Reversible Phase Transition Research Articles

Unusual Triple-State Switching of Thermally Induced Birefringence in a Two-Dimensional Perovskite Ferroelectric.

Birefringent crystals hold a significant position in optical and optoelectronic fields due to their capability to control polarized light. Despite various chemical strategies devoted to designing birefringent crystals, it remains a challenge to switch and manipulate birefringence under physical stimuli. Here we present an unusual triple-state switching of birefringence in a 2D perovskite ferroelectric, (N-methylcyclohexylammonium)2PbCl4 (1), which exhibits two reversible phase transitions at 361 and 373 K. The in-plane birefringence of 1 (Δnbc) shows three distinctive states inside the bc plane, namely, the low-, high-, and zero-Δnbc states. Strikingly, a huge augmentation of Δnbc is solidly confirmed up to ∼400% between its low and high states, far beyond other birefringent materials. The origin of this triple-state switching of birefringence involves the variation of the ferroelastic strain and domain in the vicinity of the phase transition. As an entirely new mode of switching birefringence, this work facilitates the further development of new intelligent nonlinear optics.

High-quality VO2 thin films sputter-deposited on borosilicate glass substrates for modulating solar transmission and thermal emission

M1-phase VO2 exhibits a reversible phase transition between the insulating and metallic states at T = ∼341 K, and VO2-based smart windows have been extensively studied. The smart window application requires the growth of high-quality VO2 films with a large resistivity change and small hysteresis width (ΔT) on glass substrates using a scalable deposition method such as sputtering. However, the polymorphic nature of VO2 makes it challenging to obtain high-quality VO2 films on ordinary window glasses (borosilicate and soda-lime glasses). Thus far, VO2 films sputtered on glass substrates have exhibited resistivity changes of 1.5–2 orders of magnitude and ΔT = 3–19 °C. In this study, we show that high-quality VO2 films with a resistivity change of 2.5−3.0 orders of magnitude and ΔT = 2 °C can be grown on borosilicate glass substrates via radio-frequency sputtering followed by thermal annealing. The simultaneous achievement of such a large resistivity change and small hysteresis width is highly encouraging not only for smart windows but also for other applications. With respect to the modulation of solar transmission and thermal emission with temperature, the performance levels of the produced VO2 films were 70−75 % of those expected from pure M1-phase VO2 films.

Enhancing Optical Properties of Zn-Mn Solid Solution Hybrid Halides for Wide Color Gamut Backlight Displays.

Hybrid metal halides display a range of optical properties and hold promise for various applications such as solid-state lighting, anti-counterfeiting measures, backlight displays, and X-ray detection. The incorporation of zinc into (C13H26N)2MnBr4 aims to enhance its structural rigidity and improve its narrow band green light emission properties. The resulting (C13H26N)2ZnBr4 compound exhibits an identical crystal structure to (C13H26N)2MnBr4, indicating the potential for a solid solution of varying Zn and Mn ratios within this structural framework. (C13H26N)2Zn0.2Mn0.8Br4 exhibits significantly enhanced properties, including a photoluminescence quantum yield of 92%, a minimum full width at half maximum of 43nm, and 85% retention of room temperature emission at 420K. Additionally, crystals of (C13H26N)2ZnCl4 and (C7H18N)2ZnX4 (X = Br, I) are synthesized, with (C7H18N)2ZnBr4 displaying luminescent color changes dependent on excitation. (C7H18N)2Zn0.2Mn0.8Br4 demonstrates reversible phase transitions and alterations in optical properties. A white light-emitting diode utilizing (C13H26N)2Zn0.2Mn0.8Br4 and commercial phosphors exhibited a color gamut of 112.2% of the National Television Standards Committee 1931 Standard. This investigation introduces a stable and highly efficient narrow-band green phosphor suitable for displays.

