Air-Stable Li2S Cathode for Quasi-Solid-State Anode-Free Batteries with High Volumetric Energy

Anode-free batteries can maximize the energy density but their development is hindered by a lack of Li-rich cathodes for compensating the irreversible Li loss. Li₂S cathode is particularly appealing to this desire due to 2.6–4.7 folds more Li content and 4.2–6.8 times higher capacity than conventional intercalation cathodes. But its practical application is hindered by poor stability against moisture attacking in the air. Herein, a facile expendable polymer sheathing strategy toward air-stable Li₂S cathodes with high capacities for developing high-performance quasi-solid-state anode-free batteries without risk of cell leakage is reported. Tight protection by dense polymer barrier dramatically prolongs the lifetime of Li₂S cathode by 2,000 times at least in the air. Such air-stable Li₂S cathode allows for high compatibility of anode-free battery production with commercial schemes. More attractively, the polymer protective layer can in situ transform to multifunctional gel polymer electrolyte for releasing ionic pathways and enhancing cell performance by inhibiting LiPS loss and smoothing Li plating. With air-stable Li₂S cathode, the quasi-solid-state anode-free cells are assembled in ambient environment to deliver superb volumetric energy density of 1093 Wh L⁻¹. This study may shed new light to push the commercialization of high-energy and reliable anode-free batteries forward.     

High-Efficiency Organic Solar Cells Enabled by Chalcogen Containing Branched Chain Engineering: Balancing Short-Circuit Current and Open-Circuit Voltage,Enhancing Fill Factor

The elaborate balance between the open-circuit voltage (V_OC) and the short-circuit current density (J_SC) is critical to ensure efficient organic solar cells (OSCs). Herein, the chalcogen containing branched chain engineering is employed to address this dilemma. Three novel nonfullerene acceptors (NFAs), named BTP-2O , BTP-O-S , and BTP-2S , featuring different peripheral chalcogen containing branched chains are synthesized. Compared with symmetric BTP-2O and BTP-2S grafting two alkoxy or alkylthio branched chains, the asymmetric BTP-O-S grafting one alkoxy and one alkylthio branched chains shows mediate absorption range, applicable miscibility, and favorable crystallinity. Benefiting from the enhanced π–π stacking and charge transport, an optimal power conversion efficiency (PCE) of 17.3% is obtained for the PM6: BTP-O-S -based devices, with a good balance between V_OC (0.912 V) and J_SC (24.5 mA cm⁻²), and a high fill factor (FF) of 0.775, which is much higher than those of BTP-2O (16.1%) and BTP-2S -based (16.4%) devices. Such a result represents one of the highest efficiencies among the binary OSCs with V_OC surpassing 0.9 V. Moreover, the BTP-O-S -based devices fabricated by using green solvent yield a satisfactory PCE of 17.1%. This work highlights the synergistic effect of alkoxy and alkylthio branched chains for high-performance OSCs by alleviating voltage loss and enhancing FF.     

Mitigating Detrimental Effect of Self-Doping Near the Anode in Highly Efficient Organic Solar Cells

Poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) has been one of the most established hole transport layers (HTL) in organic solar cells (OSCs) for several decades. However, the presence of PSS⁻ ions is known to deteriorate device performance via a number of mechanisms including diffusion to the HTL-active layer interface and unwanted local chemical reactions. In this study, it is shown that PSS⁻ ions can also result in local p-doping in the high efficiency donor:non-fullerene acceptor blends – resulting in photocurrent loss. To address these issues, a facile and effective approach is reported to improve the OSC performance through a two-component hole transport layer (HTL) consisting of a self-assembled monolayer of 2PACz ([2-(9H-Carbazol-9-yl)ethyl]phosphonic acid) and PEDOT:PSS. The power conversion efficiency (PCE) of 17.1% using devices with PEDOT:PSS HTL improved to 17.7% when the PEDOT:PSS/2PACz two-component HTL is used. The improved performance is attributed to the overlaid 2PACz layer preventing the formation of an intermixed p-doped PSS⁻ ion rich region (≈5–10 nm) at the bulk heterojunction-HTL contact interface, resulting in decreased recombination losses and improved stability. Moreover, the 2PACz monolayer is also found to reduce electrical shunts that ultimately yield improved performance in large area devices with PCE enhanced from 12.3% to 13.3% in 1 cm² cells.     

