Robust method for uniform coating of carbon nanotubes with V2O5 for next-generation transparent electrodes and Li-ion batteries.

Composites comprising vanadium-pentoxide (V2O5) and single-walled carbon nanotubes (SWCNTs) are promising components for emerging applications in optoelectronics, solar cells, chemical and electrochemical sensors, etc. We propose a novel, simple, and facile approach for SWCNT covering with V2O5 by spin coating under ambient conditions. With the hydrolysis-polycondensation of the precursor (vanadyl triisopropoxide) directly on the surface of SWCNTs, the nm-thick layer of oxide is amorphous with a work function of 4.8 eV. The material recrystallizes after thermal treatment at 600 °C, achieving the work function of 5.8 eV. The key advantages of the method are that the obtained coating is uniform with a tunable thickness and does not require vacuuming or heating during processing. We demonstrate the groundbreaking results for two V2O5/SWCNT applications: transparent electrode and cathode for Li-ion batteries. As a transparent electrode, the composite shows stable sheet resistance of 160 Ω sq-1 at a 90% transmittance (550 nm) - the best performance reported for SWCNTs doped by metal oxides. As a cathode material, the obtained specific capacity (330 mA h g-1) is the highest among all the other V2O5/SWCNT cathodes reported so far. This approach opens new horizons for the creation of the next generation of metal oxide composites for various applications, including optoelectronics and electrochemistry.

Revealing the static and dynamic nanomechanical properties of diatom frustules-Nature's glass lace.

Diatoms are single cell microalgae enclosed in silica exoskeletons (frustules) that provide inspiration for advanced hybrid nanostructure designs mimicking multi-scale porosity to achieve outstanding mechanical and optical properties. Interrogating the structure and properties of diatoms down to nanometer scale leads to breakthrough advances reported here in the nanomechanical characterization of Coscinodiscus oculus-iridis diatom pure silica frustules, as well as of air-dried and wet cells with organic content. Static and dynamic mode Atomic Force Microscopy (AFM) and in-SEM nanoindentation revealed the peculiarities of diatom response with separate contributions from material nanoscale behavior and membrane deformation of the entire valve. Significant differences in the nanomechanical properties of the different frustule layers were observed. Furthermore, the deformation response depends strongly on silica hydration and on the support from the internal organic content. The cyclic loading revealed that the average compliance of the silica frustule is 0.019 m/N and increases with increasing number of cycles. The structure-mechanical properties relationship has a direct impact on the vibrational properties of the frustule as a complex micrometer-sized mechanical system. Lessons from Nature's nanostructuring of diatoms open up pathways to new generations of nano- and microdevices for electronic, electromechanical, photonic, liquid, energy storage, and other applications.

Sulfate-Containing Composite Based on Ni-Rich Layered Oxide LiNi0.8Mn0.1Co0.1O2 as High-Performance Cathode Material for Li-ion Batteries.

Composite positive electrode materials (1-x) LiNi0.8Mn0.1Co0.1O2∙xLi2SO4 (x = 0.002-0.005) for Li-ion batteries have been synthesized via conventional hydroxide or carbonate coprecipitation routes with subsequent high-temperature lithiation in either air or oxygen atmosphere. A comparative study of the materials prepared from transition metal sulfates (i.e., containing sulfur) and acetates (i.e., sulfur-free) with powder X-ray diffraction, electron diffraction, high angle annular dark field transmission electron microscopy, energy-dispersive X-ray spectroscopy, and electron energy loss spectroscopy revealed that the sulfur-containing species occur as amorphous Li2SO4 at the grain boundaries and intergranular contacts of the primary NMC811 crystallites. This results in a noticeable enhancement of rate capability and capacity retention over prolonged charge/discharge cycling compared to their sulfur-free analogs. The improvement is attributed to suppressing the high voltage phase transition and the associated accumulation of anti-site disorder upon cycling and improving the secondary agglomerates' mechanical integrity by increasing interfacial fracture toughness through linking primary NMC811 particles with soft Li2SO4 binder, as demonstrated with nanoindentation experiments. As the synthesis of the (1-x) LiNi0.8Mn0.1Co0.1O2∙xLi2SO4 composites do not require additional operational steps to introduce sulfur, these electrode materials might demonstrate high potential for commercialization.

Solid-electrolyte interphase nucleation and growth on carbonaceous negative electrodes for Li-ion batteries visualized with in situ atomic force microscopy.

