Energy & Environmental Science最新文献

Understanding the thermal origins of performance instabilities and hysteresis in perovskite solar cells (PSCs) is essential for advancing their long-term stability and reliable operation. In this perspective, we develop a novel coupled multiphysics mathematical framework that integrates layer-resolved optical absorption, non-isothermal electronic–ionic transport, and a layer-resolved, self-consistent energy balance with explicit bulk and interfacial heat-generation pathways. These pathways include hot-carrier thermalization, Joule heating, Peltier effects, radiative/non-radiative recombination, and parasitic optical absorption. This mathematical framework extends PSC characterization beyond conventional J–V analysis by introducing temperature–voltage (T–V) and heat–voltage (P–V) characteristics curves, enabling quantitative tracking of transient self-heating and its interactions with electronic–ionic dynamics. It is shown that PSCs develop internal thermal inertia that evolves on timescales comparable to ionic relaxation under bias sweeps, leading to strongly scan-rate-dependent heating. At intermediate scan rates, this thermo-electro-ionic coupling produces non-monotonic temperature evolution with dual-peak profiles during forward sweeps and pronounced T–V hysteresis, coinciding with S-shaped J–V distortions that are shifted to lower scan rates relative to isothermal predictions. The scan-rate-dependent heating can be resolved into interfacial- and bulk-dominated regimes: interfacial heating governs the temperature evolution at low-to-intermediate scan rates, bulk heating controls the profile at intermediate-to-high rates, while rapid sweeps leave insufficient time for heat to accumulate, ultimately driving the response toward an ion-frozen, quasi-isothermal limit. These distinct thermal regimes reshape carrier extraction asymmetry, internal field screening, and mobile-ion redistribution, thereby aggravating or mitigating hysteresis relative to isothermal electronic–ionic transport predictions. Neglecting thermo-electro-ionic effects underestimates transient temperature rises by >10 K and misidentify the scan-rate window associated with S-shaped J–V distortions. By integrating these multiphysics effects, the framework provides a diagnostic tool for next-generation PSC characterization and identifies design strategies such as interface engineering, nanostructural thermal management, and scan-protocol optimization to enhance device performance and stability under real-world operating conditions.

Decoupling Li⁺ transport from polymer segmental dynamics is crucial for enhancing ionic conductivity (σ) and transference number (t₊) in solid polymer electrolytes (SPEs). Herein, by studying four ether-based SPEs with varying oxygen density, we identify a transition from polymer relaxation-limited ion transport in poly(ethylene oxide) (PEO) to ion hopping-dominant transport in poly(tetrahydrofuran) (PTHF), poly(1,3-dioxolane) (PDOL), and poly(trioxymethylene) (PTOM). Molecular dynamics simulations and solid-state ⁷Li nuclear magnetic resonance reveal origins of the transition. In PTHF, weak solvation with lithium bond characteristics contributes to a less-shielded Li⁺ environment, while in PDOL and PTOM, the discontinuous coordination (DC) structure and multi-chain binding are pivotal. The presence of DC structures is experimentally confirmed by in situ attenuated total reflection Fourier transform infrared spectroscopy and supported by quantum chemistry calculations. As a result, PDOL and PTOM exhibit t₊ values exceeding 0.5 and enhanced σ values of 4.3 × 10⁻³ and 8.5 × 10⁻³ S cm⁻¹ at 373 K, respectively. The Li/SPEs/LiFePO₄ cell with ex situ-prepared PDOL achieves a superior capacity retention of 90.8% after 50 cycles. This work underscores the significance of functional group spacing in tuning the transport mechanisms and demonstrates how the decoupling strategy can guide the bottom-up design of advanced SPEs.

