Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Li‐rich manganese based oxides (LRMOs) are considered an attractive high‐capacity cathode for advanced Li‐ion batteries; however, their poor cyclability and gradual voltage fading have hindered their practical applications. Herein, an efficient and facile strategy is proposed to stabilize the lattice structure of LRMOs by surface modification of polyacrylic acid (PAA). The PAA‐coated LRMO electrode exhibits only 104 mV of the voltage fading after 100 cycles and 88% capacity retention over 500 cycles. The structural stability is attributed to the carboxyl groups in PAA chains reacting with oxygen species on the surface of LRMO to form a uniform and tightly coated film, which significantly suppresses the dissolution of transition metal elements from the cathode materials into the electrolyte. Importantly, a H⁺/Li⁺ exchange reaction takes place between the LRMO and PAA, generating a proton‐doped surface layer. Density functional theory calculations and experimental evidence demonstrates that the H⁺ ions in the surface lattice efficiently inhibit the migration of transition metal ions, leading to a stabilized lattice structure. This surface modification approach may provide a new route to building a stable Li‐rich oxide cathode with high capacity retention and low voltage fading for practical Li‐ion battery applications.     

Phosphorene as Cathode Material for High‐Voltage,Anti‐Self‐Discharge Zinc Ion Hybrid Capacitors

Output voltage and self‐discharge rate are two important performance indices for supercapacitors, which have long been overlooked, though these play a very significant role in their practical application. Here, a zinc anode is used to construct a zinc ion hybrid capacitor. Expanded operating voltage of the hybrid capacitor is obtained with novel electrolytes. In addition, significantly improved anti‐self‐discharge ability is achieved. The phosphorene‐based zinc ion capacitor exploiting a “water in salt” electrolyte with a working potential can reach 2.2 V, delivering 214.3 F g^?1 after 5000 cycles. The operating voltage is further extended to 2.5 V through the use of an organic solvent as the electrolyte; the solvent is prepared by adding 0.2 m ZnCl₂ into the tetraethylammonium tetrafluoroborate in propylene carbonate (Et₄NBF₄/PC) solvent, and it exhibits 105.9 F g^?1 even after 9500 cycles. More importantly, the phosphorene‐based capacitors possess excellent anti‐self‐discharge performance. The capacitors retain 76.16% of capacitance after resting for 300 h. The practical application of the zinc ion capacitor is demonstrated through a flexible paper‐based printed microcapacitor. It is believed that the developed zinc ion capacitor can effectively resolve the severe self‐discharge problem of supercapacitors. Moreover, high‐voltage zinc ion capacitors provide more opportunities for the application of supercapacitors.     

Vacancy in Ultrathin 2D Nanomaterials toward Sustainable Energy Application

The unique physicochemical properties of (2D) nanomaterials make them well‐suited for use in sustainable energy applications. Many of these materials can be further improved with vacancy engineering. This review details recent progress in the vacancy engineering of ultrathin 2D nanomaterials. For clarity, it mainly focuses on various ultrathin 2D materials in three categories: X_a&X_aY_b‐, M_aX_b‐, or M_aX_bY_c‐structured materials. Recently developed vacancies in different types of ultrathin 2D materials, as well as their preparation and characterization, are described. Emphasis is placed on the potential electrochemical energy storage and conversion applications of these materials. This review considers the relationship between vacancy properties and material categories of various ultrathin 2D materials in terms of application requirements, preparation, and characterization techniques. The challenges and future outlook of this promising field are summarized.     

Tin Halide Perovskites: Progress and Challenges

The chemical composition engineering of lead halide perovskites via a partial or complete replacement of toxic Pb with tin has been widely reported as a feasible process due to the suitable ionic radius of Sn and its possibility of existing in the +2 state. Interestingly, a complete replacement narrows the bandgap while a partial replacement gives an anomalous phenomenon involving a further narrowing of bandgap relative to the pure Pb and Sn halide perovskite compounds. Unfortunately, the merits of this anomalous behavior have not been properly harnessed. Although promising progress has been made to advance the properties and performance of Sn‐based perovskite systems, their photovoltaic (PV) parameters are still significantly inferior to those of the Pb‐based analogs. This review summarizes the current progress and challenges in the preparation, morphological and photophysical properties of Sn‐based halide perovskites, and how these affect their PV performance. Although it can be argued that the Pb halide perovskite systems may remain the most sought after technology in the field of thin film perovskite PV, prospective research directions are suggested to advance the properties of Sn halide perovskite materials for improved device performance.     