Li-ion battery performance and life cycle strongly depend on a passivation layer called solid-electrolyte interphase (SEI). Its structure and composition are studied in great details, while its formation process remains elusive due to difficulty of in situ measurements of battery electrodes. Here we provide a facile methodology for in situ atomic force microscopy (AFM) measurements of SEI formation on cross-sectioned composite battery electrodes allowing for direct observations of SEI formation on various types of carbonaceous negative electrode materials for Li-ion batteries. Using this approach, we observed SEI nucleation and growth on highly oriented pyrolytic graphite (HOPG), MesoCarbon MicroBeads (MCMB) graphite, and non-graphitizable amorphous carbon (hard carbon). Besides the details of the formation mechanism, the electrical and mechanical properties of the SEI layers were assessed. The comparative observations revealed that the electrode potentials for SEI formation differ depending on the nature of the electrode material, whereas the adhesion of SEI to the electrode surface clearly correlates with the surface roughness of the electrode. Finally, the same approach applied to a positive LiNi1/3Mn1/3Co1/3O2 electrode did not reveal any signature of cathodic SEI thus demonstrating fundamental differences in the stabilization mechanisms of the negative and positive electrodes in Li-ion batteries.

Unraveling the Impact of Hole Transport Materials on Photostability of Perovskite Films and p-i-n Solar Cells.

We investigated the impact of a series of hole transport layer (HTL) materials such as Poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), NiOx, poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine (PTAA), and polytriarylamine (PTA) on photostability of thin films and solar cells based on MAPbI3, Cs0.15FA0.85PbI3, Cs0.1MA0.15FA0.75PbI3, Cs0.1MA0.15FA0.75Pb(Br0.15I0.85)3, and Cs0.15FA0.85Pb(Br0.15I0.85)3 complex lead halides. Mixed halide perovskites showed reduced photostability in comparison with similar iodide-only compositions. In particular, we observed light-induced recrystallization of all perovskite films except MAPbI3 with the strongest effects revealed for Br-containing systems. Moreover, halide and ß FAPbI3 phase segregations were also observed mostly in mixed-halide systems. Interestingly, coating perovskite films with the PCBM layer spectacularly suppressed light-induced growth of crystalline domains as well as segregation of Br-rich and I-rich phases or ß FAPbI3. We strongly believe that all three effects are promoted by the light-induced formation of surface defects, which are healed by adjacent PCBM coating. While comparing different hole-transport materials, we found that NiOx and PEDOT:PSS are the least suitable HTLs because of their interfacial (photo)chemical interactions with perovskite absorbers. On the contrary, polyarylamine-type HTLs PTA and PTAA form rather stable interfaces, which makes them the best candidates for durable p-i-n perovskite solar cells. Indeed, multilayered ITO/PTA(A)/MAPbI3/PCBM stacks revealed no aging effects within 1000 h of continuous light soaking and delivered stable and high power conversion efficiencies in solar cells. The obtained results suggest that using polyarylamine-type HTLs and simple single-phase perovskite compositions pave a way for designing stable and efficient perovskite solar cells.

Origins of irreversible capacity loss in hard carbon negative electrodes for potassium-ion batteries.

Hard carbon (HC) is considered as a negative electrode material for potassium-ion batteries, but it suffers from significant irreversible capacity loss at the first discharge cycle. Here, we investigated the possible reasons of this capacity loss with a combination of in situ AFM and various ex situ TEM techniques (high resolution TEM and high angle annular dark field scanning TEM imaging, and STEM-EELS and STEM-EDX spectroscopic mapping) targeting the electrode/electrolyte interphase formation process in the carbonate-based electrolyte with and without vinylene carbonate (VC) as an additive. The studied HC consists of curved graphitic layers arranged into short packets and round cages, the latter acting as traps for K+ ions causing low Coulombic efficiency between cycling. Our comparative study of solid electrolyte interphase (SEI) formation in the carbonate-based electrolyte with and without the VC additive revealed that in the pristine electrolyte, the SEI consists mostly of inorganic components, whereas adding VC introduces a polymeric organic component to the SEI, increasing its elasticity and stability against fracturing upon HC expansion/contraction during electrochemical cycling. Additionally, significant K+ loss occurs due to Na+ for K+ exchange in Na-carboxymethyl cellulose used as a binder. These findings reflect the cumulative impact of the internal HC structure, SEI properties, and binder nature into the electrochemical functional properties of the HC-based anodes for K-ion batteries.

Reduction of Methylammonium Cations as a Major Electrochemical Degradation Pathway in MAPbI3 Perovskite Solar Cells.

Herein, we reveal for the first time a comprehensive mechanism of poorly investigated electrochemical decomposition of CH3NH3PbI3 using a set of microscopy techniques (optical, AFM, PL) and ToF-SIMS. We demonstrate that applied electric bias induces the oxidation of I- to I2, which remains trapped in the film in the form of polyiodides, and hence, the process can be conceivably reversed by reduction. On the contrary, reduction of organic methylammonium cation produces volatile products, which leave the film and thus make the degradation irreversible. Our results lead to a paradigm change when considering design principles for improving the stability of complex lead halide materials as those featuring organic cations rather than halide anions as the most electric field-sensitive components. Suppressing the electrochemical degradation of complex lead halides represents a crucial challenge, which should be addressed in order to bring the operational stability of perovskite photovoltaics to commercially interesting benchmarks.