Thermoelectric (TE) technology can convert human body heat into useful electricity, providing a promising solution to develop self-powered wearable electronics, in which both high output voltage density and power density are urgently required. However, the existing TE devices usually possess low voltage density in the wearing condition, greatly limiting their real applications. In this work, we propose a novel highly integrated blade structure, which can achieve ultrahigh output voltage and power densities. The finite element simulation gives the optimal geometric dimensions and integration numbers of the TE legs for the blade structure. In the experiment, we successfully fabricated the blade TE device by using the recently discovered Ag-based ductile inorganic TE materials with the TE leg density and aspect ratio of 300 cm⁻² and 1250 cm⁻¹, respectively. Such high values have not been simultaneously achieved for the TE devices reported before. An ultrahigh voltage density of up to 869.6 mV cm⁻² is achieved when the blade device is worn on the human body, which is at least one order of magnitude higher than the existing TE devices. Likewise, the blade TE devices also exhibit high power density up to 114.1 µW cm⁻², among the highest values reported so far. The electricity converted from body heat by the blade TE device can directly power an electronic watch, showing great potential to be used in real applications.

Monolithic perovskite/silicon tandem solar cells have emerged as a compelling route, combining the certified power conversion efficiencies exceeding 34% for laboratory-scale devices with more cost-effective manufacturing compared to market-established silicon photovoltaics. Despite deployment in pilot processing lines beyond the lab stage, this technology still faces scaling challenges from perovskite sub-cells, such as the incompatibility with contemporary mass production lines and the upscaling efficiency deficit, that are expected to be resolved within a few years to achieve commercial viability. Here, we comprehensively elaborate the scalable deposition and drying methods of perovskite sub-cells on silicon substrates and review their recent advanced progress. We assess the merits and limitations of these competing methods, providing a systematic framework for achieving efficient and durable large-area perovskite/silicon tandem solar cells suitable for industrial production.

To advance the practical application of potassium-ion batteries (PIBs), the lack of robust electrolytes must be addressed, as the prevailing fluorinated solvents present a cost-prohibitive and environmentally unsustainable solution. Here, we propose an asymmetric alkylation strategy to overcome this limitation, engineering a fluorine-free, high-flash-point, and green ether-based electrolyte. This design reconstitutes the solvent coordination geometry through dual steric hindrance, which concurrently weakens cation–solvent binding and modulates the electronic structure of the solvation cluster. Consequently, the designed electrolyte demonstrates exceptional interfacial compatibility, enabling the high-voltage K₂Mn[Fe(CN)₆]‖graphite and K₂Mn[Fe(CN)₆]‖hard carbon full-cells to achieve capacity retention rates of 75.75% after 1400 cycles at 0.33C and 80.09% after 1500 cycles at 0.5C, respectively. Moreover, this stability is preserved at elevated temperatures, with both full-cells exhibiting stable operation over hundreds of cycles. This work establishes an effective electrolyte design strategy for realizing high-performance, cost-effective, and environmentally friendly PIBs.

Lithium–sulfur (Li–S) batteries promise exceptional theoretical energy density but face persistent challenges, notably polysulfide shuttling and sluggish redox kinetics. High-entropy materials (HEMs), leveraging their distinctive configurational entropy and unparalleled compositional tunability, offer a transformative approach to engineer electrochemical interfaces and address these critical limitations. This review comprehensively surveys the recent advancements in the rational design and application of HEMs for Li–S batteries. We first analyze the structural and electronic characteristics of HEMs and clarify how they enhance sulfur utilization, suppress lithium polysulfide (LiPS) shuttling by anchoring intermediates, and accelerate LiPS redox reactions through tailored electronic structures. Subsequently, state-of-the-art design strategies are critically examined, including atomic-scale elemental selection, advanced synthetic methodologies, and multidimensional structural engineering. These strategies enable fabrication of components such as sulfur hosts with optimized adsorption and catalytic sites, separator modifiers that regulate ion-selective transport, and protective interlayers that mitigate lithium dendrite growth. Furthermore, we systematically review cutting-edge characterization techniques and computational methods that detail the mechanisms behind entropy-mediated improvements in battery performance. Finally, critical challenges and promising future research directions are highlighted for the development of next-generation HEM-based energy storage systems, and the insights presented in this review will guide the rational design and practical implementation of HEMs in advanced Li–S batteries.

