Accelerated Redox Reactions Enable Stable Tin-Lead Mixed Perovskite Solar Cells.

The facile oxidation of Sn2+ to Sn4+ poses an inherent challenge that limits the efficiency and stability of tin-lead mixed (Sn-Pb) perovskite solar cells (PSCs) and all-perovskite tandem devices. In this work, we discover the sustainable redox reactions enabling self-healing Sn-Pb perovskites, where their intractable oxidation degradation can be recovered to their original state under light soaking. Quantitative and operando spectroscopies are used to investigate the redox chemistry, revealing that metallic Pb0 from the photolysis of perovskite reacts with Sn4+ to regenerate Pb2+ and Sn2+ spontaneously. Given the sluggish redox reaction kinetics, V3+ /V2+ ionic pair is designed as an effective redox shuttle to accelerate the recovery of Sn-Pb perovskites from oxidation. The target Sn-Pb PSCs enabled by V3+ /V2+ ionic pair deliver an improved power conversion efficiency (PCE) of 21.22 % and excellent device lifespan, retaining nearly 90 % of its initial PCE after maximum power point tracking under light for 1,000 hours.

Solvent-derived Fluorinated Secondary Interphase for Reversible Zn-graphite Dual-ion Batteries.

The irreversibility of anion intercalation-deintercalation is a fundamental issue in determining the cycling stability of a dual-ion battery (DIB). In this work, we demonstrate that using a partially fluorinated carbonate solvent can drive a beneficial fluorinated secondary interphase layer formation. Such layer facilitates reversible anion (de-)intercalation processes by impeding solvent molecule co-intercalation and the associated graphite exfoliation. The enhanced reversibility of anion transport contributes to the overall cycling stability for a Zn-graphite DIB-a high Coulombic efficiency of 98.5 % after 800 cycles, with an attractive discharge capacity of 156 mAh g-1 and a mid-point discharge voltage of ≈1.7 V (at 0.1 A g-1 ). In addition, the formed fluorinated secondary interphase suppresses the self-discharge behavior, preserving 29 times of the capacity retention rate compared to the battery with a commonly used carbonate solvent, after standing for 24 hours. This work provides a simple and effective strategy for addressing the critical challenges in graphite-based DIBs and contributes to fundamental understanding to help accelerate their practical application.

On the disparity in reporting Li-rich layered oxide cathode materials.

Lithium-rich layered oxides are considered one of the most promising cathode materials for next generation lithium-ion batteries due to their extraordinary specific capacity of over 280 mA h g-1 and superior energy density of over 1000 W h kg-1. Despite the excellent performance, LRLOs still suffer from low Coulombic efficiency, serious capacity/voltage decay upon cycling, voltage hysteresis, short lifespan, and poor rate capability. Driven by the thirst for high-energy-density battery technologies, various strategies have been developed to address these issues with great progress being achieved in the past several years. However, the emerging disparity among the published results severely precludes meaningful comparisons between different LRLOs and material modification strategies, which has become an impediment to the development and commercialization of LRLOs. Although the significance of standardization has been recognized in the battery community, the standardization of LRLOs is worth particular attention due to their complicated compositions and unique electrochemical properties. This perspective analyzes the underlying parameters that can cause varied and even controversial results observed in LRLOs, from the synthesis procedure to the electrochemical evaluation procedure, followed by preliminary suggestions for the standard protocols of chemical compositions, synthesis pathways, calcination conditions, electrode preparation, battery fabrication, and battery testing. Hopefully, this perspective can help build a reliable baseline for LRLO research, thus aligning the huge research effort toward the practical applications of LRLOs.

In Situ Bonding Regulation of Surface Ligands for Efficient and Stable FAPbI3 Quantum Dot Solar Cells.

