Triboelectrification‐Enabled Self‐Charging Lithium‐Ion Batteries

Li‐ion batteries as energy storage devices need to be periodically charged for sustainably powering electronic devices owing to their limited capacities. Here, the feasibility of utilizing Li‐ion batteries as both the energy storage and scavenging units is demonstrated. Flexible Li‐ion batteries fabricated from electrospun LiMn₂O₄ nanowires as cathode and carbon nanowires as anode enable a capacity retention of 90% coulombic efficiency after 50 cycles. Through the coupling between triboelectrification and electrostatic induction, the adjacent electrodes of two Li‐ion batteries can deliver an output peak voltage of about 200 V and an output peak current of about 25 µA under ambient wind‐induced vibrations of a hexafluoropropene–tetrafluoroethylene copolymer film between the two Li‐ion batteries. The self‐charging Li‐ion batteries have been demonstrated to charge themselves up to 3.5 V in about 3 min under wind‐induced mechanical excitations. The advantages of the self‐charging Li‐ion batteries can provide important applications for sustainably powering electronics and self‐powered sensor systems.     

Exploiting Lithium‐Depleted Cathode Materials for Solid‐State Li Metal Batteries

Solid‐state lithium metal batteries (SSLMBs) may become one of the high‐energy density storage devices for the next generation of electric vehicles. High safety and energy density can be achieved by utilizing solid electrolytes and Li metal anodes. Therefore, developing cathode materials which can match with Li metal anode efficiently is indispensable. In SSLMBs, Li metal anodes can afford the majority of active lithium ions, then lithium‐depleted cathode materials can be a competitive candidate to achieve high gravimetric energy density as well as save lithium resources. Li_0.33MnO₂ lithium‐depleted material is chosen, which also has the advantages of low synthesis temperature and low cost (cobalt‐free). Notably, solid‐state electrolyte can greatly alleviate the problem of manganese dissolution in the electrolyte, which is beneficial to improve the cycling stability of the battery. Thus, SSLMBs enable practical applications of lithium‐depleted cathode materials.     

All‐Manganese‐Based Binder‐Free Stretchable Lithium‐Ion Batteries

Advanced electrode materials with bendability and stretchability are critical for the rapid development of fully flexible/stretchable lithium‐ion batteries. However, the sufficiently stretchable lithium‐ion battery is still underdeveloped that is one of the biggest challenges preventing from realizing fully deformable power sources. Here, a low‐temperature hydrothermal synthesis of a cathode material for stretchable lithium‐ion battery is reported by the in situ growth of LiMn₂O₄ (LMO) nanocrystals inside 3D carbon nanotube (CNT) film networks. The LMO/CNT film composite has demonstrated the chemical bonding between the LMO active materials and CNT scaffolds, which is the most important characteristic of the stretchable electrodes. When coupled with a wrinkled MnO_x /CNT film anode, a binder‐free, all‐manganese‐based stretchable full battery cell is assembled which delivers a high average specific capacity of ≈97 mA h g^?1 and stabilizes after over 300 cycles with an enormous strain of 100%. Furthermore, combining with other merits such as low cost, natural abundance, and environmentally friendly, the all‐manganese design is expected to accelerate the practical applications of stretchable lithium‐ion batteries for fully flexible and biomedical electronics.     

MnMoO4 Electrocatalysts for Superior Long‐Life and High‐Rate Lithium‐Oxygen Batteries

Lithium‐oxygen batteries represent a significant scientific challenge for high‐rate and long‐term cycling using oxygen electrodes that contain efficient electrocatalysts. The mixed transition metal oxide catalysts provide the most efficient catalytic activity for partial heterogeneous surface cations with oxygen vacancies as the active phase. They include multiple oxidation states and oxygen vacancies. Here, using a combination of transmission electron microscopy, differential electrochemical mass spectrometry, X‐ray photoelectron spectroscopy, and electrochemical properties to probe the surface of the MnMoO₄ nanowires, it is shown that the intrinsic MnMoO₄ oxygen vacancies on the oxygen electrode are an effective strategy to achieve a high reversibility and high efficiency for lithium‐oxygen (Li‐O₂) batteries. The modified MnMoO₄ nanowires exhibit a highly stable capacity at a fixed capacity of 5000 mA h g_sp^?1 (calculated weight of Super P carbon black) during 50 cycles, a high‐rate capability at a current rate of 3000 mA g_sp^?1 during 70 cycles, and a long‐term reversible capacity during 188 cycles at a fixed capacity of 1000 mA h g_sp^?1. It is demonstrated that this strategy for creating mixed transition metal oxides (e.g., MnMoO₄) may pave the way for the new structural design of electrocatalysts for Li‐O₂ batteries.     

