Ultra‐Lightweight 3D Carbon Current Collectors: Constructing All‐Carbon Electrodes for Stable and High Energy Density Dual‐Ion Batteries

Dual‐ion batteries (DIBs) attract great interest because they allow two types of ions for reversibly intercalating into electrodes, resulting in various advantages. However, there are three critical problems using graphite‐based cathodes, namely, low active material proportion in the electrodes, current collector corrosion, and massive cathode variation. For addressing these problems, an ultra‐lightweight 3D carbon current collector (CCC) is developed to fabricate all‐carbon electrodes as both cathodes and anodes. Compared with the conventional DIBs using Al and Cu foils as current collectors, the DIBs with 3D CCC of electrically conductive pathways and sufficient ionic diffusion channels deliver enhanced specific capacity stabilized around 140 and 120 mAh g^?1 at 0.5 and 1C, respectively. The electrochemically inert 3D CCC could essentially promote the energy density when calculating the entire electrode mass, along with long‐life cycle stability of 1000 cycles at 5C and no electrochemical corrosion on either anodes or cathodes. With an in situ optical microscope, the cathode expansion is found to massively reduce because the porous 3D CCC could effectively alleviate the huge volume. The results suggest a novel strategy for achieving low‐cost and high energy density DIBs with both mechanically and electrochemically stable features.     

Highly Conductive,Lightweight, Low‐Tortuosity Carbon Frameworks as Ultrathick 3D Current Collectors

The growing demand for advanced energy storage techniques and devices has driven the energy storage market to strive for higher performance, longer cycling life, and better safety. Thick electrode design enabling more electroactive materials has the potential to significantly improve the energy density on device level yet faces major challenges of slow ion transport and high deformability. Here, inspired by natural wood materials with aligned channels along the tree growth direction, a highly conductive, lightweight, and low‐tortuosity carbon framework (CF) directly carbonized from natural wood as an ultrathick 3D current collector is demonstrated. Benefiting from the uniqueness of the multichanneled CF, an ultrathick 3D electrode of lithium iron phosphate filled carbon framework with a large thickness of 800 µm and active material mass loading of 60 mg cm^?2 delivers a rational capacity of 7.6 mAh cm^?2 (95 Ah L^?1 based on volume), long cycling life, and lower deformability with enhanced mechanical properties. This work presents a design concept for thick electrode toward high performance energy storage devices that are not limited to lithium‐ion batteries.     

Flexible,Scalable, and Highly Conductive Garnet‐Polymer Solid Electrolyte Templated by Bacterial Cellulose

Solid‐state electrolytes are a promising candidate for the next‐generation lithium‐ion battery, as they have the advantages of eliminating the leakage hazard of liquid solvent and elevating stability. However, inherent limitations such as the low ionic conductivity of solid polymer electrolytes and the high brittleness of inorganic ceramic electrolytes severally impede their practical application. Here, an inexpensive, facile, and scalable strategy to fabricate a hybrid Li₇La₃Zr₂O₁₂ (LLZO) and poly(ethylene oxide)‐based electrolyte by exploiting bacterial cellulose as a template is reported. The well‐organized LLZO network significantly enhances the ionic conductivity by extending long transport pathways for Li ions, exhibiting an elevated conductivity of 1.12 × 10^?4 S cm^?1. In addition, the hybrid electrolyte presents a structural flexibility, with minor impedance increase after bending. The facile and applicable approach establishes new principles for the strategy of designing scalable and flexible hybrid polymer electrolytes that can be utilized for high‐energy‐density batteries.     

Jabuticaba‐Inspired Hybrid Carbon Filler/Polymer Electrode for Use in Highly Stretchable Aqueous Li‐Ion Batteries

Stretchable electronics are considered as next‐generation devices; however, to realize stretchable electronics, it is first necessary to develop a deformable energy device. Of the various components in energy devices, the fabrication of stretchable current collectors is crucial because they must be mechanically robust and have high electrical conductivity under deformation. In this study, the authors present a conductive polymer composite composed of Jabuticaba‐like hybrid carbon fillers containing carbon nanotubes and carbon black in a simple solution process. The hybrid carbon/polymer (HCP) composite is found to effectively retain its electrical conductivity, even when under high strain of ≈200%. To understand the behavior of conductive fillers in the polymer matrix when under mechanical strain, the authors investigate the microstructure of the composite using an in situ small‐angle X‐ray scattering analysis. The authors observe that the HCP produces efficient electrical pathways for filler interconnections upon stretching. The authors develop a stretchable aqueous rechargeable lithium‐ion battery (ARLB) that utilizes this HCP composite as a stretchable current collector. The ARLB exhibits excellent rate capability (≈90 mA h g^?1 at a rate of 20 C) and outstanding capacity retention of 93% after 500 cycles. Moreover, the stretchable ARLB is able to efficiently deliver power even when under 100% strain.     