Quantum dots (QDs) of formamidinium lead triiodide (FAPbI3 ) perovskite hold great potential, outperforming their inorganic counterparts in terms of phase stability and carrier lifetime, for high-performance solar cells. However, the highly dynamic nature of FAPbI3 QDs, which mainly originates from the proton exchange between oleic acid and oleylamine (OAm) surface ligands, is a key hurdle that impedes the fabrication of high-efficiency solar cells. To tackle such an issue, here, protonated-OAm in situ to strengthen the ligand binding at the surface of FAPbI3 QDs, which can effectively suppress the defect formation during QD synthesis and purification processes is selectively introduced. In addition, by forming a halide-rich surface environment, the ligand density in a broader range for FAPbI3 QDs without compromising their structural integrity, which significantly improves their optoelectronic properties can be modulated. As a result, the power conversion efficiency of FAPbI3 QD solar cells (QDSCs) is enhanced from 7.4% to 13.8%, a record for FAPbI3 QDSCs. Furthermore, the suppressed proton exchange and reduced surface defects in FAPbI3 QDs also enhance the stability of QDSCs, which retain 80% of the initial efficiency upon exposure to ambient air for 3000 hours.

Coordination Chemistry Engineered Polymeric Carbon Nitride Photoanode with Ultralow Onset Potential for Water Splitting.

Construction of an intimate film/substrate interface is of great importance for a photoelectrode to achieve efficient photoelectrochemical performance. Inspired by coordination chemistry, a polymeric carbon nitride (PCN) film is intimately grown on a Ti-coated substrate by an in situ thermal condensation process. The as-prepared PCN photoanode exhibits a record low onset potential (Eonset ) of -0.38 V versus the reversible hydrogen electrode (RHE) and a decent photocurrent density of 242 µA cm-2 at 1.23 VRHE for water splitting. Detailed characterization confirms that the origin of the ultralow onset potential is mainly attributed to the substantially reduced interfacial resistance between the Ti-coated substrate and the PCN film benefitting from the constructed interfacial sp2 N→Ti coordination bonds. For the first time, the ultralow onset potential enables the PCN photoanode to drive water splitting without external bias with a stable photocurrent density of ≈9 µA cm-2 up to 1 hour.

Heterocyclic Conjugated Polymer Nanoarchitectonics with Synergistic Redox-Active Sites for High-Performance Aluminium Organic Batteries.

The development of cost-effective and long-life rechargeable aluminium ion batteries (AIBs) shows promising prospects for sustainable energy storage applications. Here, we report a heteroatom π-conjugated polymer featuring synergistic C=O and C=N active centres as a new cathode material in AIBs using a low-cost AlCl3 /urea electrolyte. Density functional theory (DFT) calculations reveal the fused C=N sites in the polymer not only benefit good π-conjugation but also enhance the redox reactivity of C=O sites, which enables the polymer to accommodate four AlCl2 (urea)2 + per repeating unit. By integrating the polymer with carbon nanotubes, the hybrid cathode exhibits a high discharge capacity and a long cycle life (295 mAh g-1 at 0.1 A g-1 and 85 mAh g-1 at 1 A g-1 over 4000 cycles). The achieved specific energy density of 413 Wh kg-1 outperforms most Al-organic batteries reported to date. The synergistic redox-active sites strategy sheds light on the rational design of organic electrode materials.

Epitaxial growth of an atom-thin layer on a LiNi0.5Mn1.5O4 cathode for stable Li-ion battery cycling.

Transition metal dissolution in cathode active material for Li-based batteries is a critical aspect that limits the cycle life of these devices. Although several approaches have been proposed to tackle this issue, this detrimental process is not yet overcome. Here, benefitting from the knowledge developed in the semiconductor research field, we apply an epitaxial method to construct an atomic wetting layer of LaTMO3 (TM = Ni, Mn) on a LiNi0.5Mn1.5O4 cathode material. Experimental measurements and theoretical analyses confirm a Stranski-Krastanov growth, where the strained wetting layer forms under thermodynamic equilibrium, and it is self-limited to monoatomic thickness due to the competition between the surface energy and the elastic energy. Being atomically thin and crystallographically connected to the spinel host lattices, the LaTMO3 wetting layer offers long-term suppression of the transition metal dissolution from the cathode without impacting its dynamics. As a result, the epitaxially-engineered cathode material enables improved cycling stability (a capacity retention of about 77% after 1000 cycles at 290 mA g-1) when tested in combination with a graphitic carbon anode and a LiPF6-based non-aqueous electrolyte solution.

