Search arXivSearch

arXiv subjects

Monojit Bag

Publications and source records attributed to Monojit Bag.

6 recordsLinked to original sources

Binder chemistry sets the interfacial balance constant in CsPbBr$_3$ nanocrystal supercapacitor electrodes

Previous work on lead-free tin halide perovskites showed that the binder instead sets the electrolyte concentration at which capacitance is maximised, following the relationship $100 \times [\mathrm{Li}^+]_{\mathrm{opt}} + \mathrm{PVDF}_{\mathrm{wt}\%} = ξ_{\mathrm{Int}}$ with $ξ_{\mathrm{Int}} = 25 \pm 2.5$, established by varying the loading of a single polymer. Whether $ξ_{\mathrm{Int}}$ is universal or specific to that polymer has not been tested. Here, four binders spanning fluorinated (PVDF), carboxylic (PAA), cellulosic (CMC) and sulfonic (PEDOT:PSS) chemistry are compared on $\mathrm{CsPbBr_3}$ nanocrystal electrodes at four LiTFSI concentrations in acetonitrile, with binder loading fixed at 15 wt% and all other formulation variables held constant. The relationship applies to $\mathrm{CsPbBr_3}$: PVDF at 15 wt% gives an optimum at 0.10--0.15 M and 112 F g$^{-1}$, against 126 F g$^{-1}$ reported for $\mathrm{CsSnCl_3}$ under the same conditions, extending the result to a different B-site cation, halide and crystal system. PVDF and CMC optimise at 0.10 M, giving $ξ_{\mathrm{Int}} = 25$, while PAA and PEDOT:PSS optimise at 0.15 M, giving $ξ_{\mathrm{Int}} = 30$, with maximum values of 188 F g$^{-1}$ for PAA and 146 mF cm$^{-2}$ for PEDOT:PSS. The two binders showing the shift carry ionisable acid groups at high density, indicating that $ξ_{\mathrm{Int}}$ expressed in weight percent requires a binder-specific value. In all four electrodes, $\mathrm{CsPbBr_3}$ converts to $\mathrm{PbBr_2}$ and CsBr during electrochemical characterisation, and the surface lead content of the PEDOT:PSS electrode decreases.

cond-mat.mtrl-sci

Sodium Incorporation in CsPbBr$_{3-x}$I$_x$ Nanocrystal Electrodes: Lattice Contraction and the Suppression of Field-Driven Iodine Expulsion

Mixed-halide perovskite nanocrystal electrodes fail in supercapacitors through field-driven halide segregation. In undoped $\mathrm{CsPbBr_2I}$, this appears as a capacitance that climbs to 218% of its first-cycle value by cycle 1378 and then collapses to 39% by cycle 2500, with complete loss of the iodine signal from the cycled electrode. This work tests whether sodium incorporation suppresses that failure mode. Na-doped $\mathrm{CsPbBr_{3-x}I_x}$ ($x = 0, 1, 2$) nanocrystals were prepared by ligand-assisted reprecipitation at a Na/Pb precursor ratio of 1.25:1.00 and compared with undoped analogues in 0.1 M tetrabutylammonium tetrafluoroborate in anhydrous dichloromethane. Sodium contracts the pseudocubic lattice parameter of $\mathrm{CsPbBr_3}$ from $5.908 \pm 0.029$ to $5.851 \pm 0.019$ $\mathring{\mathrm{A}}$ after correction for specimen displacement. Specific capacitance at 0.3 A g$^{-1}$ rises for every composition, from 42 to 75, from 63 to 96, and from 56 to 84.5 F g$^{-1}$. Na-$\mathrm{CsPbBr_2I}$ gives the lowest charge-transfer resistance at 175 $Ω$ and the highest ion diffusion coefficient at $1.6 \times 10^{-16}$ m$^2$ s$^{-1}$, and power-law exponents between 0.33 and 0.45 at all potentials examined show that charge storage is limited by ion transport through the pore network rather than by the interfacial process. In the sodium-containing (Na-$\mathrm{CsPbBr_2I}$) electrode, the capacitance rise reaches only 115% at cycle 600, no collapse follows, and 97% is retained at 2500 cycles, the excess above the first-cycle value being reduced by a factor of 7.9. Iodine is retained at unchanged binding energy, and the Br:I ratio measured by elemental mapping is 2.30 after cycling against 2.25 before.

