Search

Highlights: A class of solvent-free covalent organic framework (COF) single-ion conductors (Li-COF@P) has been designed via ion–dipole interaction as opposed to traditional ion–ion interaction, promoting ion dissociation and Li+ migration through directional ionic channels. The Li-COF@P enabled long cycle life (88.3% after 2000 cycles) in all-solid-state Li organic batteries (ASSLOBs) under ambient operating conditions, which outperformed those of previously reported ASSOLBs. This Li-COF@P strategy holds promise as a viable alternative to the currently prevalent inorganic solid electrolytes. Single-ion conductors based on covalent organic frameworks (COFs) have garnered attention as a potential alternative to currently prevalent inorganic ion conductors owing to their structural uniqueness and chemical versatility. However, the sluggish Li+ conduction has hindered their practical applications. Here, we present a class of solvent-free COF single-ion conductors (Li-COF@P) based on weak ion–dipole interaction as opposed to traditional strong ion–ion interaction. The ion (Li+ from the COF)–dipole (oxygen from poly(ethylene glycol) diacrylate embedded in the COF pores) interaction in the Li-COF@P promotes ion dissociation and Li+ migration via directional ionic channels. Driven by this single-ion transport behavior, the Li-COF@P enables reversible Li plating/stripping on Li-metal electrodes and stable cycling performance (88.3% after 2000 cycles) in organic batteries (Li metal anode||5,5'-dimethyl-2,2'-bis-p-benzoquinone (Me2BBQ) cathode) under ambient operating conditions, highlighting the electrochemical viability of the Li-COF@P for all-solid-state organic batteries. [ABSTRACT FROM AUTHOR]

Despite the enormous interest in Li metal as an ideal anode material, the uncontrollable Li dendrite growth and unstable solid electrolyte interphase have plagued its practical application. These limitations can be attributed to the sluggish and uneven Li+ migration towards Li metal surface. Here, we report olefin‐linked covalent organic frameworks (COFs) with electronegative channels for facilitating selective Li+ transport. The triazine rings and fluorinated groups of the COFs are introduced as electron‐rich sites capable of enhancing salt dissociation and guiding uniform Li+ flux within the channels, resulting in a high Li+ transference number (0.85) and high ionic conductivity (1.78 mS cm−1). The COFs are mixed with a polymeric binder to form mixed matrix membranes. These membranes enable reliable Li plating/stripping cyclability over 700 h in Li/Li symmetric cells and stable capacity retention in Li/LiFePO4 cells, demonstrating its potential as a viable cationic highway for accelerating Li+ conduction. [ABSTRACT FROM AUTHOR]

Highlights: Mechanistic understanding of ion transport phenomena in composite solid-state electrolytes (CSEs) for practical solid-state batteries is conducted. Percolation threshold formation of the inorganic (LPSCl) phase in the CSEs depends on elasticity of the gel polymer electrolyte (GPE) phase. Manipulating the solvation/desolvation behavior of the GPE phase facilitates ion conduction across the LPSCl-GPE interfaces. Despite the enormous interest in inorganic/polymer composite solid-state electrolytes (CSEs) for solid-state batteries (SSBs), the underlying ion transport phenomena in CSEs have not yet been elucidated. Here, we address this issue by formulating a mechanistic understanding of bi-percolating ion channels formation and ion conduction across inorganic-polymer electrolyte interfaces in CSEs. A model CSE is composed of argyrodite-type Li6PS5Cl (LPSCl) and gel polymer electrolyte (GPE, including Li+-glyme complex as an ion-conducting medium). The percolation threshold of the LPSCl phase in the CSE strongly depends on the elasticity of the GPE phase. Additionally, manipulating the solvation/desolvation behavior of the Li+-glyme complex in the GPE facilitates ion conduction across the LPSCl-GPE interface. The resulting scalable CSE (area = 8 × 6 (cm × cm), thickness ~ 40 μm) can be assembled with a high-mass-loading LiNi0.7Co0.15Mn0.15O2 cathode (areal-mass-loading = 39 mg cm–2) and a graphite anode (negative (N)/positive (P) capacity ratio = 1.1) in order to fabricate an SSB full cell with bi-cell configuration. Under this constrained cell condition, the SSB full cell exhibits high volumetric energy density (480 Wh Lcell−1) and stable cyclability at 25 °C, far exceeding the values reported by previous CSE-based SSBs. [ABSTRACT FROM AUTHOR]