Affinity Laminated Chromatography Membrane Built‐in Electrodes for Suppressing Polysulfide Shuttling in Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries are promising candidates for energy storage, but suffer from capacity and cycling challenges caused by the serious shuttling effect of polysulfide (PS) ions. To address these issues, a sodium alginate (SA)‐derived affinity laminated chromatography membrane built‐in electrode is designed. This is the first attempt to utilize this type of membrane, which is widely used for the selective adsorption of proteins, in the battery field. An ordered multilayer structure throughout the electrode can easily be obtained, and the number of membrane layers can be also conveniently controlled by varying the cross‐linking time of SA. The PS shuttling effect is efficiently suppressed and the permeability of PSs is reduced by enveloping the carbon/sulfur powder in ultrathin laminated chromatography membranes. As a result, these designed electrodes deliver a superhigh initial capacity of 1492 mA h g^?1, with a capacity retention almost 20% higher than the contrast. This low‐cost and easily mass‐producible strategy inspired by affinity chromatography is expected to effectively solve the PS shuttling problem toward high‐loading and long‐lifetime Li–S batteries in practice.     

In Situ Conversion of Cu3P Nanowires to Mixed Ion/Electron‐Conducting Skeleton for Homogeneous Lithium Deposition

The introduction of 3D wettable current collectors is one of the practical strategies toward realizing high reversibility of lithium (Li) metal anodes, yet its effect is usually insufficient owing to single electron‐conductive skeleton. Here, homogeneous Li deposition behavior and enhanced Coulombic efficiency is reported for electrochemically lithiated Cu₃P nanowires, owing to the formation of a mixed ion/electron‐conducting skeleton (MIECS). In particular, by evaluating the Gibbs free energy change, the possible chemical reaction between Cu₃P and molten Li is used to construct a MIECS containing Li₃P and Cu–Li alloy phase. The successful conversion of Cu₃P nanowires to Li₃P and Cu–Li alloy nanocomposite not only greatly reduces the surface energy between molten Li and Cu₃P, but also induces uniform Li stripping/plating behavior via balanced ion/electron transport. Thus, the as‐obtained Li@MIECS composite anode displays superior cycling stability in both symmetric cells and full cells. This work provides a promising option for the preparation of high‐performance composite Li anodes containing MIECS by thermally pre‐storing Li.     

Oxygen‐Deficient Blue TiO2 for Ultrastable and Fast Lithium Storage

Developing a titanium dioxide (TiO₂)‐based anode with superior high‐rate capability and long‐term cycling stability is important for efficient energy storage. Herein, a simple one‐step approach for fabricating blue TiO₂ nanoparticles with oxygen vacancies is reported. Oxygen vacancies can enlarge lattice spaces, lower charge transfer resistance, and provide more active sites in TiO₂ lattices. As a result, this blue TiO₂ electrode exhibits a highly reversible capacity of 50 mAh g^?1 at 100 C (16 800 mA g^?1) even after 10 000 cycles, which is attributable to the combination of surface capacitive process and remarkable diffusion‐controlled insertion revealed by the kinetic analysis. The strategy of employing oxygen‐deficient nanoparticles may be extended to the design of other robust semiconductor materials as electrodes for energy storage.     

Conductive Hole‐Selective Passivating Contacts for Crystalline Silicon Solar Cells

Defect state passivation and conductivity of materials are always in opposition; thus, it is unlikely for one material to possess both excellent carrier transport and defect state passivation simultaneously. As a result, the use of partial passivation and local contact strategies are required for silicon solar cells, which leads to fabrication processes with technical complexities. Thus, one material that possesses both a good passivation and conductivity is highly desirable in silicon photovoltaic (PV) cells. In this work, a passivation‐conductivity phase‐like diagram is presented and a conductive‐passivating‐carrier‐selective contact is achieved using PEDOT:Nafion composite thin films. A power conversion efficiency of 18.8% is reported for an industrial multicrystalline silicon solar cell with a back PEDOT:Nafion contact, demonstrating a solution‐processed organic passivating contact concept. This concept has the potential advantages of omitting the use of conventional dielectric passivation materials deposited by costly high‐vacuum equipment, energy‐intensive high‐temperature processes, and complex laser opening steps. This work also contributes an effective back‐surface field scheme and a new hole‐selective contact for p‐type and n‐type silicon solar cells, respectively, both for research purposes and as a low‐cost surface engineering strategy for future Si‐based PV technologies.