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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.  相似文献   

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Hybrid organic/inorganic perovskite solar cells are invigorating the photovoltaic community due to their remarkable properties and efficiency. However, many perovskite solar cells show an undesirable current–voltage (IV) hysteresis in their forward and reverse voltage scans, working to the detriment of device characterization and performance. This hysteresis likely arises from slow ion migration in the bulk perovskite active layer to interfaces which may induce charge trapping. It is shown that interfacial chemistry between the perovskite and charge transport layer plays a critical role in ion transport and IV hysteresis in perovskite‐based devices. Specifically, phenylene vinylene polymers containing cationic, zwitterionic, or anionic pendent groups are utilized to fabricate charge transport layers with specific interfacial ionic functionalities. The interfacial‐adsorbing boundary induced by the zwitterionic polymer in contact with the perovskite increases the local ion concentration, which is responsible for the observed IV hysteresis. Moreover, the ion adsorbing properties of this interface are exploited for perovskite‐based memristors. This fundamental study of IV hysteresis in perovskite‐based devices introduces a new mechanism for inducing memristor behavior by interfacial ion adsorption.  相似文献   

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The combined effect of lithium‐ion diffusion, potential‐concentration gradient, and stress plays a critical role in the rate capability and cycle life of Si‐based anodes of lithium‐ion batteries. In this work, Si nanofilm anodes are shown to exhibit an asymmetric rate performance: around 72% of the total available capacity can be delivered during de‐lithiation under a high current density of 420 A g‐1 (100C where C is the charge‐rate) in 22 s; in striking contrast, only 1% capacity can be delivered during lithiation. A mathematical model of single‐ion diffusion is established to elucidate the asymmetric rate performance, which can be mainly attributed to the potential‐concentration profile associated with the active material and the ohmic voltage shift under high currents; the difference in chemical diffusion coefficients during lithiation and de‐lithiation also plays a role. This clarifies that the charge and discharge rates of lithium‐ion‐battery electrodes should be evaluated separately due to the asymmetric effect in the electrochemical system.  相似文献   

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The development of alternative anode materials with higher volumetric and gravimetric capacity allowing for fast delithiation and, even more important, lithiation is crucial for next‐generation lithium‐ion batteries. Herein, the development of a completely new active material is reported, which follows an insertion‐type lithiation mechanism, metal‐doped CeO2. Remarkably, the introduction of carefully selected dopants, herein exemplified for iron, results in an increase of the achievable capacity by more than 200%, originating from the reduction of the dopant to the metallic state and additional space for the lithium ion insertion due to a significant off‐centering of the dopant atoms in the crystal structure, away from the original Ce site. In addition to the outstanding performance of such materials in high‐power lithium‐ion full‐cells, the selective reduction of the iron dopant under preservation of the crystal structure of the host material is expected to open up a new field of research.  相似文献   

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Toward improved understanding and control of the interactions of Li metal anodes with their processing environments, a combined X‐ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and density functional theory (DFT) characterization of the effects that O2, CO2, and N2, the main gases in dry‐atmosphere battery production lines, induced on a reproducibly clean Li surface at room temperature is presented here. XPS measurements demonstrate that O2 is ten times more effective than CO2 at oxidizing metal Li. Notably, pure N2 is shown to not dissociate on clean metal Li. UPS results indicate that decomposition of O2 (CO2) reduces the work function of the Li surface by almost 1 eV, therefore increasing the reduction energy drive for the treated substrate by comparison to bare metallic Li. DFT simulations semiquantitatively account for these results on the basis of the effects of dissociative gas adsorption on the surface dipole density of the Li surface.  相似文献   

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Despite the wide application of lithium‐ion batteries in portable electronic devices and electric vehicles, the demand for new battery systems with the merits of high voltage, environmental friendliness, safety, and cost efficiency is still quite urgent. This perspective focuses on dual‐ion batteries (DIBs), in which, both the cations and anions are involved in the battery reaction. An anion's intercalation/deintercalation process on the cathode side allows the DIBs to operate at high voltages, which is favorable for enhanced energy density. However, electrolytes with a wide electrochemical window and suitable anion‐intercalation materials with highly reversible capacities should be developed. The progress of research into stable organic electrolytes, ionic liquids, and their effects on the electrochemical performances of DIBs are first discussed. Thereafter, the anion‐host materials including graphitic materials, organic materials, and their working mechanisms are discussed in detail. In addition, recently emerging DIB systems with high‐capacity anodes, or sodium‐, potassium‐ion involved battery reactions are also reviewed. The authors' recent work, demonstrating a generalized DIB construction using metal foil as both current collector and alloying anode material, which is successfully extended into lithium‐, sodium‐, and potassium‐based DIBs, is also discussed.  相似文献   