Solid Solvation Assisted Electrical Doping Conserves High-Performance in 500 nm Active Layer Organic Solar Cells

Organic solar cells (OSCs) process fascinating solution-printing capability to achieve low-cost and large-scale manufacture. However, the rapid power conversion efficiency (PCE) decay with active layer thickness enlargement inhibits the implement of OSCs’ potential advantages. To overcome the bottlenecks of PCE decay in thick active layer OSCs, the electrical doping with componential selectivity in bulk heterojunction (BHJ) film is achieved by introducing a solid solvation additive. Benefiting from the higher exciton splitting efficiency together with the longer drift (L_dr) and diffusion (L_diff) lengths, an OSC with 100 nm BHJ film demonstrates a PCE increment from 16.44% to 18.24% with prolonged dark and illuminated storage stabilities. Applying the solid solvation assisted (SSA) doping method in the OSCs with 500 nm active layer, the PCE significantly increases by 31.9%, from the original value of 11.79% to 15.55%. It further improves to 15.84% in a ternary blend thick-film device, which is the record value to the best of our knowledge. Besides, the SSA doping narrows the PCE gap between the 0.04 and 1 cm² devices. All improvements demonstrate the great potential of SSA doping for OSC commercial manufacture, since it optimizes the photovoltaic performance under all practical conditions of long-term, thick-film, and large-area.     

Energy Transfer Induced by TADF Polymer Enables the Recycling of Excitons in Perovskite Solar Cells

Formamidinium lead triiodide (FAPbI₃) has been demonstrated as the most efficient perovskite system to date, due to its excellent thermal stability and an ideal bandgap approaching the Shockley-Queisser limit. Whereas, there are intrinsic quantum confinement effects in FAPbI₃, which lead to unwanted non-radiative recombination. Additionally, the black α-phase of FAPbI₃ is unstable under room temperature due to the significant residual tensile stress in the film. To simultaneously address the above issues, a thermally-activated delayed fluorescence polymer P1 is designed in the study to modify the FAPbI₃ film. Owing to the spectral overlap between the photoluminescence of P1 and absorption of the above-bandgap quantum wells of FAPbI₃, the Förster energy transfer occurs at the P1/FAPbI₃ interface, which further triggers the Dexter energy transfer within FAPbI₃. The exciton “recycling” can thus be realized, which reduces the non-radiative recombination losses in perovskite solar cells (PSCs). Moreover, P1 is found to introduce compressive stress into FAPbI₃, which relieves the tensile stress in perovskite. Consequently, the PSCs with P1 treatment achieve an outstanding power conversion efficiency (PCE) of 23.51%. Moreover, with the alleviation of stress in the perovskite film, flexible PSCs (f-PSCs) also deliver a high PCE of 21.40%.     

Mitigating Surface Deficiencies of Perovskite Single Crystals Enables Efficient Solar Cells with Enhanced Moisture and Reverse-Bias Stability

Metal halide perovskite single crystals are promising for diverse optoelectronic applications due to their outstanding properties. In comparison to the bulk, the crystal surface suffers from high defect density and is moisture sensitive; however, surface modification strategies of perovskite single crystals are relatively deficient. Herein, solar cells based on methylammonium lead triiodide (MAPbI₃) thin single crystals are selected as a prototype to improve single-crystal perovskite devices by surface modification. The surface trap passivation and protection against moisture of MAPbI₃ thin single crystals are achieved by one bifunctional molecule 3-mercaptopropyl(dimethoxy)methylsilane (MDMS). The sulfur atom of MDMS can coordinate with bare Pb²⁺ of MAPbI₃ single crystals to reduce surface defect density and nonradiative recombination. As a result, the modified devices show a remarkable efficiency of 22.2%, which is the highest value for single-crystal MAPbI₃ solar cells. Moreover, MDMS modification mitigates surface ion migration, leading to enhanced reverse-bias stability. Finally, the cross-link of silane molecules forms a protective layer on the crystal surface, which results in enhanced moisture stability of both materials and devices. This work provides an effective way for surface modification of perovskite single crystals, which is important for improving the performance of single-crystal perovskite solar cells, photodetectors, X-ray detectors, etc.     

Advanced Characterization and Optimization of NiOx:Cu-SAM Hole-Transporting Bi-Layer for 23.4% Efficient Monolithic Cu(In,Ga)Se2-Perovskite Tandem Solar Cells

