Environmentally Robust Memristor Enabled by Lead‐Free Double Perovskite for High‐Performance Information Storage

Memristors are emerging as a rising star of new computing and information storage techniques. However, the practical applications are severely challenged by their instability toward harsh conditions, including high moisture, high temperatures, fire, ionizing irradiation, and mechanical bending. In this work, for the first time, lead‐free double perovskite Cs₂AgBiBr₆ is utilized for environmentally robust memristors, enabling highly efficient information storage. The memory performance of the typical indium‐tin‐oxide/Cs₂AgBiBr₆/Au sandwich‐like memristors is retained after 1000 switching cycles, 10⁵ s of reading, and 10⁴ times of mechanical bending, comparable to other halide perovskite memristors. Most importantly, the memristive behavior remains robust in harsh environments, including humidity up to 80%, temperatures as high as 453 K, an alcohol burner flame for 10 s, and ⁶⁰Co γ‐ray irradiation for a dosage of 5 × 10⁵ rad (SI), which is not achieved by any other memristors and commercial flash memory techniques. The realization of an environmentally robust memristor from Cs₂AgBiBr₆ with a high memory performance will inspire further development of robust electronics using lead‐free double perovskites.     

Robust Tin‐Based Perovskite Solar Cells with Hybrid Organic Cations to Attain Efficiency Approaching 10%

The stability of a tin‐based perovskite solar cell is a major challenge. Here, hybrid tin‐based perovskite solar cells in a new series that incorporate a nonpolar organic cation, guanidinium (GA⁺), in varied proportions into the formamidinium (FA⁺) tin triiodide perovskite (FASnI₃) crystal structure in the presence of 1% ethylenediammonium diiodide (EDAI₂) as an additive, are reported. The device performance is optimized at a precursor ratio (GAI:FAI) of 20:80 to attain a power conversion efficiency (PCE) of 8.5% when prepared freshly; the efficiencies continuously increase to attain a record PCE of 9.6% after storage in a glove‐box environment for 2000 h. The hybrid perovskite works stably under continuous 1 sun illumination for 1 h and storage in air for 6 days without encapsulation. Such a tin‐based perovskite passes all harsh standard tests, and the efficiency of a fresh device, 8.3%, is certified. The great performance and stability of the device reported herein attains a new milestone for lead‐free perovskite solar cells on a path toward commercial development.     

Lead‐Free Antiferroelectric Silver Niobate Tantalate with High Energy Storage Performance

Antiferroelectric materials that display double ferroelectric hysteresis loops are receiving increasing attention for their superior energy storage density compared to their ferroelectric counterparts. Despite the good properties obtained in antiferroelectric La‐doped Pb(Zr,Ti)O₃‐based ceramics, lead‐free alternatives are highly desired due to the environmental concerns, and AgNbO₃ has been highlighted as a ferrielectric/antiferroelectric perovskite for energy storage applications. Enhanced energy storage performance, with recoverable energy density of 4.2 J cm^?3 and high thermal stability of the energy storage density (with minimal variation of ≤±5%) over 20–120 °C, can be achieved in Ta‐modified AgNbO₃ ceramics. It is revealed that the incorporation of Ta to the Nb site can enhance the antiferroelectricity because of the reduced polarizability of B‐site cations, which is confirmed by the polarization hysteresis, dielectric tunability, and selected‐area electron diffraction measurements. Additionally, Ta addition in AgNbO₃ leads to decreased grain size and increased bulk density, increasing the dielectric breakdown strength, up to 240 kV cm^?1 versus 175 kV cm^?1 for the pure counterpart, together with the enhanced antiferroelectricity, accounting for the high energy storage density.     

Direct Observation of Halide Migration and its Effect on the Photoluminescence of Methylammonium Lead Bromide Perovskite Single Crystals

Optoelectronic devices based on hybrid perovskites have demonstrated outstanding performance within a few years of intense study. However, commercialization of these devices requires barriers to their development to be overcome, such as their chemical instability under operating conditions. To investigate this instability and its consequences, the electric field applied to single crystals of methylammonium lead bromide (CH₃NH₃PbBr₃) is varied, and changes are mapped in both their elemental composition and photoluminescence. Synchrotron‐based nanoprobe X‐ray fluorescence (nano‐XRF) with 250 nm resolution reveals quasi‐reversible field‐assisted halide migration, with corresponding changes in photoluminescence. It is observed that higher local bromide concentration is correlated to superior optoelectronic performance in CH₃NH₃PbBr₃. A lower limit on the electromigration rate is calculated from these experiments and the motion is interpreted as vacancy‐mediated migration based on nudged elastic band density functional theory (DFT) simulations. The XRF mapping data provide direct evidence of field‐assisted ionic migration in a model hybrid‐perovskite thin single crystal, while the link with photoluminescence proves that the halide stoichiometry plays a key role in the optoelectronic properties of the perovskite.     