In situ observation of reversible phase transitions in Gd-doped ceria driven by electron beam irradiation

Ceria-based oxides are widely utilized in diverse energy-related applications, with attractive functionalities arising from a defective structure due to the formation of mobile oxygen vacancies (VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document}). Notwithstanding its significance, behaviors of the defective structure and VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} in response to external stimuli remain incompletely explored. Taking the Gd-doped ceria (Ce0.88Gd0.12O2-δ) as a model system and leveraging state-of-the-art transmission electron microscopy techniques, reversible phase transitions associated with massive VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} rearrangement are stimulated and visualized in situ with sub-Å resolution. Electron dose rate is identified as a pivotal factor in modulating the phase transition, and both the VO⋅⋅\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${V}_{O}^{\\cdot \\cdot }$$\\end{document} concentration and the orientation of the newly formed phase can be altered via electron beam. Our results provide indispensable insights for understanding and refining the microscopic pathways of phase transition as well as defect engineering, and could be applied to other similar functional oxides.

Boosting the intrinsic kinetics of lithium vanadium phosphate via an electrochemically active cross-link framework

The monoclinic lithium vanadium phosphate Li3V2(PO4)3 (LVP) is considered a promising cathode for lithium-ion batteries (LIBs) due to its high working voltage (>4.0 V, vs. Li+/Li) and high theoretical specific capacity (197 mAh g−1). However, the electrochemical procedure accompanied by three-electron reactions in LVP has proven challenging due to the complexity or asymmetry of the reaction pathways, thus limiting its wide application. Herein, an electrochemically active cross-link framework of LVP, LiFe0.3Mn0.7PO4 (LFMP) and graphene are successfully synthesized by an in situ catalytic process, which enables stable cycling and high-rate capabilities up to 4.8 V (vs. Li+/Li). Graphene-like carbon can be formed in situ with VOx as the catalyst and polyvinyl alcohol as the carbon source, and LFMP also inhibits the growth of LVP particles, allowing rapid Li+ and electron transport in the cathodes. Both in situ and ex situ X-ray diffraction prove that the cross-link framework efficiently smooths the lattice mismatch and achieves highly reversible structural phase transitions. The prepared 0.9LVP·0.1LFMP is able to provide a superior rate capability of 123 mAh g−1 at 20 C. After 150 cycles, the 0.9LVP·0.1LFMP shows 97.4 % capacity retention even under a voltage of 4.8 V (vs. Li+/Li). This work develops a new strategy for the future design of high-voltage and high-power cathode materials for LIBs.

Revealing the role of B-site cations in the antiferroelectricity of NaNbO3-based perovskites

The promising prospects of antiferroelectric perovskite oxides in the realm of energy storage applications hinge on the unique field-induced phase transitions. Once the transition is triggered by the application of an electric field, characteristic double polarization loops appear. However, NaNbO3-based materials that exhibit a reversible phase transition are still rare, which hinders the practical applications of lead-free antiferroelectrics. Here, the impact of materials chemistry on the competition between antiferroelectric and ferroelectric states is demonstrated in a series of NaNbO3-based solid solutions with varying perovskite B-site cations, while the A-site is fixed as strontium. The crystal structure is analyzed on the basis of Rietveld refinement of high-energy X-ray diffraction data. The phase transition behavior as well as the antiferroelectric and ferroelectric properties are probed by a series of electrical measurements. The antiferroelectric phase is universally observed for all investigated materials in the virgin state. The SrTiO3-substituted system shows an irreversible phase transition similar to that of pure NaNbO3. In contrast, double polarization hysteresis loops are observed in the SrHfO3-, SrZrO3-, and SrSnO3-substituted systems. It is confirmed that compounds that can reduce the tolerance factor of the system contribute to the stabilization of the antiferroelectric order, while those that can reduce the electronegativity difference lead to more pronounced double loops. The competition between antiferroelectricity and ferroelectricity is linked to the competition between covalent and ionic bonding in perovskites.

Reversible Structural Phase Transitions in Zero-Dimensional Cu(I)-Based Metal Halides for Dynamically Tunable Emissions.

