegard's rule and further enforces the bandgap bowing effect in Cs2Ag1-xNaxBiCl6.

Synthesis of phase pure Sb2S3 in open atmosphere has been a long-time challenging task due to the oxidation of metal. Here, we demonstrate a robust, one-step solution approach for synthesis of Sb2S3 thin films in open air atmosphere. One-step thermolysis of Sb-MPA complex obtained by mixing antimony chloride and 3-Mercaptopropionic acid (3-MPA) in polar and non-polar solvents yields phase pure thin films. Upon changing the concentration of sulphur in the solvent and polarity of solvent, different microstructures of Sb2S3 such as nanostripes, nanorods and tubular morphology evolve. Irrespective of sulphur concentration in the precursor solution, Sb2S3 thin films are always phase pure and formed in stoichiometric composition. The films are photoconductive in nature and morphology of Sb2S3 influences the photoconductivity. This novel and facile methodology will open new avenues for direct deposition of Sb2S3 thin films for wide range of applications including optoelectronics, photovoltaics and photocatalysis research.