Nanoconfined Topochemical Conversion from MXene to Ultrathin Non-Layered TiN Nanomesh toward Superior Electrocatalysts for Lithium-Sulfur Batteries.

2D non-layered materials (2DNLMs) featuring massive undercoordinated surface atoms and obvious lattice distortion have shown great promise in catalytic/electrocatalytic applications, but their controllable synthesis remains challenging. Here, a new type of ultrathin carbon-wrapped titanium nitride nanomesh (TiN NM@C) is prepared using a rationally designed nano-confinement topochemical conversion strategy. The ultrathin 2D geometry with well-distributed pores offers TiN NM@C plentiful exposed active sites and rapid charge transfer, leading to outstanding electrocatalytic performance tackling the sluggish sulfur redox kinetics in lithium-sulfur batteries (LSBs). LSBs employing TiN NM@C electrocatalyst deliver excellent rate capabilities (e.g., 304 mAh g-1 at 10 C), greatly outperforming that of using TiN nanoparticles embedded in carbon nanosheets (TiN NPs@C) as a benchmark. More impressively, a free-standing electrode for LSBs with a high sulfur loading of 7.3 mg cm-2 is demonstrated, showing a high peak areal capacity of 5.6 mAh cm-2 at a high current density of 6.1 mA cm-2 . This work provides a new avenue for the facile and controllable fabrication of 2DNLMs with impressive electrocatalysis for LSBs as well as other energy conversion and storage technologies.

Designing efficient Bi2Fe4O9 photoanodes via bulk and surface defect engineering.

The Bi2Fe4O9 photoanode material is modified through a combined bulk and surface defect engineering (BSDE) strategy, delivering the highest photoresponse for Bi2Fe4O9 based materials. This work shows the advantage of BSDE in achieving efficient solar water splitting.

Biomimetic Sn4P3 Anchored on Carbon Nanotubes as an Anode for High-Performance Sodium-Ion Batteries.

Recently, Sn4P3 has emerged as a promising anode for sodium-ion batteries (SIBs) due to the high specific capacity. However, the use of Sn4P3 has been impeded by capacity fade and an inferior rate performance. Herein, a biomimetic heterostructure is reported by using a simple hydrothermal reaction followed by thermal treatment. This bottlebrush-like structure consists of a stem-like carbon nanotube (CNT) as the electron expressway and mechanical support; fructus-like Sn4P3 nanoparticles as the active material; and the permeable stoma-like thin carbon coating as the buffer layer. Having benefited from the biomimetic structure, a superior electrochemical performance is obtained in the SIBs. It exhibits a high capacity of 742 mA h g-1 after 150 cycles at 0.2C, and superior rate performance with 449 mA h g-1 at 2C after 500 cycles. Moreover, the sodium storage mechanism is confirmed by cyclic voltammetry and ex situ X-ray diffraction and transmission electron microscopy. In situ electrochemical impedance spectroscopy was adopted to analyze the reaction dynamics. This research represents a further step toward figuring out the inferior electrochemical performance of other metal phosphide materials.

Lattice distortion induced internal electric field in TiO2 photoelectrode for efficient charge separation and transfer.

Providing sufficient driving force for charge separation and transfer (CST) is a critical issue in photoelectrochemical (PEC) energy conversion. Normally, the driving force is derived mainly from band bending at the photoelectrode/electrolyte interface but negligible in the bulk. To boost the bulky driving force, we report a rational strategy to create effective electric field via controllable lattice distortion in the bulk of a semiconductor film. This concept is verified by the lithiation of a classic TiO2 (Li-TiO2) photoelectrode, which leads to significant distortion of the TiO6 unit cells in the bulk with well-aligned dipole moment. A remarkable internal built-in electric field of ~2.1 × 102 V m-1 throughout the Li-TiO2 film is created to provide strong driving force for bulky CST. The photoelectrode demonstrates an over 750% improvement of photocurrent density and 100 mV negative shift of onset potential upon the lithiation compared to that of pristine TiO2 film.

Hollow structured cathode materials for rechargeable batteries.