Exploring structural phase transitions and luminescence mechanisms in zero-dimensional (0D) metal halides poses significant challenges, that are crucial for unlocking the full potential of tunable optical properties and diversifying their functional capabilities. Herein, we have designed two inter-transformable 0D Cu(I)-based metal halides, namely (C19H18P)2CuI3 and (C19H18P)2Cu4I6, through distinct synthesis conditions utilizing identical reactants. Their optical properties and luminescence mechanisms were systematically elucidated by experiments combined with density functional theory calculations. The bright cyan-fluorescent (C19H18P)2CuI3 with high photoluminescence quantum yield (PLQY) of 77 % is attributed to the self-trapped exciton emission. Differently, the broad yellow-orange fluorescence of (C19H18P)2Cu4I6 displays a remarkable PLQY of 83 %. Its luminescence mechanism is mainly attributed to the combined effects of metal/halide-to-ligand charge transfer and cluster-centered charge transfer, which effects stem from the strong Cu-Cu bonding interactions in the (Cu4I6)2- clusters. Moreover, (C19H18P)2CuI3 and (C19H18P)2Cu4I6 exhibit reversible structural phase transitions. The elucidation of the phase transitions mechanism has paved the way for an unforgeable anti-counterfeiting system. This system dynamically shifts between cyan and yellow-orange fluorescence, triggered by the phase transitions, bolstering security and authenticity. This work enriches the luminescence theory of 0D metal halides, offering novel strategies for optical property modulation and fostering optical applications.

Elastin-like polypeptide-functionalized nanobody for column-free immunoaffinity purification of aflatoxin B1.

A column-free immunoaffinity purification (CFIP) technique for sample preparation of aflatoxin B1 (AFB1) was developed using an AFB1-specific nanobody (named G8) and an elastin-like polypeptide (ELP). The reversible phase transition between liquid and solid in response to temperature changes was exhibited by the ELP which was derived from human elastin. The G8 was tagged with ELPs of various lengths (20, 40, 60, and 80 repeat units) at the C-terminus using recursive directional ligation (RDL). Coding sequences were then subcloned into pET30a at the multiple cloning sites. Bioactive recombinant proteins were produced by expressing them as inclusion bodies in Escherichia coli BL21 (DE3), then dissolved and refolded. Analysis by indirect competitive enzyme-linked immunosorbent assay (icELISA) and transition temperature (Tt) measurement confirmed that the refolded G8-ELPs preserved the ability to recognize AFB1 as well as phase transition when the temperature rose above Tt. To establish the optimal conditions for cleaning AFB1, the effects of various parameters on recovery were investigated. The recovery in ELISA tests was 95 ± 3.67% under the optimized CFIP workflow. Furthermore, the CFIP-prepared samples were applied for high-performance liquid chromatography (HPLC) detection. The recovery in the CFIP-HPLC test ranged from 54 ± 1.86% to 98 ± 3.58% for maize, rice, soy sauce, and vegetable oil samples. To the best of our knowledge, this is the first report combining the function of both nanobody and ELP to develop a cleanup technique for small molecules in a complex matrix. The CFIP for the sample pretreatment was easy to use and inexpensive. In contrast to conventional immunosensitivity materials, the reagent utilized in the CFIP was entirely biosynthesized without any chemical coupling reactions. This suggests that the nanobody-ELP may serve as a useful dual-functional reagent for the development of sample cleaning or purification methods.