Light or Heat: What Is Killing Lead Halide Perovskites under Solar Cell Operation Conditions?

We report the first systematic assessment of intrinsic photothermal stability of a large panel of complex lead halides APbX3 incorporating different univalent cations (A = CH3NH3+, [NH2CHNH2]+, Cs+) and halogen anions (X = Br, I) using a series of analytical techniques such as UV-vis and X-ray photoelectron spectroscopy, X-ray diffraction, EDX analysis, atomic force and scanning electron microscopy, ESR spectroscopy, and mass spectrometry. We show that heat stress and light soaking induce a severe degradation of perovskite films even in the absence of oxygen and moisture. The stability of complex lead halides increases in the order MAPbBr3 < MAPbI3 < FAPbI3 < FAPbBr3 < CsPbI3 < CsPbBr3, thus featuring all-inorganic perovskites as the most promising absorbers for stable perovskite solar cells. An important correlation was found between the stability of the complex lead halides and the volatility of univalent cation halides incorporated in their structure. The established relationship provides useful guidelines for designing new complex metal halides with immensely improved stability.

Impressive Radiation Stability of Organic Solar Cells Based on Fullerene Derivatives and Carbazole-Containing Conjugated Polymers.

We explored the radiation stability of carbazole-based electron-donor conjugated polymers, acceptor fullerene derivative [60]PCBM, and their blends as active layer components of organic solar cells. An exposure to Î³ rays induced evident degradation effects in bulk samples of the pristine fullerene acceptor ([60]PCBM) and two investigated electron-donor conjugated polymers: PCDTBT and PCDTTBTBTT. The most severe radiation damage occurred in [60]PCBM as can be concluded from the significant losses in open circuit voltage, fill factor, and efficiency of photovoltaic (PV) devices comprising the exposed fullerene acceptor. Conjugated polymers PCDTBT and PCDTTBTBTT showed substantially different radiation stabilities: the samples of PCDTTBTBTT exposed to 200 Gy lost ∼25% of their nominal photovoltaic efficiency due to a substantial decay of all device parameters, while PCDTBT alone showed just a minor aging under the same conditions. The fullerene-polymer composites were much more resistant with respect to the radiation damage than the bulk samples of pristine materials. In particular, the PCDTBT/[60]PCBM composite films demonstrated an outstanding radiation stability while maintaining more than 80% of the initial photovoltaic efficiency after exposure to γ rays with a maximum absorbed dose of 6500 Gy. Considering an average annual radiation dose of 160 Gy according to the NASA estimations for satellites at geocentric Earth orbits, organic solar cells based on PCDTBT/[60]PCBM blends hold a promise to deliver lifetimes well above 10 years. The revealed impressive radiation stability of PCDTBT/[60]PCBM blends in combination with other advantages of organic solar cells, for example, their mechanical flexibility and lightweight, points to a bright future of this PV technology in space industry applications.

γ-Ray-Induced Degradation in the Triple-Cation Perovskite Solar Cells.

We report on the impact of γ radiation (0-500 Gy) on triple-cation Cs0.15MA0.10FA0.75Pb(Br0.17I0.83)3 perovskite solar cells. A set of experiments was designed to reveal the individual contributions of the hole-collecting bottom electrode, perovskite absorber, and electron transport layer (ETL) to the overall solar cell degradation under radiation exposure. We show that the glass/ITO/PEDOT:PSS hole-collecting electrode withstands a 500 Gy dose without any losses in the solar cell performance. In contrast, the perovskite absorber films and PC61BM ETL are very sensitive to γ rays, as can be concluded from the radiation-induced decay of the solar cell efficiency by ∼32-41%. Red shift of the perovskite emission bands and strong enhancement of the photoluminescence suggest that γ rays induce phase segregation of iodine-rich and bromine-rich domains, which represents the first reported example of the radiation-induced halide phase separation in perovskite films. The degradation pathway revealed here emphasizes the need for developing a new generation of metal halide absorbers and ETL materials with improved radiation stability to enable potential space applications of perovskite photovoltaics.

Reversible and Irreversible Electric Field Induced Morphological and Interfacial Transformations of Hybrid Lead Iodide Perovskites.