Solvent‐Free Synthesis of Thin,Flexible, Nonflammable Garnet‐Based Composite Solid Electrolyte for All‐Solid‐State Lithium Batteries

Thin solid‐state electrolytes with nonflammability, high ionic conductivity, low interfacial resistance, and good processability are urgently required for next‐generation safe, high energy density lithium metal batteries. Here, a 3D Li_6.75La₃Zr_1.75Ta_0.25O₁₂ (LLZTO) self‐supporting framework interconnected by polytetrafluoroethylene (PTFE) binder is prepared through a simple grinding method without any solvent. Subsequently, a garnet‐based composite electrolyte is achieved through filling the flexible 3D LLZTO framework with a succinonitrile solid electrolyte. Due to the high content of garnet ceramic (80.4 wt%) and high heat‐resistance of the PTFE binder, such a composite electrolyte film with nonflammability and high processability exhibits a wide electrochemical window of 4.8 V versus Li/Li⁺ and high ionic transference number of 0.53. The continuous Li⁺ transfer channels between interconnected LLZTO particles and succinonitrile, and the soft electrolyte/electrode interface jointly contribute to a high ambient‐temperature ionic conductivity of 1.2 × 10^?4 S cm^?1 and excellent long‐term stability of the Li symmetric battery (stable at a current density of 0.1 mA cm^?2 for over 500 h). Furthermore, as‐prepared LiFePO₄|Li and LiNi_0.5Mn_0.3Co_0.2O₂|Li batteries based on the thin composite electrolyte exhibit high discharge specific capacities of 153 and 158 mAh g^?1 respectively, and desirable cyclic stabilities at room temperature.     

Comparison of Quinone‐Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long‐Term Stability with Tetrasubstituted Quinones

Quinones are appealing targets as organic charge carriers for aqueous redox flow batteries (RFBs), but their utility continues to be constrained by limited stability under operating conditions. The present study evaluates the stability of a series of water‐soluble quinones, with redox potentials ranging from 605–885 mV versus NHE, under acidic aqueous conditions (1 m H₂SO₄). Four of the quinones are examined as cathodic electrolytes in an aqueous RFB, paired with anthraquinone‐2,7‐disulfonate as the anodic electrolyte. The RFB data complement other solution stability tests and show that the most stable electrolyte is a tetrasubstituted quinone containing four sulfonated thioether substituents. The results highlight the importance of substituting all C–H positions of the quinone in order to maximize the quinone stability and set the stage for design of improved organic electrolytes for aqueous RFBs.     

Metal‐Organic Framework Cathodes Based on a Vanadium Hexacyanoferrate Prussian Blue Analogue for High‐Performance Aqueous Rechargeable Batteries

Despite the unique advantages of the metal‐organic framework of Prussian blue analogues (PBAs), including a favorable crystallographic structure and facile diffusion kinetics, the capacity of PBAs delivered in aqueous systems has been limited to ≈60 mA h g^?1 because only single species of transition metal ions incorporated into the PBAs are electrochemically activated. Herein, vanadium hexacyanoferrate (V/Fe PBA) is proposed as a breakthrough to this limitation, and its electrochemical performance as a cathode for aqueous rechargeable batteries (ARBs) is investigated for the first time. V/Fe PBAs are synthesized by a simple co‐precipitation method with optimization of the acidity and molar ratios of precursor solutions. The V/Fe PBAs provide an improved capacity of 91 mA h^?1 under a current density of 110 mA g^?1 (C‐rate of ≈1.2 C), taking advantage of the multiple‐electron redox reactions of V and Fe ions. Under an extremely fast charge/discharge rate of 3520 mA g^?1, the V/Fe PBA exhibits a sufficiently high discharge capacity of 54 mA h g^?1 due to its opened structure and 3D hydrogen bonding networks. V/Fe PBA‐based ARBs are the most promising candidates for large‐scale stationary energy storage systems due to their high electrochemical performance, reasonable cost, and high efficiency.     