Thermodynamic investigation of reduced barium molybdates

Precise identification and thermodynamic assessment of the various phases in spent nuclear fuel are necessary for the accurate dynamic modeling of nuclear fuel. The Thermodynamics of Advanced Fuels – International Database (TAF-ID) compiles high-quality, self-consistent, and reliable thermodynamic data of various phases in chemical systems of interest for the international nuclear industry, such as the Ba-Mo-O ternary system. The thermodynamic properties of compounds in the Ba-Mo-O ternary system, especially those of hexavalent Mo, have been extensively studied and included in computational thermodynamic assessments. In contrast, compounds with Mo in reduced oxidation states, such as BaMo6O10 and Ba3Mo18O28, have been excluded from such assessments due to a lack of experimentally assessed thermodynamic data. In this work, high-quality samples of the aforementioned compounds were synthesized, and the first experimental assessment of their heat capacities in the temperature range 300–600 K were obtained. Furthermore, a reversible phase transition was identified at ∼380 K for BaMo6O10. The collected experimentally-assessed thermodynamic data from this work and initial calculated estimations of standard enthalpies of formation and entropies for these compounds were successfully integrated into a preliminary, updated Ba-Mo-O thermodynamic assessment using the CALPHAD method. Key thermodynamic properties of the newly included compounds (i.e., standard enthalpy of formation and entropy) were calculated using the new Ba-Mo-O assessment.

Low temperature phase transitions in the visible and near-infrared (VNIR) reflectance spectra of (NH4)2HPO4 and (NH4)HSO4 salts

The detection of ammonium bearing crystalline solids in salt-water systems on icy bodies and solar system bodies could provide information about the ascent of these salts from a deep reservoir within the hydrosphere. Due to their chemical-physical properties, NH4+ compounds play a key role both in the internal dynamics of celestial bodies and in the potential habitability of ocean worlds. In this work we analysed the reflectance spectra of two synthetic NH4+ salts: ammonium hydrogen phosphate (NH4)2HPO4 and ammonium hydrogen sulphate (NH4)HSO4 in the 1–4.2 μm spectral range at low temperature, between 110 and 290 K. For (NH4)2HPO4 we also examined the effect of three different grain sizes (150–125 μm; 125–80 μm; 80–32 μm). The collected reflectance spectra show absorption features related to NH4+ group overtone and combination modes in the 1–2.5 μm range. In particular, the bands located at ∼1.09 μm (3ν3), ∼1.30 μm (2ν3 + ν4), ∼1.58 μm (2ν3), ∼2.02 μm (ν2 + v3) and ∼ 2.2 μm (v3 + v4) could be useful to discriminate these salts. The low temperature spectra, compared to those at ambient temperature, reveal finer structures, displaying sharper and narrower absorption bands. The selected NH4+-bearing salts are subjected to reversible low temperature phase transitions, which are revealed in the spectra by a progressive growth and shift of the bands toward shorter wavelengths with a drastic change of their depth. We performed laboratory measurements of ammonium (NH4+) compounds to address the limited data available expanding the existing database. The collected cryogenic spectra can be directly compared with remote sensing data from planetary missions of the upcoming decade such as NASA's Europa Clipper, and ESA's JUICE and the newly launched James Webb Space Telescope expanding the existing database of ammonium compounds at cryogenic temperature.

Reversible phase transition poly(benzyl methacrylate)/ionic liquid electrolytes for effective overheating protection in lithium batteries

Battery safety is influenced by various factors, with thermal runaway being one of the most significant concerns. While most studies have concentrated on developing one-time, self-activating mechanism for thermal protection, such as temperature-responsive electrodes, and thermal-shutdown separators, these methods only provide irreversible protection. Recently, reversible temperature-sensitive electrolytes have emerged as promising alternatives, offering both thermo-reversibility and self-protective properties. However, further research is crucial to fully understand these thermal-shutdown electrolytes. In this study, we propose lower critical solution temperature (LCST) phase behavior poly(benzyl methacrylate)/imidazolium-based ionic liquid mixtures to prepare temperature-sensitive electrolytes that provide reversible thermal shutdown protection of batteries. This electrolyte features an appropriate protection temperature (∼105°C) and responds quickly within a 1 min at 105°C, causing cells to hardly discharge as the voltage suddenly drops to 3.38 V, and providing efficient thermal shutdown protection within 30 min. Upon cooling back to room temperature, the battery regains its original performance. Additionally, the electrolyte exhibits excellent cycling stability with the capacity retention of the battery is 91.6% after 500 cycles. This work provides a viable solution for preventing batteries from thermal runaway triggered by overheating.