We report reversible and irreversible strain effects and interfacial atomic mixing in MAPbI3/ITO under influence of external electric bias and photoillumination. Using conductive-probe atomic force microscopy, we locally applied a bias voltage between the MAPbI3/ITO and the conductive tip and observed local dynamic strain effects and current under conditions of forward bias. We found that the reversible part of the strain is associated with a current spike at the current onset stage and can therefore be related to an electrochemical process accompanied by local molar volume change. Similar partly reversible surface deformation was observed when the tip-sample contact was illuminated by light. Time-of-flight secondary ion mass spectrometry of electrically biased regions revealed massive atomic mixing at the buried MAPbI3/ITO interface, while the top MAPbI3 surface, subjected to strong morphological damage at the tip-surface contact, revealed less significant chemical decomposition.

Exploring the Photovoltaic Performance of All-Inorganic Ag2PbI4/PbI2 Blends.

We present an all-inorganic photoactive material composed of Ag2PbI4 and PbI2, which shows unexpectedly good photovoltaic performance in planar junction solar cells delivering external quantum efficiencies of ∼60% and light power conversion efficiencies of ∼3.9%. The revealed characteristics are among the best reported to date for metal halides with nonperovskite crystal structure. Most importantly, the obtained results suggest a possibility of reaching high photovoltaic efficiencies for binary and, probably, also ternary blends of different inorganic semiconductor materials. This approach, resembling the bulk heterojunction concept guiding the development of organic photovoltaics for two decades, opens wide opportunities for rational design of novel inorganic and hybrid materials for efficient and sustainable photovoltaic technologies.

Probing the Intrinsic Thermal and Photochemical Stability of Hybrid and Inorganic Lead Halide Perovskites.

We report a careful and systematic study of thermal and photochemical degradation of a series of complex haloplumbates APbX3 (X = I, Br) with hybrid organic (A+ = CH3NH3) and inorganic (A+ = Cs+) cations under anoxic conditions (i.e., without exposure to oxygen and moisture by testing in an inert glovebox environment). We show that the most common hybrid materials (e.g., MAPbI3) are intrinsically unstable with respect to the heat- and light-induced stress and, therefore, can hardly sustain the real solar cell operation conditions. On the contrary, the cesium-based all-inorganic complex lead halides revealed far superior stability and, therefore, provide an impetus for creation of highly efficient and stable perovskite solar cells that can potentially achieve pragmatic operational benchmarks.

Highly Efficient All-Inorganic Planar Heterojunction Perovskite Solar Cells Produced by Thermal Coevaporation of CsI and PbI2.

We report here all inorganic CsPbI3 planar junction perovskite solar cells fabricated by thermal coevaporation of CsI and PbI2 precursors. The best devices delivered power conversion efficiency (PCE) of 9.3 to 10.5%, thus coming close to the reference MAPbI3-based devices (PCE ≈ 12%). These results emphasize that all inorganic lead halide perovskites can successfully compete in terms of photovoltaic performance with the most widely used hybrid materials such as MAPbI3.

Giant Electric-Field-Induced Strain in PVDF-Based Battery Separator Membranes Probed by Electrochemical Strain Microscopy.

Efficiency of lithium-ion batteries largely relies on the performance of battery separator membrane as it controls the mobility and concentration of Li-ions between the anode and cathode electrodes. Recent advances in electrochemical strain microscopy (ESM) prompted the study of Li diffusion and transport at the nanoscale via electromechanical strain developed under an application of inhomogeneous electric field applied via the sharp ESM tip. In this work, we observed unexpectedly high electromechanical strain developed in polymer membranes based on porous poly(vinylidene fluoride) (PVDF) and poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) and, using it, could study a dynamics of electroosmotic flow of electrolyte inside the pores. We show that, independently of the separator membrane, electric field-induced deformation observed by ESM on wetted membrane surfaces can reach up to 10 nm under a moderate bias of 1 V (i.e., more than an order of magnitude higher than that in best piezoceramics). Such a high strain is explained by the electroosmotic flow in a porous media composed of PVDF. It is shown that the strain-based ESM method can be used to extract valuable information such as average pore size, porosity, elasticity of membrane in electrolyte solvent, and membrane-electrolyte affinity expressed in terms of zeta potential. Besides, such systems can, in principle, serve as actuators even in the absence of apparent piezoelectricity in amorphous PVDF.

Single- and multi-frequency detection of surface displacements via scanning probe microscopy.

Piezoresponse force microscopy (PFM) provides a novel opportunity to detect picometer-level displacements induced by an electric field applied through a conducting tip of an atomic force microscope (AFM). Recently, it was discovered that superb vertical sensitivity provided by PFM is high enough to monitor electric-field-induced ionic displacements in solids, the technique being referred to as electrochemical strain microscopy (ESM). ESM has been implemented only in multi-frequency detection modes such as dual AC resonance tracking (DART) and band excitation, where the response is recorded within a finite frequency range, typically around the first contact resonance. In this paper, we analyze and compare signal-to-noise ratios of the conventional single-frequency method with multi-frequency regimes of measuring surface displacements. Single-frequency detection ESM is demonstrated using a commercial AFM.