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The growing demand for bioelectronics has generated widespread interest in implantable energy storage. These implantable bioelectronic devices, powered by a complementary battery/capacitor system, have faced difficulty in miniaturization without compromising their functionality. This paper reports on the development of a promising high‐rate cathode material for implantable power sources based on Li‐exchanged Na1.5VOPO4F0.5 anchored on reduced graphene oxide (LNVOPF‐rGO). LNVOPF is unique in that it offers dual charge storage mechanisms, which enable it to exhibit mixed battery/capacitor electrochemical behavior. In this work, electrochemical Li‐ion exchange of the LNVOPF structure is characterized by operando X‐ray diffraction. Through designed nanostructuring, the charge storage kinetics of LNVOPF are improved, as reflected in the stored capacity of 107 mAh g?1 at 20C. A practical full cell device composed of LNVOPF and T‐Nb2O5, which serves as a pseudocapacitive anode, is fabricated to demonstrate not only high energy/power density storage (100 Wh kg?1 at 4000 W kg?1) but also reliable pulse capability and biocompatibility, a desirable combination for applications in biostimulating devices. This work underscores the potential of miniaturizing biomedical devices by replacing a conventional battery/capacitor couple with a single power source.  相似文献   

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While lithium ion batteries with electrodes based on intercalation compounds have dominated the portable energy storage market for decades, the energy density of these materials is fundamentally limited. Today, rapidly growing demand for this type of energy storage is driving research into materials that utilize alternative reaction mechanisms to enable higher energy densities. Transition metal compounds are one such class of materials, with storage enabled by “conversion” reactions, where the material is converted to new compound upon lithiation. MoS2 is one example of this type of material that has generated a large amount of interest recently due to its high theoretical lithium storage capacity compared to graphite. Here, cryogenic scanning transmission electron microscopy techniques are used to reveal the atomic‐scale processes that occur during reaction of a model monolayer MoS2 system by enabling the unaltered atomic structure to be determined at various levels of lithiation. It is revealed that monolayer MoS2 can undergo a conversion reaction even with no substrate, and that the resulting particles are smaller than those that form in bulk MoS2, likely due to the more limited 2D diffusion. Additionally, while bilayer MoS2 undergoes intercalation with a corresponding phase transition before conversion, monolayer MoS2 does not.  相似文献   

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Understanding and optimizing the temperature effects of Li‐ion diffusion by analyzing crystal structures of layered Li(NixMnyCoz)O2 (NMC) (x + y + z = 1) materials is important to develop advanced rechargeable Li‐ion batteries (LIBs) for multi‐temperature applications with high power density. Combined with experiments and ab initio calculations, the layer distances and kinetics of Li‐ion diffusion of LiNixMnyCozO2 (NMC) materials in different states of Li‐ion de‐intercalation and temperatures are investigated systematically. An improved model is also developed to reduce the system error of the “Galvanostatic Intermittent Titration Technique” with a correction of NMC particle size distribution. The Li‐ion diffusion coefficients of all the NMC materials are measured from ?25 to 50 °C. It is found that the Li‐ion diffusion coefficient of LiNi0.6Mn0.2Co0.2O2 is the largest with the minimum temperature effect. Ab initio calculations and XRD measurements indicate that the larger Li slab space benefits to Li‐ion diffusion with minimum temperature effect in layered NMC materials.  相似文献   

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Sluggish solid‐phase diffusion has been an essential issue in developing intercalation electrode materials using multivalent ions. Compared to monovalent Li ions, the diffusion of multivalent ions is still not well understood. Here, combining first‐principles calculations with electrochemical experiments, it is shown that the diffusion of divalent Mg ions is significantly facilitated in Li–Mg dual‐ion systems, and the activation energy is remarkably reduced by the concerted interactions of the preceding Li ions and following Mg ions. Thus, making dual‐ion systems is a promising way to construct high‐energy‐density, rechargeable batteries with multivalent ions. This work will provide a new perspective on solid‐phase diffusion that is typically a rate‐controlling process in battery systems and fuel cell devices.  相似文献   

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While the practical application of electrode materials depends intensively on the Li+ ion storage mechanisms correlating ultimately with the coulombic efficiency, reversible capacity, and morphology variation of electrode material upon cycling, only intercalation‐type electrode materials have proven viable for commercialization up to now. This paper reviews the promising anode materials of metal vanadates (MxVyOz, M = Co, Cu, Mn, Fe, Zn, Ni, Li) that have high capacity, low cost, and abundant resource, and also discusses the related Li+ ion storage mechanism. It is concluded that most of these (MxVyOz, M = Co, Cu, Mn, Fe, Zn, Ni) exhibit irreversible redox reactions upon lithiation/delithiation accompanied by large volume expansion, which is not favorable for industrial applications. In particular, Li3VO4 with specific intercalation Li+ ion storage mechanism and compatible merits of safety and energy density exhibits great potential for practical application. This review systematically summarizes the latest progress in Li3VO4 research, including the representative fabrication approaches for advanced morphology and state‐of‐the‐art technologies to boost performance and the morphology variation associated with Li+ ion storage mechanisms. Furthermore, an outlook on where breakthroughs for Li3VO4 may be most likely achieved will be provided.  相似文献   

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