Zinc–air batteries are considered promising candidates for the next generation of batteries due to their significant advantages in theoretical specific capacity, safety, and environmental friendliness. The combination of gel polymer electrolytes and zinc–air batteries further expands future energy storage applications. However, traditional alkaline gel zinc–air batteries are usually constructed by post-stacking methods, and their poor interfacial contact and weakened long-term durability in the ambient air hinders practical applications. Here, we synthesized a non-alkaline gel electrolyte with a liquid–solid phase transition mechanism utilizing agar, and constructed an integrated gel zinc–air battery by direct injection and encapsulation methods. This strategy realizes the integrated assembly of non-alkaline gel zinc–air full batteries, thereby obtaining all-round high stability. The agar gel electrolyte endows the battery with outstanding performance, including a high output specific capacity (706 mAh g Zn⁻¹), a long discharge duration (270 h at 0.1 mA cm⁻²), and a significant operational life (850 h at 0.2 mA cm⁻²). Importantly, the integrated zinc–air pouch battery can achieve a high zinc utilization rate of over 80% in various discharge states and exhibit satisfactory cycling stability (>200 h at 0.1 mA cm⁻²). This technology alleviates the current challenges of gel zinc batteries, and highlights the direction for the development of non-alkaline gel zinc–air full batteries.

The lithium-mediated nitrogen reduction reaction (Li-NRR) is currently the most promising strategy for electrochemical ammonia synthesis. In this study, we present an operando grazing incidence wide angle X-ray scattering (GI WAXS) investigation using an improved electrochemical flow cell that enables hydrogen oxidation at the anode and thereby eliminates the need of a sacrificial proton donor. The improved cell design also increases nitrogen availability and mass transport, achieving ammonia faradaic efficiencies (FEs) up to 36%. This setup allows direct analysis of reaction intermediates and the solid electrolyte interphase (SEI) using state-of-the-art diglyme-based electrolytes. We identify lithium amide (LiNH₂) as the only stable, crystalline intermediate, providing direct insight into the Li-NRR mechanism. Notably, in diglyme-based electrolytes, the SEI composition differs significantly from that in tetrahydrofuran-based systems, with reduced LiF content and the formation of previously unreported crystalline diglyme–lithium salt complexes. These species likely influence ammonia selectivity and long-term stability. Our findings highlight how the electrolyte composition and cell architecture govern Li-NRR selectivity and efficiency, offering a foundation for the rational design of next-generation SEI layers and solid electrolytes to enable scalable electrochemical ammonia synthesis.

Mitigating surface-initiated structural degradation, which propagates inward and depletes all active particles is critical for improving the cycle lifespan of Co-free ultrahigh-Ni NMA (LiNi_1−x−yMn_xAl_yO₂, 1 − x − y − z ≥ 0.9) cathodes. Herein, an epitaxially grown lattice-coherent surface with stabilized low-valence Ni states and refined primary particles has been precisely implemented in LiNi_0.9Mn_0.05Al_0.05O₂ by designing the internal composition distribution within secondary particles, thereby simultaneously ameliorating surface chemistry and mechanical integrity. Key findings indicate that the Mn⁴⁺ species retained on the particle crust facilitate the formation of a localized layer of coherent Li/Ni anti-site defects on the periphery of the primary particles located on the surface of the secondary particle, which stabilizes the intrinsic nature of the surface lattice. Meanwhile, the thermally driven and inward diffusion of Mn, which acts as an oxygen carrier, during calcination ameliorates the local oxygen environment and suppresses interface-fusion intermediate phases (cation mixing) to refine the primary particles. The robust morphological integrity provided by refined primary particles prevents intergranular cracks, confining interfacial parasitic reactions to the surface region of the secondary particles protected by the lattice-coherent epitaxial surface. This universal approach optimally balances surface stabilization with charge transfer, significantly enhancing capacity retention and rate capability for the NMA cathode while opening a new avenue for next-generation Co-free ultrahigh-Ni cathodes.