The performance of five hole-transporting layers (HTLs) is investigated in both single-junction perovskite and Cu(In, Ga)Se₂ (CIGSe)-perovskite tandem solar cells: nickel oxide (NiO_x,), copper-doped nickel oxide (NiO_x:Cu), NiO_x+SAM, NiO_x:Cu+SAM, and SAM, where SAM is the [2-(3,-6Dimethoxy-9H-carbazol-9yl)ethyl]phosphonic acid (MeO-2PACz) self-assembled monolayer. The performance of the devices is correlated to the charge-carrier dynamics at the HTL/perovskite interface and the limiting factors of these HTLs are analyzed by performing time-resolved and absolute photoluminescence ((Tr)PL), transient surface photovoltage (tr-SPV), and X-ray/UV photoemission spectroscopy (XPS/UPS) measurements on indium tin oxide (ITO)/HTL/perovskite and CIGSe/HTL/perovskite stacks. A high quasi-Fermi level splitting to open-circuit (QFLS-V_oc) deficit is detected for the NiO_x-based devices, attributed to electron trapping and poor hole extraction at the NiO_x-perovskite interface and a low carrier effective lifetime in the bulk of the perovskite. Simultaneously, doping the NiO_x with 2% Cu and passivating its surface with MeO-2PACz suppresses the electron trapping, enhances the holes extraction, reduces the non-radiative interfacial recombination, and improves the band alignment. Due to this superior interfacial charge-carrier dynamics, NiO_x:Cu+SAM is found to be the most suitable HTL for the monolithic CIGSe-perovskite tandem devices, enabling a power-conversion efficiency (PCE) of 23.4%, V_oc of 1.72V, and a fill factor (FF) of 71%, while the remaining four HTLs suffer from prominent V_oc and FF losses.     

Passivating Defects of Perovskite Solar Cells with Functional Donor-Acceptor–Donor Type Hole Transporting Materials

In this study, a series of donor–acceptor–donor (D-A-D) type small molecules based on the fluorene and diphenylethenyl enamine units, which are distinguished by different acceptors, as holetransporting materials (HTMs) for perovskite solar cells is presented. The incorporation of the malononitrile acceptor units is found to be beneficial for not only carrier transportation but also defects passivation via Pb–N interactions. The highest power conversion efficiency of over 22% is achieved on cells based on V1359, which is higher than that of spiro-OMeTAD under identical conditions. This st shows that HTMs prepared via simplified synthetic routes are not only a low-cost alternative to spiro-OMeTAD but also outperform in efficiency and stability state-of-art materials obtained via expensive cross-coupling methods.     

Reducing Hysteresis and Enhancing Performance of Perovskite Solar Cells Using Low‐Temperature Processed Y‐Doped SnO2 Nanosheets as Electron Selective Layers

Despite the rapid increase of efficiency, perovskite solar cells (PSCs) still face some challenges, one of which is the current–voltage hysteresis. Herein, it is reported that yttrium‐doped tin dioxide (Y‐SnO₂) electron selective layer (ESL) synthesized by an in situ hydrothermal growth process at 95 °C can significantly reduce the hysteresis and improve the performance of PSCs. Comparison studies reveal two main effects of Y doping of SnO₂ ESLs: (1) it promotes the formation of well‐aligned and more homogeneous distribution of SnO₂ nanosheet arrays (NSAs), which allows better perovskite infiltration, better contacts of perovskite with SnO₂ nanosheets, and improves electron transfer from perovskite to ESL; (2) it enlarges the band gap and upshifts the band energy levels, resulting in better energy level alignment with perovskite and reduced charge recombination at NSA/perovskite interfaces. As a result, PSCs using Y‐SnO₂ NSA ESLs exhibit much less hysteresis and better performance compared with the cells using pristine SnO₂ NSA ESLs. The champion cell using Y‐SnO₂ NSA ESL achieves a photovoltaic conversion efficiency of 17.29% (16.97%) when measured under reverse (forward) voltage scanning and a steady‐state efficiency of 16.25%. The results suggest that low‐temperature hydrothermal‐synthesized Y‐SnO₂ NSA is a promising ESL for fabricating efficient and hysteresis‐less PSC.     

The Formation of Calcified Nanospherites during Micropetrosis Represents a Unique Mineralization Mechanism in Aged Human Bone

Osteocytes—the central regulators of bone remodeling—are enclosed in a network of microcavities (lacunae) and nanocanals (canaliculi) pervading the mineralized bone. In a hitherto obscure process related to aging and disease, local plugs in the lacuno‐canalicular network disrupt cellular communication and impede bone homeostasis. By utilizing a suite of high‐resolution imaging and physics‐based techniques, it is shown here that the local plugs develop by accumulation and fusion of calcified nanospherites in lacunae and canaliculi (micropetrosis). Two distinctive nanospherites phenotypes are found to originate from different osteocytic elements. A substantial deviation in the spherites' composition in comparison to mineralized bone further suggests a mineralization process unlike regular bone mineralization. Clearly, mineralization of osteocyte lacunae qualifies as a strong marker for degrading bone material quality in skeletal aging. The understanding of micropetrosis may guide future therapeutics toward preserving osteocyte viability to maintain mechanical competence and fracture resistance of bone in elderly individuals.