Phase selection in multicomponent oxides is frequently constrained by sluggish solid-state diffusion and competing reaction pathways. Here, acid–base control of solution-precipitated lanthanide tellurite precursors is used as a kinetic strategy for the low-temperature, phase-selective formation of Ln2Te6O15 and Ln2Te4O11 (Ln = lanthanide). Varying the LnCl3:Na2TeO3:HCl ratio defines four nominal precursor regimes: non-protonated Ln2(TeO3)3, partially protonated Ln(TeO3)(HTeO3), highly protonated Ln(HTeO3)3, and an over-protonated H2TeO3/TeO2-rich boundary. Across the productive 2:3:0–1:3:3 window, increasing nominal protonation lowers the crystallization temperature of La2Te6O15 from 600 to 420 °C and the minimum temperature for XRD-phase-pure La2Te4O11 formation from 840 to 540 °C after 6 h. Excessive protonation disrupts the connected Ln–Te–O precursor network and yields TeO2-rich products. The approach is applicable to all 14 nonradioactive lanthanides examined and enables equimolar 14-cation high-entropy derivatives with homogeneous elemental distributions. Rietveld refinements support the targeted cubic and monoclinic structures, while Yb3+/Er3+ codoping links the precursor-controlled phase pathway to structural order and upconversion emission. To our knowledge, the resulting series includes the first single-lanthanide preparations of Ln2Te6O15 for Ln = Ce, Er, Tm, Yb, and Lu, as well as the first 14-cation (La–Lu)2Te6O15 and (La–Lu)2Te4O11 derivatives. These results establish precursor protonation as a practical kinetic handle for phase-selective synthesis of compositionally complex oxides at reduced temperatures.
Zero-strain Li4Ti5O12 (LTO) anode is repurposed as a mechanistic probe to decouple interfacial failure modes in sulfide-based all-solid-state batteries. Neutron diffraction reveals multi-site Li+ occupancy and Br-induced local structural disorder in the LPSCB (Li5.5PS4.5Cl0.8Br0.7) electrolyte. Combined DFT calculations, solid-state NMR, in situ EIS, and GITT confirm that the LTO/LPSCB interface is intrinsically chemically inert, with a binding energy of −0.41 eV, a net charge transfer of only ∼0.024 e, and no detectable macroscopic Li+ exchange across the interface. Electrochemically, the LTO anode delivers high reversible capacity, excellent long-term stability (79.3% retention after 300 cycles at 1C), and robust rate capability even at elevated temperatures, with a Li+ diffusion coefficient (10-5–10-9 cm2 s-1) substantially surpassing those of graphite and silicon. In full-cell comparisons, the LTO-based cell shows the lowest polarization overpotential and negligible volume change (−0.2%), whereas graphite and silicon anodes suffer from severe interfacial cracking and contact loss. The spinel framework and redox reversibility of LTO remain intact, confirming minimal chemical degradation at the anode/electrolyte interface. When benchmarked against graphite and high-strain silicon anodes, the zero-strain LTO cell exhibits negligible volume change and intact interfacial contact, establishing that mechanical strain is the dominant driver of interfacial degradation. A strain–chemistry coupled design framework is thereby established, providing a quantitative pathway for decoupling failure mechanisms toward durable sulfide-based all-solid-state batteries.
Both the electrochemical and mechanical properties of solid-state electrolytes are crucial for achieving stable battery performance, while the widely studied NASICON-type electrolytes such as Na3Zr2Si2PO12 (NZSP) still suffer from poor conductivity and a tendency to Na metal penetration. To address these problems simultaneously, we propose an integrated chemistry-structure-mechanics design principle, in which aliovalent Sc/Mg co-doping (chemistry) regulates lattice framework and grain-boundary evolution (structure), thereby enhancing mechanical robustness (mechanics) without compromising ionic transport. The optimized sample (Na3.4Zr1.7Sc0.2Mg0.1Si2PO12) achieves a high room-temperature conductivity of 1.26 & times; 10(-3) S cm(-1) and a 25% increase in hardness compared with the Mg-free analogue. The solid-state cell assembled with this electrolyte (Na/Na3.4Zr1.7Sc0.2Mg0.1Si2PO12/Na3V2(PO4)3) shows excellent cycling stability in a wide temperature range of 0-80 degrees C, and retains 90% of its initial capacity after 440 cycles at 30 degrees C and 1C. These results demonstrate that aliovalent co-doping to concurrently optimize lattice chemistry and ceramic microstructure is an effective route to high-performance NASICON electrolytes.
In this work, we propose a ligand–antisolvent synergistic regulation strategy to synthesize Cs–Pb–Br materials with dual antibacterial and encryption functions. An amphiphilic ligand derived from 5-bromovaleric acid (5-BVA) and oleamide (OAm) is employed with two green antisolvents (water and ethanol). The use of water as an antisolvent yields high-purity CsPbBr3 quantum dots (QDs) with water stability exceeding 50 days. These QDs exhibit potent antibacterial activity through electrostatic interactions with bacterial cell membranes achieving up to 99.8% inhibition at a low concentration of 120 μg/ml. In contrast, ethanol as the antisolvent leads to a mixed CsPbBr3/CsPb2Br5 phase. This mixed phase exhibits water-triggered fluorescence activation originating from CsPbBr3 recrystallization alongside a thermal quenching effect that enables reversible on–off fluorescence switching upon cooling–heating cycles. This water-induced fluorescence activation effect combined with reversible thermal quenching properties enables multi-level encryption. Ultimately this ligand-antisolvent synergistic regulation strategy not only offers theoretical guidance for the rational and tailored design of multifunctional perovskites but also establishes a foundation for their practical applications in complex optoelectronic and biological environments.
Manganese (Mn)-based materials, owing to their high theoretical capacity, low cost, environmental benignity, and multiple accessible valence states, are attractive cathode candidates for aqueous zinc-ion batteries (AZIBs). However, their practical application is often hindered by intrinsically sluggish electron transport, slow Zn2+ diffusion kinetics, and structural instability associated with Jahn–Teller distortion during cycling. Herein, we reported a heterostructured manganese selenide/manganese oxide@carbon (MnSe/MnO@C) composite derived from metal-organic frameworks (MOFs) via a simple thermolysis of Mn MOFs under an inert atmosphere, followed by selenization. The carbonization of Mn MOFs generates a carbonaceous framework favorable for charge transport, while the formation of the heterostructured MnSe/MnO@C introduces abundant heterointerfaces and electrochemically active sites. These structural features are consistent with the reduced charge-transfer resistance and enhanced reaction kinetics observed for the MnSe/MnO@C electrode. Furthermore, when used as the cathode material for AZIBs, the MnSe/MnO@C electrode revealed superior specific capacity and improved cyclability, exhibiting 225 mA h g−1 at 0.5 A g−1 after 500 charge-discharge cycles. Surprisingly, the electrode could achieve a reversible specific capacity of 191 mA h g−1 at 2 A g−1. The ex-situ characterization indicates a mixed Zn2+/H+ co-storage mechanism accompanied by reversible structural evolution without causing significant morphological damage. This study provides insights into the synthesis of MnSe/MnO@C, electrochemical activation, and remarkable AZIB performances, which leads to a better understanding of its potential applications.
