Project description:All-solid-state batteries have recently gained considerable attention due to their potential improvements in safety, energy density, and cycle-life compared to conventional liquid electrolyte batteries. Sodium all-solid-state batteries also offer the potential to eliminate costly materials containing lithium, nickel, and cobalt, making them ideal for emerging grid energy storage applications. However, significant work is required to understand the persisting limitations and long-term cyclability of Na all-solid-state-based batteries. In this work, we demonstrate the importance of careful solid electrolyte selection for use against an alloy anode in Na all-solid-state batteries. Three emerging solid electrolyte material classes were chosen for this study: the chloride Na2.25Y0.25Zr0.75Cl6, sulfide Na3PS4, and borohydride Na2(B10H10)0.5(B12H12)0.5. Focused ion beam scanning electron microscopy (FIB-SEM) imaging, X-ray photoelectron spectroscopy (XPS), and electrochemical impedance spectroscopy (EIS) were utilized to characterize the evolution of the anode-electrolyte interface upon electrochemical cycling. The obtained results revealed that the interface stability is determined by both the intrinsic electrochemical stability of the solid electrolyte and the passivating properties of the formed interfacial products. With appropriate material selection for stability at the respective anode and cathode interfaces, stable cycling performance can be achieved for Na all-solid-state batteries.
Project description:We have developed a proof of concept electrode design to covalently graft poly(methyl methacrylate) brushes directly to silicon thin film electrodes via surface-initiated atom transfer radical polymerization. This polymer layer acts as a stable artificial solid electrolyte interface that enables surface passivation despite large volume changes during cycling. Thin polymer layers (75?nm) improve average first cycle coulombic efficiency from 62.4% in bare silicon electrodes to 76.3%. Average first cycle reversible capacity was improved from 3157 to 3935 mAh g-1, and average irreversible capacity was reduced from 2011 to 1020 mAh g-1. Electrochemical impedance spectroscopy performed on silicon electrodes showed that resistance from solid electrolyte interface formation increased from 79 to 1508 ? in untreated silicon thin films over 26 cycles, while resistance growth was lower - from 98 to 498 ? - in silicon films functionalized with PMMA brushes. The lower increase suggests enhanced surface passivation and lower electrolyte degradation. This work provides a pathway to develop artificial solid electrolyte interfaces synthesized under controlled reaction conditions.
Project description:The ripple effect induced by uncontrollable Zn deposition is considered as the Achilles heel for developing high-performance aqueous Zn-ion batteries. For this problem, this work reports a design concept of 3D artificial array interface engineering to achieve volume stress elimination, preferred orientation growth and dendrite-free stable Zn metal anode. The mechanism of MXene array interface on modulating the growth kinetics and deposition behavior of Zn atoms were firstly disclosed on the multi-scale level, including the in-situ optical microscopy and transient simulation at the mesoscopic scale, in-situ Raman spectroscopy and in-situ X-ray diffraction at the microscopic scale, as well as density functional theory calculation at the atomic scale. As indicated by the electrochemical performance tests, such engineered electrode exhibits the comprehensive enhancements not only in the resistance of corrosion and hydrogen evolution, but also the rate capability and cyclic stability. High-rate performance (20 mA cm-2) and durable cycle lifespan (1350 h at 0.5 mA cm-2, 1500 h at 1 mA cm-2 and 800 h at 5 mA cm-2) can be realized. Moreover, the improvement of rate capability (214.1 mAh g-1 obtained at 10 A g-1) and cyclic stability also can be demonstrated in the case of 3D MXene array@Zn/VO2 battery. Beyond the previous 2D closed interface engineering, this research offers a unique 3D open array interface engineering to stabilize Zn metal anode, the controllable Zn deposition mechanism revealed is also expected to deepen the fundamental of rechargeable batteries including but not limited to aqueous Zn metal batteries.
Project description:Potassium (K) metal is a promising alkali metal anode for its high abundance. However, dendrite on K anode is a serious problem which is even worse than Li. Artificial SEI (ASEI) is one of effective routes for suppressing dendrite. However, there are still some issues of the ASEI made by the traditional methods, e.g. weak adhesion, insufficient/uneven reaction, which deeply affects the ionic diffusion kinetics and the effect of inhibiting dendrites. Herein, through a unique self-catalysis tribo-electrochemistry reaction, a continuous and compact protective layer is successfully constructed on K metal anode in seconds. Such a continuous and compact protective layer can not only improve the K+ diffusion kinetics, but also strongly suppress K dendrite formation by its hard mechanical properties derived from rigid carbon system, as well as the improved K+ conductivity and lowered electronic conductivity from the amorphous KF. As a result, the potassium symmetric cells exhibit stable cycles last more than 1000 h, which is almost 500 times that of pristine K.
Project description:Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet-type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10-3 to 10-4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.