Hollow structuring has been intensively studied as an effective strategy to improve the electrochemical performance of the electrode materials for rechargeable batteries in terms of specific capacity, rate capability, and cycling performance. To date, hollow structured anode materials have been extensively investigated, while hollow structured cathode materials (HSCMs) are relatively less explored because of the difficulties in morphological control as well as the concern of reduced volumetric capacities. In this paper, we provide an overview of the research advances in the synthesis and evolution of HSCMs for metal (Li, Na, etc.) ion batteries. Attributing to the advantages of hollow structures including high surface area, excellent accessibility to active sites, and enhanced mass transport and diffusion, hollow structuring can significantly improve the performance of high-capacity cathode materials with low kinetics, such as lithium rich layered oxides, silicates, and V2O5. It is anticipated that the precise and facile control of the spatial configuration can balance the electrochemical performance of HSCMs and the volumetric capacities of HSCMs, leading to practical high-performance batteries.

Polyethylenimine Expanded Graphite Oxide Enables High Sulfur Loading and Long-Term Stability of Lithium-Sulfur Batteries.

To realize practical lithium-sulfur batteries (LSBs) with long cycling life, designing cathode hosts with a high specific surface area (SSA) is recognized as an efficient way to trap the soluble polysulfides. However, it is also blamed for diminishing the volumetric energy density and being susceptible to side reactions. Herein, polyethylenimine intercalated graphite oxide (PEI-GO) with a low SSA of 4.6 m2 g-1 and enlarged interlayer spacing of 13 Å is proposed as a superior sulfur host, which enables homogeneous distribution of high sulfur content (73%) and facilitates Li+ transfer in thick sulfur electrode. LSBs with a moderate sulfur loading (3.4 mg S cm-2 ) achieve an initial capacity of 1157 and 668 mAh g-1 after 500 cycles at 0.5 C. Even when the sulfur loading is increased to 7.3 mg cm-2 , the electrode still delivers a high areal capacity of 4.7 mAh cm-2 (641 mAh g-1 ) after 200 cycles at 0.2 C. The excellent electrochemical properties of PEI-GO are mainly attributed to the homogeneous distribution of sulfur in PEI-GO and the strong chemical interactions between polysulfides and amine groups, which can mitigate the loss of active phases and contribute to the better cycling stability.

Multifunctional Effects of Sulfonyl-Anchored, Dual-Doped Multilayered Graphene for High Areal Capacity Lithium Sulfur Batteries.

Li-S batteries (LSBs) require a minimum 6 mAh cm-2 areal capacity to compete with the state-of-the-art lithium ion batteries (LIBs). However, this areal capacity is difficult to achieve due to a major technical issue-the shuttle effect. Nonpolar carbon materials limit the shuttle effect through physical confinement. However, the polar polysulfides (PSs) only provide weak intermolecular interactions (0.1-0.7 eV) with these nonpolar carbon materials. The physically encapsulated PSs inside the nonpolar carbon scaffold eventually diffuses out and starts shuttling. Chemically interactive hosts are more effective at interacting with the PSs due to high binding energies. Herein, a multifunctional separator coating of nitrogen-doped multilayer graphene (NGN) and -SO3 - containing Nafion (N-NGN) is used to mitigate PS shuttling and to produce a high areal capacity LSB. The Nafion is used as a binder instead of PVDF to provide an additional advantage of -SO3 - to chemically bind the PS. The motive of this research is to investigate the effect of highly electronegative N and -SO3 - (N-NGN) in comparison with the -OH, -COOH, and -SO3 - groups from a hydroxyl graphene and Nafion composite (N-OHGN) to mitigate PS shuttling in LSBs. The highly conductive doped graphene architecture (N-NGN) provides efficient pathways for both electrons and ions, which accelerates the electrochemical conversion at high sulfur loading. Moreover, the electron-rich pyridine N and -SO3 - show strong chemical affinity with the PS through polar-polar interactions, which is proven by the superior electrochemical performance and density functional theory calculations. Further, the N-NGN (5 h) produces a maximum areal capacity of 12.0 and 11.0 mAh cm-2, respectively, at 15 and 12 mg cm-2 sulfur loading. This areal capacity limit is significantly higher than the required areal capacity of LSBs for commercial application, which shows the significant strength of N-NGN as an excellent separator coating for LSBs.