Hollow MXene Spheres and 3D Macroporous MXene Frameworks for Na‐Ion Storage

2D transition metal carbides and nitrides, named MXenes, are attracting increasing attentions and showing competitive performance in energy storage devices including electrochemical capacitors, lithium‐ and sodium‐ion batteries, and lithium–sulfur batteries. However, similar to other 2D materials, MXene nanosheets are inclined to stack together, limiting the device performance. In order to fully utilize MXenes' electrochemical energy storage capability, here, processing of 2D MXene flakes into hollow spheres and 3D architectures via a template method is reported. The MXene hollow spheres are stable and can be easily dispersed in solvents such as water and ethanol, demonstrating their potential applications in environmental and biomedical fields as well. The 3D macroporous MXene films are free‐standing, flexible, and highly conductive due to good contacts between spheres and metallic conductivity of MXenes. When used as anodes for sodium‐ion storage, these 3D MXene films exhibit much improved performances compared to multilayer MXenes and MXene/carbon nanotube hybrid architectures in terms of capacity, rate capability, and cycling stability. This work demonstrates the importance of MXene electrode architecture on the electrochemical performance and can guide future work on designing high‐performance MXene‐based materials for energy storage, catalysis, environmental, and biomedical applications.     

Organic Functional Molecules towards Information Processing and High‐Density Information Storage

In this Progress Report, we discuss our recent achievements in design and synthesis of new functional molecules towards information processing at the molecular level and high‐density information storage. These include: 1) new molecular switches, logic gates, and combinational logic circuits based on molecules and ensembles with photochromic spiropyran units that undergo reversible structural transformation among multistates, in response to external inputs such as light, protons, and metal ions; 2) high‐density information storage, mainly focusing on nanometer‐scale electrical recording based on the conductance transition of organic molecules, and multimode data storage on multiresponsive molecules. Relevant progress and an outlook in this area are also discussed.

     

Free‐Standing Crystalline@Amorphous Core–Shell Nanoarrays for Efficient Energy Storage

Structures comprising high capacity active material are highly desirable in the development of advanced electrodes for energy storage devices. However, the structure degradation of such material still remains a challenge. The construction of amorphous and crystalline heterostructure appears to be a novel and effectual strategy to figure out the problem, owing to the distinct properties of the amorphous protective layer. Herein, crystalline‐Co₃O₄@amorphous‐TiO₂ core–shell nanoarrays directly grown on the carbon cloth substrate are rationally designed to construct the free‐standing electrode. In the unique structure, the 3D porous nanoarrays provide increased availability of electrochemical active sites, and the array with a unique heterostructure of crystalline Co₃O₄ core and amorphous TiO₂ shell exhibits intriguing synergistic properties. Besides, the amorphous TiO₂ protective layer shows elastic behavior to mitigate the volume effect of Co₃O₄. Benefiting from these structural advantages, the as‐prepared free‐standing electrode exhibits superior lithium storage properties, including high coulombic efficiency, outstanding cyclic stability, and rate capability. Pouch cells with high flexibility are also fabricated and show remarkable electrochemical performances, holding great potential for flexible electronic devices in the future.     

Ideal Three‐Dimensional Electrode Structures for Electrochemical Energy Storage

Three‐dimensional electrodes offer great advantages, such as enhanced ion and electron transport, increased material loading per unit substrate area, and improved mechanical stability upon repeated charge–discharge. The origin of these advantages is discussed and the criteria for ideal 3D electrode structure are outlined. One of the common features of ideal 3D electrodes is the use of a 3D carbon‐ or metal‐based porous framework as the structural backbone and current collector. The synthesis methods of these 3D frameworks and their composites with redox‐active materials are summarized, including transition metal oxides and conducting polymers. The structural characteristics and electrochemical performances are also reviewed. Synthesis of composite 3D electrodes is divided into two types — template‐assisted and template‐free methods — depending on whether a pre‐made template is required. The advantages and drawbacks of both strategies are discussed.     

Hybrid Nanostructures for Energy Storage Applications

Materials engineering plays a key role in the field of energy storage. In particular, engineering materials at the nanoscale offers unique properties resulting in high performance electrodes and electrolytes in various energy storage devices. Consequently, considerable efforts have been made in recent years to fulfill the future requirements of electrochemical energy storage using these advanced materials. Various multi‐functional hybrid nanostructured materials are currently being studied to improve energy and power densities of next generation storage devices. This review describes some of the recent progress in the synthesis of different types of hybrid nanostructures using template assisted and non‐template based methods. The potential applications and recent research efforts to utilize these hybrid nanostructures to enhance the electrochemical energy storage properties of Li‐ion battery and supercapacitor are discussed. This review also briefly outlines some of the recent progress and new approaches being explored in the techniques of fabrication of 3D battery structures using hybrid nanoarchitectures.     