Project description:All-solid-state sodium batteries have great potential for large-scale energy storage applications. However, constructing a compatible Na anode/solid-state electrolyte (SSE) interface is still challenging because most SSEs are unstable toward Na metal. A succinonitrile (SN) SSE shows high room-temperature ionic conductivity (10-3 S cm-1) but easily deteriorates if in contact with Na metal, leading to continuously increased interfacial resistance. Here we present an extremely simple approach to introduce a compact NaF-rich interphase on a Na surface via chemical reactions between fluoroethylene carbonate-Na+ and Na metal, resulting in a compatible Na anode/SN-based electrolyte interface. The in situ formed NaF-rich interphase can not only prevent side reactions between the SN-based electrolyte and Na anode but also regulate the uniform deposition of dendrite-free Na. As a result, the symmetric cells show a low overpotential of 150 mV after cycling for 4000 h. Furthermore, all-solid-state Na-CO2 batteries (4Na + 3CO2 ↔ 2Na2CO3 + C) with the compatible interface can run for 50 cycles with a small overpotential increase of 0.33 V. This work provides a promising method to build a stable interface that enables the use of an SSE which is unstable toward Na in Na metal batteries.
Project description:The Zn metal anode experiences dendritic growth and side reactions in aqueous zinc batteries. The regulation of the interface environment would provide efficient modification without largely affecting the aqueous nature of bulk electrolytes. Herein, we show that the ethylene carbonate (EC) additive is able to adsorb on the Zn surface from the ZnSO4 electrolyte. Together with the higher dielectric constant of EC than water, Zn2+ preferentially forms EC-rich solvation structures at the interface even with a low overall EC content of 4%. An inorganic-organic solid-electrolyte interface (SEI) is also generated. Thanks to the increased energy levels of the lowest unoccupied molecular orbital of EC-rich solvation structures and the stable SEI, side reactions are suppressed and the Zn2+ transference number increases to allow uniform Zn growth. As a result, the cycle life of Zn stripping/plating in symmetric Zn cells extends from 108 h to 1800 h after the addition of 4% EC. Stable cycling for 180 h is realized with 35% depth of discharge in the 4% EC electrolyte, superior to the initial cell failure with EC-free electrolyte. The capacity retention of the Zn//V6O13·H2O full cell with N/P = 1.3 also increases from 51.1% to 80.5% after 500 cycles with the help of EC.
Project description:The concept 'the interface is the device' is embodied in a wide variety of interfacial electronic phenomena and associated applications in oxide materials, ranging from catalysts and clean energy systems to emerging multifunctional devices. Many device properties are defined by the band alignment, which is often influenced by interface dipoles. On the other hand, the ability to purposefully create and control interface dipoles is a relatively unexplored degree of freedom for perovskite oxides, which should be particularly effective for such ionic materials. Here we demonstrate tuning the band alignment in perovskite metal-semiconductor heterojunctions over a broad range of 1.7 eV. This is achieved by the insertion of positive or negative charges at the interface, and the resultant dipole formed by the induced screening charge. This approach can be broadly used in applications where decoupling the band alignment from the constituent work functions and electron affinities can enhance device functionality.
Project description:Aqueous zinc ion batteries (AZIBs) are promising electrochemical energy storage devices due to their high theoretical specific capacity, low cost, and environmental friendliness. However, uncontrolled dendrite growth poses a serious threat to the reversibility of Zn plating/stripping, which impacts the stability of batteries. Therefore, controlling the disordered dendrite growth remains a considerable challenge in the development of AZIBs. Herein, a ZIF-8-derived ZnO/C/N composite (ZOCC) interface layer was constructed on the surface of the Zn anode. The homogeneous distribution of zincophilic ZnO and the N element in the ZOCC facilitates directional Zn deposition on the (002) crystal plane. Moreover, the conductive skeleton with a microporous structure accelerates Zn2+ transport kinetics, resulting in a reduction in polarization. As a result, the stability and electrochemical properties of AZIBs are improved. Specifically, the ZOCC@Zn symmetric cell sustains over 1150 h at 0.5 mA cm-2 with 0.25 mA h cm-2, while the ZOCC@Zn half-cell achieves an outstanding Coulombic efficiency of 99.79% over 2000 cycles. This work provides a simple and effective strategy for improving the lifespan of AZIBs.
Project description:Progress towards the integration of technology into living organisms requires power devices that are biocompatible and mechanically flexible. Aqueous zinc ion batteries that use hydrogel biomaterials as electrolytes have emerged as a potential solution that operates within biological constraints; however, most of these batteries feature inferior electrochemical properties. Here, we propose a biocompatible hydrogel electrolyte by utilising hyaluronic acid, which contains ample hydrophilic functional groups. The gel-based electrolyte offers excellent anti-corrosion ability for zinc anodes and regulates zinc nucleation/growth. Also, the gel electrolyte provides high battery performance, including a 99.71% Coulombic efficiency, over 5500 hours of long-term stability, improved cycle life of 250 hours under a high zinc utilization rate of 80%, and high biocompatibility. Importantly, the Zn//LiMn2O4 pouch cell exhibits 82% capacity retention after 1000 cycles at 3 C. This work presents a promising gel chemistry that controls zinc behaviour, offering great potential in biocompatible energy-related applications and beyond.