Reversible Single‐Pulse Laser‐Induced Phase Change of Sb2S3 Thin Films: Multi‐Physics Modeling and Experimental Demonstrations

AbstractPhase change materials (PCMs) have gained a tremendous interest as a means to actively tune nanophotonic devices through the large optical modulation produced by their amorphous to crystalline reversible transition. Recently, materials such as Sb2S3 emerged as particularly promising low loss PCMs, with both large refractive index modulations and transparency in the visible and near‐infrared. Controlling the local and reversible phase transition in this material is of major importance for future applications, and an appealing method to do so is to exploit pulsed lasers. Yet, the physics and limits involved in the optical switching of Sb2S3 are not yet well understood. Here, the reversible laser‐induced phase transition of Sb2S3 is investigated, focusing specifically on the mechanisms that drive the optically induced amorphization, with multi‐physics considerations including the optical and thermal properties of the PCM and its environment. The laser energy threshold for reversibly changing the phase of the PCM is determined through both theoretical analysis and experimental investigation, not only between fully amorphous and crystalline states but also between partially recrystallized states. Then, the non‐negligible impact of the material's polycrystallinity and anisotropy on the power thresholds for optical switching is revealed. Finally, the challenges related to laser amorphization of thick Sb2S3 layers are addressed, as well as strategies to overcome them. These results enable a qualitative and quantitative understanding of the physics behind the optically‐induced reversible change of phase in Sb2S3 layers.

Synthesis, the Reversible Isostructural Phase Transition, and the Dielectric Properties of a Functional Material Based on an Aminobenzimidazole-Iron Thiocyanate Complex.

By introducing disordered molecules into a crystal structure, the motion of the disordered molecules easily induces the formation of multidimensional frameworks in functional crystal materials, allowing for structural phase transitions and the realization of various dielectric properties within a certain temperature range. Here, we prepared a novel ionic complex [C7H8N3]3[Fe(NCS)6]·H2O (1) between 2-aminobenzimidazole and ferric isothiocyanate from ferric chloride hexahydrate, ammonium thiocyanate, and 2-aminobenzimidazole using the evaporation of the solvent method. The main components, the single-crystal structure, and the thermal and dielectric properties of the complex were characterized using infrared spectroscopy, elemental analysis, single-crystal X-ray diffraction, powder XRD, thermogravimetric analysis, differential scanning calorimetry, variable-temperature and variable-frequency dielectric constant tests, etc. The analysis results indicated that compound 1 belongs to the P21/n space group. Within the crystal structure, the [Fe(NCS)6]3- anion formed a two-dimensional hydrogen-bonded network with the organic cation through S···S interactions and hydrogen bonding. The disorder-order motion of the anions and cations within the crystal and the deformation of the crystal frameworks lead to a significant reversible isostructural phase transition and multiaxial dielectric anomalies of compound 1 at approximately 240 K.

Exploring Phase Transition and Structural Complexity in the Mixed Cation Uranium Oxide CaUNb2O8.

The structures and high-temperature phase transition of CaUNb2O8 were studied in situ using synchrotron X-ray and neutron powder diffraction. Rietveld refinements provided an accurate description of the crystal structures of both the monoclinic fergusonite-type I2/b structure observed at room temperature and the tetragonal scheelite-type I41/a structure found at high temperatures. Bond valence sum analysis showed Nb5+ to be octahedrally coordinated in the monoclinic fergusonite-type structure, akin to other ANbO4 materials. Rietveld analysis of the variable temperature data allowed for the determination of accurate unit cell parameters and atomic coordinates, as well as revealing a reversible phase transition around ∼750 °C. The Nb-O bond distances display anomalous behavior, with a discontinuity in the longer Nb-O(1') distance coinciding with the phase transition suggestive of a reconstructive phase transition. Mode analysis identified the Γ2+ mode as the primary mode that drives the phase transition; this is linearly coupled to the induced spontaneous strain within the monoclinic fergusonite-type structure. Analysis of the temperature dependence of the Nb(z) positional parameter, as well as of the ϵ1-ϵ2 and ϵ6 strain parameters, showed that the phase transition is not strictly second order, with the critical exponent β ≠ 1/2. This study demonstrates the complex structural features of mixed cation metal oxides at elevated temperatures.