cond-mat.mtrl-sci

An Interfacial Balance Rule Governs Binder-Electrolyte Coupling in Lead-Free Perovskite Energy Storage

Electrode binders are conventionally regarded as inert structural components. Here, we show that in lead-free perovskite supercapacitors, the binder defines the optimal electrolyte composition. Across a factorial matrix of poly(vinylidene fluoride) (PVDF) loadings and LiTFSI concentrations in CsSnCl$_3$ electrodes, the capacitance optimum shifts systematically with binder content along a single linear relationship, described by the Interfacial Balance Rule ($λ+θ=1$), where $λ$ and $θ$ are the normalized lithium-supply and polymer contributions at the optimized interfacial state. The same relationship holds for hybrid MASnCl$_3$, showing that the optimum is governed by the polymer-electrolyte interface rather than the perovskite lattice chemistry. Simulations using a pre-trained MACE machine-learned interatomic potential show that PVDF adopts a planar configuration on CsSnCl$_3$ and simultaneously interacts with cationic and anionic sites. This configuration homogenizes lithium adsorption energetics, introduces fluorine-mediated coordination, and confines lithium to a two-dimensional interfacial region while preserving lateral mobility. Tuning polymer coverage through surface density and chain length reveals a finite interfacial lithium accommodation capacity that marks the onset of out-of-plane aggregation. The Interfacial Balance Rule provides a macroscopic descriptor of this finite interfacial resource, balancing polymer-mediated lithium stabilization against limited accommodation space. Binder loading is therefore an active design parameter for polymer-regulated energy-storage interfaces.

cond-mat.mtrl-sci

Unraveling the Roles of Shallow, Deep and Auger Trapping in Charge Carrier Recombination in Triple-Cation Perovskites

Understanding charge-carrier recombination in metal halide perovskites is essential for accurately identifying the factors limiting solar cell efficiency, yet it remains challenging due to the interplay of multiple competing processes. Here, we combine time-resolved photoluminescence and excitation dependent photoluminescence quantum yield measurements over a wide range of fluences and repetition rates to investigate recombination dynamics in triple-cation perovskite thin films. By jointly analyzing these multidimensional datasets, we develop a unified model that quantitatively reproduces both photoluminescence decays and absolute quantum yields across all excitation conditions. Our results reveal the coexistence of deep and shallow traps, as well as a second-order nonradiative recombination pathway attributed to Auger-assisted trapping. Importantly, this mechanism dominates under one-sun illumination, making it a critical limiting factor for photovoltaic performance. These findings provide a comprehensive framework for understanding recombination in perovskites and highlight the importance of higher-order defect-mediated processes in determining their efficiency.

cond-mat.mtrl-sci

Raveling the Role of Dopants on Charge Carrier Kinetics of TiO$_2$ Electrodes using Electrochemical Impedance Spectroscopy

We synthesized the pure and co-doped titanium dioxide (TiO$_2$) electrodes via spin coating. We examined the optical and electronic properties of as-prepared thin film electrodes with co-doping of transition metals and non-metals. The co-doping of Cu, Zn, and N increase the absorption of the radiation in the visible region. The doping leads to the formation of defect states in the electrodes. In this article, we have studied the carrier kinetics in pristine and co-doped TiO2 electrodes. To study the role of dopants in carrier transport of the synthesized TiO2 based electrodes, the electrochemical impedance spectroscopy measurement is performed in the frequency range of 10-1 Hz to 106 Hz. The study reveals the influence of dopants on electron-hole recombination in the defect sites present in bulk and the transport mechanism of the electrons and ions to the surface/interface of the electrodes.

physics.app-ph

Universality in Intensity Modulated Photocurrent in Bulk-Heterojunction Polymer Solar Cells

We observe a universal feature in the frequency dependence of intensity modulated photocurrent Iph based on studies of a variety of efficient bulk-heterojunction polymer solar cells (BHJ-PSCs). This feature of Iph appears in the form of a local maximum in the 5 kHz < frequency < 10 kHz range and is observed to be largely independent of the external parameters such as modulated light intensity (Lac), wavelength, temperature (T), and external field (EF) over a wide range. Simplistic kinetic models involving carrier generation, recombination and extraction processes are used to interpret the overall essential features of Iph and correlate it to the device parameters.

cond-mat.mtrl-sci