All‐Solid‐State Lithium‐Ion Microbatteries Using Silicon Nanofilm Anodes: High Performance and Memory Effect

All‐solid‐state thin film lithium batteries are promising devices to power the next generations of autonomous microsystems. Nevertheless, some industrial constraints such as the resistance to reflow soldering (260 °C) and to short‐circuiting necessitate the replacement of the lithium anode. In this study, a 2 V lithium‐ion system based on amorphous silicon nanofilm anodes (50–200 nm thick), a LiPON electrolyte, and a new lithiated titanium oxysulfide cathode Li_1.2TiO_0.5S_2.1 is prepared by sputtering. The determination of the electrochemical behavior of each active material and of whole systems with different configurations allows the highlighting of the particular behavior of the Li_xSi electrode and the understanding of its consequences on the performance of Li‐ion cells. Lithium‐ion microbatteries processed with industrial tools and embedded in microelectronic packages exhibit particularly high cycle life (?0.006% cycle^?1), ultrafast charge (80% capacity in 1 min), and tolerate both short‐circuiting and reflow soldering. Moreover, the perfect stability of the system allows the assignment of some modifications of the voltage curve and a slow and reversible capacity fade occurring in specific conditions, to the formation of Li₁₅Si₄ and to the expression of a “memory effect.” These new findings will help to optimize the design of future Li‐ion systems using nanosized silicon anodes.     

Recent Progress on Stability Enhancement for Cathode in Rechargeable Non‐Aqueous Lithium‐Oxygen Battery

The pressing demand on the electronic vehicles with long driving range on a single charge has necessitated the development of next‐generation high‐energy‐density batteries. Non‐aqueous Li‐O₂ batteries have received rapidly growing attention due to their higher theoretical energy densities compared to those of state‐of‐the‐art Li‐ion batteries.To make them practical for commercial applications, many critical issues must be overcome, including low round‐trip efficiency and poor cycling stability, which are intimately connected to the problems resulting from cathode degradation during cycling. Encouragingly, during the past years, much effort has been devoted to enhancing the stability of the cathode using a variety of strategies and these have effectively surmounted the challenges derived from cathode deteriorations,thus endowing Li‐O₂ batteries with significantly improved electrochemical performances. Here, a brief overview of the general development of Li‐O₂ battery is presented. Then, critical issues relevant to the cathode instability are discussed and remarkable achievements in enhancing the cathode stability are highlighted. Finally, perspectives towards the development of next generation highly stable cathode are also discussed.     

Li3N as a Cathode Additive for High‐Energy‐Density Lithium‐Ion Batteries

The formation of a solid‐electrolyte interphase on the anode surface of an Li‐ion battery using an organic liquid electrolyte robs Li⁺ irreversibly form the cathode on the initial charge if the cells are fabricated in the discharged state. In order to increase the cathode capacity, the use of Li₃N as a sacrificial source of Li⁺ on the initial charge has been evaluated chemically and electrochemically as an additive to an LiCoO₂ cathode. Li₃N is shown to be chemically stable in a dry atmosphere as small particles with fresh surfaces and can increase the reversible capacities of a full cell without compromising the rate capability of the cells.     

Effect of Componential Proportion in Bimetallic Electrocatalysts on the Aprotic Lithium‐Oxygen Battery Performance

Rechargeable lithium‐oxygen (Li‐O₂) batteries are one of the most promising technologies for next‐generation energy storage, which is also a critical part of the future renewable energy portfolio; however, its commercialization is still hindered by several challenges. The high charge overpotential, in particular, not only causes problems by increasing the possibility of electrolyte decomposition but also induces a low round‐trip efficiency and coulombic efficiency. Here, by choosing the right component proportion in Pt‐Cu bimetallic electrocatalysts that optimize electrocatalytic activity of electrochemical reactions, especially of oxygen evolution reactions, a superior electrochemical behavior is demonstrated, with a low charge overpotential of 0.2 V and cycleability of 50 discharge/charge cycles before capacity fading. The optimized Pt‐Cu bimetallic electrocatalysts significantly reduce the charge overpotential and furthermore enhance the efficiency, stability, and cycleability of an aprotic Li‐O₂ battery.     

Sulfiphilic Few‐Layered MoSe2 Nanoflakes Decorated rGO as a Highly Efficient Sulfur Host for Lithium‐Sulfur Batteries

Lithium‐sulfur batteries (LSBs) have been regarded as a competitive candidate for next‐generation electrochemical energy‐storage technologies due to their merits in energy density. The sluggish redox kinetics of the electrochemistry and the high solubility of polysulfides during cycling result in insufficient sulfur utilization, severe polarization, and poor cyclic stability. Herein, sulfiphilic few‐layered MoSe₂ nanoflakes decorated rGO (MoSe₂@rGO) hybrid has been synthesized through a facile hydrothermal method and for the first time, is used as a conceptually new‐style sulfur host for LSBs. Specifically, MoSe₂@rGO not only strongly interacts with polysulfides but also dynamically strengthens polysulfide redox reactions. The polarization problem is effectively alleviated by relying on the sulfiphilic MoSe₂. Moreover, MoSe₂@rGO is demonstrated to be beneficial for the fast nucleation and uniform deposition of Li₂S, contributing to the high discharge capacity and good cyclic stability. A high initial capacity of 1608 mAh g^?1 at 0.1 C, a slow decay rate of 0.042% per loop at 0.25 C, and a high reversible capacity of 870 mAh g^?1 with areal sulfur loading of 4.2 mg cm^?2 at 0.3 C are obtained. The concept of introducing sulfiphilic transition‐metal selenides into the LSBs system can stimulate engineering of novel architectures with enhanced properties for various energy‐storage devices.     