Arylazo-3,5-diphenylpyrazole Derivatives: Molecular Probes Exhibiting Reversible Light-induced Phase Transitions for Energy Storage and Direct Photolithographic Patterning.

We report azopyrazole photoswitches decorated with variable N-alkyl and alkoxy chains (for hydrophobic interactions) and phenyl substituents on the pyrazoles (enabling π-π stacking), showing efficient bidirectional photoswitching and reversible light-induced phase transition (LIPT). Extensive spectroscopic, microscopic, and diffraction studies and computations confirmed the manifestation of molecular-level interactions and photoisomerization into macroscopic changes leading to the LIPT phenomena. Using differential scanning calorimetric (DSC) studies, the energetics associated with those accompanying processes were estimated. The long half-lives of Z isomers, high energy contents for isomerization and phase transitions, and the stability of phases over an extended temperature range (-60 to 80 °C) make them excellent candidates for energy storage and release applications. Remarkably, the difference in the solubility of the distinct phases in one of the derivatives allowed us to utilize it as a photoresist in photolithography applications on diverse substrates.

Second-Order Nonlinear Switching and Photoluminescence Properties of Cd-Based Hybrid Perovskite with High-Temperature Phase Transition.

Recently, organic-inorganic hybrid perovskites exhibiting facile structural phase transitions have accumulated significant attention due to their switchable second-order nonlinear optical (NLO) properties, which hold significant promise for next-generation intelligent optoelectronic devices. In this study, we present a novel one-dimensional hexagonal hybrid perovskite, (4-methoxypiperidinium)CdCl3, which undergoes a reversible high-temperature structural phase transition at 389 K. Notably, (4-methoxypiperidinium)CdCl3 demonstrates switchable second-order NLO and dielectric properties, accompanied by symmetry breaking from the centrosymmetric Pnma to noncentrosymmetric Pna21 space group. Variable-temperature structure analyses reveal that this transition is mainly driven by the order-disorder transformation of the 4-methoxypiperidinium cations. Furthermore, it also features a promising photoluminescence performance with blue-light emission and a long lifetime of 25.34 ns. It is anticipated that this study will expand the family of hybrid perovskites exhibiting high-temperature phase transitions and offer valuable guidance for the design of new NLO switching materials with superior optoelectronic properties.

Synergistic structural engineering of 3D printed matchable electrodes for long-life rechargeable nickel–bismuth batteries

Aqueous rechargeable alkaline batteries have attracted increasing attention due to their reliable safety, low cost and high electrochemical potential. However, it remains challenging to construct remarkable rechargeable batteries with desirable electrode architectures and optimized electrochemical mechanisms. Herein, 3D printed high-loading bismuth-based anodes with synergistic enhancement of three-dimensional interconnection network structure and oxygen vacancies is achieved, for which intrinsic battery charge storage mechanism is in-depth unveiled. The synergistic structural engineering significantly enhances the overall charge carrier transport of 3D printed nickel-bismuth batteries, as evidenced by the conductivity of a single-wired electrode, enabling nickel-bismuth batteries to achieve a high areal capacity of 0.17 mA h cm−2 at 6 mA cm−2, a high energy density of 97.92 μWh cm−2 and a power density of 6.41 mW cm−2. Moreover, superior cycling stability is obtained. Ex situ characterization results reveal that Bi2O2.33 undergoes a phase transition after the initial charge and discharge, while the subsequent cycles rely on the reversible phase transition mechanism between Bi and Bi2O3 for basic charge storage. The exceptional performance and revealed mechanism of 3D printed batteries offer novel ideas and understanding for constructing future rechargeable nickel-bismuth batteries with state-of-the-art behaviors.