Despite the ever‐increasing demand for transparent power sources in wireless optoelectronics, most of them have still relied on synthetic chemicals, thus limiting their versatile applications. Here, a class of transparent nanocellulose paper microsupercapacitors (TNP‐MSCs) as a beyond‐synthetic‐material strategy is demonstrated. Onto semi‐interpenetrating polymer network‐structured, thiol‐modified transparent nanocellulose paper, a thin layer of silver nanowire and a conducting polymer (chosen as a pseudocapacitive electrode material) are consecutively introduced through microscale‐patterned masks (which are fabricated by electrohydrodynamic jet printing) to produce a transparent conductive electrode (TNP‐TCE) with planar interdigitated structure. This TNP‐TCE, in combination with solid‐state gel electrolytes, enables on‐demand (in‐series/in‐parallel) cell configurations in a single body of TNP‐MSC. Driven by this structural uniqueness and scalable microfabrication, the TNP‐MSC exhibits improvements in optical transparency (T = 85%), areal capacitance (0.24 mF cm−2), controllable voltage (7.2 V per cell), and mechanical flexibility (origami airplane), which exceed those of previously reported transparent MSCs based on synthetic chemicals. [ABSTRACT FROM AUTHOR]

Polymeric single lithium (Li)‐ion conductors (SICs), along with inorganic conducting materials such as sulfides and oxides, have received significant attention as promising solid‐state electrolytes. Yet their practical applications have been plagued predominantly by sluggish ion transport. Here, a new class of quasi‐solid‐state SICs based on anion‐rectifying semi‐interpenetrating polymer networks (semi‐IPNs) with reticulated ion nanochannels are demonstrated. This semi‐IPN SIC (denoted as sSIC) features a bicontinuous and nanophase‐separated linear cationic polyurethane (cPU), which supports single‐ion conducting nanochannels, and ultraviolet‐crosslinked triacrylate polymer, which serves as a mechanical framework. The cPU phase is preferentially swollen with a liquid electrolyte and subsequently allows anion‐rectifying capability and nanofluidic transport via surface charge, which enable fast Li+ migration through ion nanochannels. Such facile Li+ conduction is further enhanced by tuning ion‐pair (i.e., freely movable anions and cations tethered to the cPU chains) interaction. Notably, the resulting sSIC provides high Li+ conductivity that exceeds those of commercial carbonate liquid electrolytes. This unusual single‐ion conduction behavior of the sSIC suppresses anion‐triggered interfacial side reactions with Li‐metal anodes and facilitates electrochemical reaction kinetics at electrodes, eventually improving rate performance and cycling retention of Li‐metal cells (comprising LiNi0.8Co0.1Mn0.1O2 cathodes and Li‐metal anodes) compared to those based on carbonate liquid electrolytes. [ABSTRACT FROM AUTHOR]

Despite their potential as post lithium‐ion batteries, solid‐state Li‐metal batteries are struggling with insufficient electrochemical sustainability and ambient operation limitations. These challenges mainly stem from lack of reliable solid‐state electrolytes. Here, a new class of single‐ion conducting quasi‐solid‐state soft electrolyte (SICSE) for practical semi‐solid Li‐metal batteries (SSLMBs) is demonstrated. The SICSE consists of an ion‐rectifying compliant skeleton and a nonflammable coordinated electrolyte. Rheology‐tuned SICSE pastes, in combination with UV curing‐assisted multistage printing, allow fabrication of seamlessly integrated SSLMBs (composed of a Li metal anode and LiNi0.8Co0.1Mn0.1 cathode) without undergoing high‐pressure/high‐temperature manufacturing steps. The single‐ion conducting capability of the SICSE plays a viable role in stabilizing the interfaces with the electrodes. The resulting SSLMB full cell exhibits stable cycling performance and bipolar configurations with tunable voltages and high gravimetric/volumetric energy densities (476 Wh kgcell−1/1102 Wh Lcell−1 at four‐stacked cells with 16.656 V) under ambient operating conditions, along with low‐temperature performance, mechanical foldability, and nonflammability. [ABSTRACT FROM AUTHOR]