An Air‐Stable and Dendrite‐Free Li Anode for Highly Stable All‐Solid‐State Sulfide‐Based Li Batteries

Li metal is a promising anode material for all‐solid‐state batteries, owing to its high specific capacity and low electrochemical potential. However, direct contact of Li metal with most solid‐state electrolytes induces severe side reactions that can lead to dendrite formation and short circuits. Moreover, Li metal is unstable when exposed to air, leading to stringent processing requirements. Herein, it is reported that the Li₃PS₄/Li interface in all‐solid‐state batteries can be stabilized by an air‐stable Li_xSiS_y protection layer that is formed in situ on the surface of Li metal through a solution‐based method. Highly stable Li cycling for over 2000 h in symmetrical cells and a lifetime of over 100 cycles can be achieved for an all‐solid‐state LiCoO₂/Li₃PS₄/Li cell. Synchrotron‐based high energy X‐ray photoelectron spectroscopy in‐depth analysis demonstrates the distribution of different components within the protection layer. The in situ formation of an electronically insulating Li_xSiS_y protection layer with highly ionic conductivity provides an effective way to prevent Li dendrite formation in high‐energy all‐solid‐state Li metal batteries.     

Graphitic Nanoshell/Mesoporous Carbon Nanohybrids as Highly Efficient and Stable Bifunctional Oxygen Electrocatalysts for Rechargeable Aqueous Na–Air Batteries

Efficient and cost‐effective bifunctional electrocatalysts for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) are of vital importance in energy conversion and storage devices. Despite the recent progress in bifunctional oxygen electrocatalysts, their unbalanced and insufficient OER and ORR activities has continued to pose challenges for the practical application of such energy devices. The design of highly integrated, high‐performance, bifunctional oxygen electrocatalysts composed of highly graphitic nanoshells embedded in mesoporous carbon (GNS/MC) is reported. The GNS/MC exhibits very high oxygen electrode activity, which is one of the best performances among nonprecious metal bifunctional oxygen electrocatalysts, and substantially outperforms Ir‐ and Pt‐based catalysts. Moreover, the GNS/MC shows excellent durability for both OER and ORR. In situ X‐ray absorption spectroscopy and square wave voltammetry reveal the roles of residual Ni and Fe entities in enhancing OER and ORR activities. Raman spectra indicate highly graphitic, defect‐rich nature of the GNS/MC, which can contribute to the enhanced OER activity and to high stability for the OER and ORR. In aqueous Na–air battery tests, the GNS/MC air cathode‐based cell exhibits superior performance to Ir/C‐ and Pt/C‐based batteries. Significantly, the GNS/MC‐based cell demonstrates the first example of rechargeable aqueous Na–air battery.     

A Conductive Molecular Framework Derived Li2S/N,P‐Codoped Carbon Cathode for Advanced Lithium–Sulfur Batteries

Li₂S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li₂S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li₂S. As a result, the Li₂S/N,P–C composite electrode delivers a stable capacity of 700 mA h g^?1 with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm^?2 at 0.5C.     

Sodium Plating from Na‐β″‐Alumina Ceramics at Room Temperature,Paving the Way for Fast‐Charging All‐Solid‐State Batteries

All‐solid‐state batteries with an alkali metal anode have the potential to achieve high energy density. However, the onset of dendrite formation limits the maximum plating current density across the solid electrolyte and prevents fast charging. It is shown that the maximum plating current density is related to the interfacial resistance between the solid electrolyte and the metal anode. Due to their high ionic conductivity, low electronic conductivity, and stability against sodium metal, Na‐β″‐alumina ceramics are excellent candidates as electrolytes for room‐temperature all‐solid‐state batteries. Here, it is demonstrated that a heat treatment of Na‐β″‐alumina ceramics in argon atmosphere enables an interfacial resistance <10 Ω cm² and current densities up to 12 mA cm^?2 at room temperature. The current density obtained for Na‐β″‐alumina is ten times higher than that measured on a garnet‐type Li₇La₃Zr₂O₁₂ electrolyte under equivalent conditions. X‐ray photoelectron spectroscopy shows that eliminating hydroxyl groups and carbon contaminations at the interface between Na‐β″‐alumina and sodium metal is key to reach such values. By comparing the temperature‐dependent stripping/plating behavior of Na‐β″‐alumina and Li₇La₃Zr₂O₁₂, the role of the alkali metal in governing interface kinetics is discussed. This study provides new insights into dendrite formation and paves the way for fast‐charging all‐solid‐state batteries.