La-doped O3-type layered oxide cathode with enhanced cycle stability for sodium-ion batteries

Despite the considerable potential of O3-type layered oxide cathodes in sodium-ion batteries due to their high theoretical capacities, the rapid capacity degradation caused by high Na+ diffusion barriers and irreversible phase transitions seriously hampers their practical application. Herein, we propose the La-doping strategy in O3-type layered oxide to decrease diffusion barriers and strengthen transition metal–oxygen (TM-O) bonds, thereby significantly improving the electrochemical performance. The strong La-O bonding facilitates highly reversible O3-P3 phase transitions during (de)sodiation and enhances the stability of lattice oxygen at high voltages. Specifically, the La-doped O3-type oxide exhibits impressive cycling stability, with the capacity retention increasing from 63 % to 80 % after 500 cycles at 1C. The full cell assembly with La-doped oxide as cathode and hard carbon as anode demonstrates a high energy density of 323.7 Wh kg−1 at 0.1C, with a capacity retention of 74.6 % after 300 cycles at 1C. This work provides new insights in La-doping to promote the commercial application of O3-type cathodes for sodium ion batteries.

Energy-Efficient Smart Window Based on a Thermochromic Hydrogel with Adjustable Critical Response Temperature and High Solar Modulation Ability.

Thermochromic smart windows realize an intelligent response to changes in environmental temperature through reversible physical phase transitions. They complete a real-time adjustment of solar transmittance, create a livable indoor temperature for humans, and reduce the energy consumption of buildings. Nevertheless, conventional materials that are used to prepare thermochromic smart windows face challenges, including fixed transition temperatures, limited solar modulation capabilities, and inadequate mechanical properties. In this study, a novel thermochromic hydrogel was synthesized from 2-hydroxy-3-butoxypropyl hydroxyethyl celluloses (HBPEC) and poly(N-isopropylacrylamide) (PNIPAM) by using a simple one-step low-temperature polymerization method. The HBPEC/PNIPAM hydrogel demonstrates a wide response temperature (24.1-33.2 °C), high light transmittance (Tlum = 87.5%), excellent solar modulation (ΔTsol = 71.2%), and robust mechanical properties. HBPEC is a functional material that can be used to adjust the lower critical solution temperature (LCST) of the smart window over a wide range by changing the degree of substitution (DS) of the butoxy group in its structure. In addition, the use of HBPEC effectively improves the light transmittance and mechanical properties of the hydrogels. After 100 heating and cooling cycles, the hydrogel still has excellent stability. Furthermore, indoor simulation experiments show that HBPEC/PNIPAM hydrogel smart windows have better indoor temperature regulation capabilities than traditional windows, making these smart windows potential candidates for energy-saving building materials.

Novel synthesis of thermoresponsive single-walled carbon nanotubes/poly(N-isopropylacrylamide) hybrids

Poly(N-isopropylacrylamide) (PNIPAM) is one of the most well studied thermoresponsive polymers and its microgels undergo a reversible volume phase transition (VPT) at temperatures close to that of the human body. Coupling this property with the unique optical properties of single-walled carbon nanotubes (SWCNT) in the near infrared (NIR) leads to interesting nanohybrids that could be used as multi-responsive sensors/actuators for biological applications.We show the synthesis of thermoresponsive SWCNT/PNIPAM hybrids using two different non-covalent strategies, preserving the nanotube optical properties such as fluorescence. The first strategy involves the dispersion of the SWCNT in water with sodium dodecyl sulfate (SDS), and subsequent in situ synthesis of PNIPAM microgels inside the SDS coatings around the nanotubes. The second strategy starts with modifying the nanotubes with a pyrene derivative, which in turn is used as the starting point for the in situ polymerization of the PNIPAM microgels, thus ensuring that the polymer grows around the nanotubes. In both cases, we obtain hybrids showing a phase transition at temperatures close to that of the human body, with the absorption and fluorescence spectra of the hybrids in the NIR changing in response to the changing dielectric environment. These systems could be used as actuators/sensors in biological systems.