Despite the ever‐growing demand for Li metals as next‐generation Li battery electrodes, little attention has been paid to their oxidation stability, which must be achieved for practical applications. Here, a new class of printable solid electrolyte interphase mimic (pSEI) for antioxidative Li metal electrodes is presented. The pSEI (≈1 µm) is directly fabricated on a thin Li metal electrode (25 µm) by processing solvent‐free, UV polymerization‐assisted printing, exhibiting its manufacturing simplicity and scalability. The pSEI is rationally designed to mimic a typical SEI comprising organic and inorganic components, in which ethoxylated trimethylolpropane triacrylate and diallyldimethylammonium bis(trifluoromethanesulfonyl)imide are introduced as an organic mimic (acting as a moisture‐repellent structural framework) and inorganic mimic (allowing facile Li‐ion transport/high Li+ transference number), respectively. Driven by the chemical/architectural uniqueness, the pSEI enables the thin Li metal electrode to show exceptional antioxidation stability and reliable full cell performance after exposure to humid environments. [ABSTRACT FROM AUTHOR]

Zinc-Ion Batteries: A Chemically Self-Charging Flexible Solid-State Zinc-Ion Battery Based on VO2 Cathode and Polyacrylamide-Chitin Nanofiber Hydrogel Electrolyte (Adv. Keywords: chemical self-charging; PAM-ChNF hydrogel electrolytes; solid-state zinc-ion batteries; VO 2 nanobelts EN chemical self-charging PAM-ChNF hydrogel electrolytes solid-state zinc-ion batteries VO 2 nanobelts 1 1 1 07/10/21 20210708 NES 210708 In article number 2003902, Wangwang Xu, Changtong Mei, Qinglin Wu and co-workers show that the robust tunnel structure of a vanadium dioxide cathode and the network of a polyacrylamide-chitin nanofiber hydrogel electrolyte provide efficient pathways for ion diffusion, leading to superior electrochemical performance of the corresponding solid-state zinc ion batteries (ssZIBs). Chemical self-charging, PAM-ChNF hydrogel electrolytes, solid-state zinc-ion batteries, VO 2 nanobelts. [Extracted from the article]

Solid Electrolyte Interphases: Printable Solid Electrolyte Interphase Mimic for Antioxidative Lithium Metal Electrodes (Adv. Funct. Driven by the unique chemical structure and energy density-favorable dimensional design, the pSEI enables a thin Li metal electrode to show exceptional anti-oxidation stability and reliable full cell performance after exposure to humid environments. Antioxidation, humid environments, lithium metal electrodes, printing, solid electrolyte interphase mimic. [Extracted from the article]

Solid electrolytes are regarded as promising candidates replacing organic liquid electrolyte due to much enhanced safety, which is able to use lithium metal as an anode material for high energy system. Among several solid electroytes, garnet-type solid electrolyte has wide electrochemical window as well as high chemical stability and ionic conductivity at room temperature. However, from an assembled full cell's point of view, high interfacial resistance between electrode and solid electrolyte is a huge obstacle which should be overcome. Herein, we synthesize high ionic conductivy of Gallium-doped garnet-type solid electrolyte (Li6.25Ga0.25La3Zr2O12) having 1.2 mS cm-1 at room temperature and then applied gel polymer electrolyte into cathode by in situ gelation method for a full cell system. The interfacial resistance is reduced by about 260 times and rate capability from 0.05C to 1C was 80%, which is superior to a hybrid of liquid electrolyte and LGLZO cell system. Initial capacity retaines 89% even after 800 cycles at 0.5C. [Display omitted] • We synthesized high ionic conductivity of solid electrolyte having 1.2 mS cm−1. • Gel polymer electrolyte was applied by in situ gelation method for a cell system. • Gel electrolyte guaranteered ionic percolation at Interface. • Initial capacity was reversibly retained 89% even after 800 cycles at 0.5C. • Cell capacity was reversibly kept after 80 °C and 100 °C heat treatment. [ABSTRACT FROM AUTHOR]