Eliminating Transition Metal Migration and Anionic Redox to Understand Voltage Hysteresis of Lithium‐Rich Layered Oxides

Lithium‐rich layered oxides are promising candidate cathode materials for the Li‐ion batteries with energy densities above 300 Wh kg^?1. However, issues such as the voltage hysteresis and decay hinder their commercial applications. Due to the entanglement of the transition metal (TM) migration and the anionic redox upon lithium extraction at high potentials, it is difficult to recognize the origin of these issues in conventional Li‐rich layered oxides. Herein, Li₂MoO₃ is chosen since prototype material to uncover the reason for the voltage hysteresis as the TM migration and anionic redox can be eliminated below 3.6 V versus Li⁺/Li in this material. On the basis of comprehensive investigations by neutron powder diffraction, scanning transmission electron microscopy, synchrotron X‐ray absorption spectroscopy, and density functional theory calculations, it is clarified that the ordering–disordering transformation of the Mo₃O₁₃ clusters induced by the intralayer Mo migration is responsible for the voltage hysteresis in the first cycle; the hysteresis can take place even without the anionic redox or the interlayer Mo migration. A similar suggestion is drawn for its iso‐structured Li₂RuO₃ (C2/c). These findings are useful for understanding of the voltage hysteresis in other complicated Li‐rich layered oxides.     

Optimization of Carbon‐ and Binder‐Free Au Nanoparticle‐Coated Ni Nanowire Electrodes for Lithium‐Oxygen Batteries

A Au nanoparticle‐coated Ni nanowire substrate without binder or carbon is used as the electrode (denoted as the Au/Ni electrode) for Li‐oxygen (Li‐O₂) batteries. A minimal amount of Au nanoparticles with sizes of <30 nm on a Ni nanowire substrate are coated using a simple electrodeposition method to the extent that maximum capacity can be utilized. This optimized, one body, Au/Ni electrode shows high capacities of 921 mAh g^?1_Au, 591 mAh g^?1_Au, and 359 mAh g^?1_Au, which are obtained at currents of 300 mAg^?1_Au, 500 mAg^?1_Au, and 1000 mAg^?1_Au respectively. More importantly, the Au/Ni electrode exhibits excellent cycle stability over 200 cycles.     

Conductive and Catalytic Triple‐Phase Interfaces Enabling Uniform Nucleation in High‐Rate Lithium–Sulfur Batteries

Rechargeable lithium–sulfur batteries have attracted tremendous scientific attention owing to their superior energy density. However, the sulfur electrochemistry involves multielectron redox reactions and complicated phase transformations, while the final morphology of solid‐phase Li₂S precipitates largely dominate the battery's performance. Herein, a triple‐phase interface among electrolyte/CoSe₂/G is proposed to afford strong chemisorption, high electrical conductivity, and superb electrocatalysis of polysulfide redox reactions in a working lithium–sulfur battery. The triple‐phase interface effectively enhances the kinetic behaviors of soluble lithium polysulfides and regulates the uniform nucleation and controllable growth of solid Li₂S precipitates at large current density. Therefore, the cell with the CoSe₂/G functional separator delivers an ultrahigh rate cycle at 6.0 C with an initial capacity of 916 mAh g^?1 and a capacity retention of 459 mAh g^?1 after 500 cycles, and a stable operation of high sulfur loading electrode (2.69–4.35 mg cm^?2). This work opens up a new insight into the energy chemistry at interfaces to rationally regulate the electrochemical redox reactions, and also inspires the exploration of related energy storage and conversion systems based on multielectron redox reactions.     

Exploiting Lithium–Ether Co‐Intercalation in Graphite for High‐Power Lithium‐Ion Batteries

The intercalation of lithium ions into graphite electrode is the key underlying mechanism of modern lithium‐ion batteries. However, co‐intercalation of lithium‐ions and solvent into graphite is considered undesirable because it can trigger the exfoliation of graphene layers and destroy the graphite crystal, resulting in poor cycle life. Here, it is demonstrated that the [lithium–solvent]⁺ intercalation does not necessarily cause exfoliation of the graphite electrode and can be remarkably reversible with appropriate solvent selection. First‐principles calculations suggest that the chemical compatibility of the graphite host and [lithium–solvent]⁺ complex ion strongly affects the reversibility of the co‐intercalation, and comparative experiments confirm this phenomenon. Moreover, it is revealed that [lithium–ether]⁺ co‐intercalation of natural graphite electrode enables much higher power capability than normal lithium intercalation, without the risk of lithium metal plating, with retention of ≈87% of the theoretical capacity at current density of 1 A g^?1. This unusual high rate capability of the co‐intercalation is attributed to the (i) absence of the desolvation step, (ii) negligible formation of the solid–electrolyte interphase on graphite surface, and (iii) fast charge‐transfer kinetics. This work constitutes the first step toward the utilization of fast and reversible [lithium–solvent]⁺ complex ion intercalation chemistry in graphite for rechargeable battery technology.