空间限域铅离子与钙钛矿纳米晶间的可逆转换与信息存储应用

发光材料在机密信息保护与防伪领域中发挥着重要作用。钙钛矿纳米晶作为一类高效低成本发光材料可通过两步法原位转换获得, 使其在信息加密、解密领域极具应用前景。本研究探索了“不可见”铅有机框架和发光MAPbBr₃钙钛矿纳米晶间的可逆转换, 以及它们在荧光打印信息存储中的应用。通过铅离子与2-甲基咪唑配位构建新型金属有机框架, 实现铅离子限域分布, 在此基础上通过与甲胺溴原位反应生成钙钛矿纳米晶。利用金属有机框架在可见/紫外光下无光响应的特性, 通过墨水打印对信息进行加密存储。加密信息经甲胺溴喷雾处理, 引发原位反应生成钙钛矿纳米晶, 在紫外光下表现出强光致发光特性, 实现信息解密。利用甲胺溴和水作为解密和加密试剂可实现荧光的多次循环显示与消除。     

Atomic Cobalt Covalently Engineered Interlayers for Superior Lithium‐Ion Storage

With the unique‐layered structure, MXenes show potential as electrodes in energy‐storage devices including lithium‐ion (Li⁺) capacitors and batteries. However, the low Li⁺‐storage capacity hinders the application of MXenes in place of commercial carbon materials. Here, the vanadium carbide (V₂C) MXene with engineered interlayer spacing for desirable storage capacity is demonstrated. The interlayer distance of pristine V₂C MXene is controllably tuned to 0.735 nm resulting in improved Li‐ion capacity of 686.7 mA h g^?1 at 0.1 A g^?1, the best MXene‐based Li⁺‐storage capacity reported so far. Further, cobalt ions are stably intercalated into the interlayer of V₂C MXene to form a new interlayer‐expanded structure via strong V–O–Co bonding. The intercalated V₂C MXene electrodes not only exhibit superior capacity up to 1117.3 mA h g^?1 at 0.1 A g^?1, but also deliver a significantly ultralong cycling stability over 15 000 cycles. These results clearly suggest that MXene materials with an engineered interlayer distance will be a rational route for realizing them as superstable and high‐performance Li⁺ capacitor electrodes.     

Recent Advances in 3D Graphene Architectures and Their Composites for Energy Storage Applications

Graphene is widely applied as an electrode material in energy storage fields. However, the strong π–π interaction between graphene layers and the stacking issues lead to a great loss of electrochemically active surface area, damaging the performance of graphene electrodes. Developing 3D graphene architectures that are constructed of graphene sheet subunits is an effective strategy to solve this problem. The graphene architectures can be directly utilized as binder‐free electrodes for energy storage devices. Furthermore, they can be used as a matrix to support active materials and further improve their electrochemical performance. Here, recent advances in synthesizing 3D graphene architectures and their composites as well as their application in different energy storage devices, including various battery systems and supercapacitors are reviewed. In addition, their challenges for application at the current stage are discussed and future development prospects are indicated.     

Highly‐Anisotropic Dion–Jacobson Hybrid Perovskite by Tailoring Diamine into CsPbBr3 for Polarization‐Sensitive Photodetection

2D materials with inherent attributes of structural anisotropy have been well applied in the field of polarization‐sensitive photodetection. However, to explore new 2D members with strong polarized‐light responses still remains a challenge. Herein, by alloying diamine molecule into the 3D prototype of CsPbBr₃, a new Dion–Jacobson (DJ) type 2D perovskite of (HDA)CsPb₂Br₇ ( 1 , where HDA²⁺ is 1,6‐hexamethylenediammonium), containing both inorganic Cs metal and organic cations is designed. The natural anisotropy characteristics of 1 are solidly elucidated by analyzing crystal structure, electric conductivity, and optical properties. Strikingly, distinct polarization‐sensitive responses are observed in 1 , owing to its strong anisotropy of optical absorption (the ratio of α_c/α_b ≈ 2.2). Consequently, crystal‐based detectors of 1 exhibit fascinating photo‐activities to polarized‐light, including high detectivity (1.5 × 10⁹ Jones), large dichroism ratio (I_ph^c/I_ph^b ≈ 1.6) and fast responding rate (200 µs). All these polarization‐sensitive performances along with intriguing phase stability make 1 a potential candidate for polarized‐light detection. This work paves a pathway toward new functionalities of DJ‐type 2D hybrid perovskites for their future optoelectronic device applications.