Cu2O Photocathodes Modified by Graphene Oxide and ZnO Nanoparticles with Improved Photocatalytic Properties.

The modification of photocathodes based on copper(I) oxide (COPC) by coating with ZnO nanoparticles or graphene oxide (GO) with different compositions and morphologies is considered. To cover the catalyst surface with graphene oxide, a technique was proposed via freezing of a sprayed aqueous suspension of graphene oxide followed by sublimation drying under vacuum conditions. This method improves the uniformity of the GO layer in comparison with the traditional drop-casting method and, as a result, improves the photocatalytic properties of the COPC. The influence of the composition and morphology of graphene oxide on the photocatalytic activity and stability of COPC has been established. ZnO nanoparticles and GO particles in contact with copper(I) oxide increase the photocurrent density by the more efficient separation of light-generated charge carriers, providing higher photocathode stability required in photocatalytic water splitting.

Quantifying Degradation Parameters of Single-Crystalline Ni-Rich Cathodes in Lithium-Ion Batteries.

Single-crystal LiNix Coy Mnz O2 (SC-NCM, x+y+z=1) cathodes are renowned for their high structural stability and reduced accumulation of adverse side products during long-term cycling. While advances have been made using SC-NCM cathode materials, careful studies of cathode degradation mechanisms are scarce. Herein, we employed quasi single-crystalline LiNi0.65 Co0.15 Mn0.20 O2 (SC-NCM65) to test the relationship between cycling performance and material degradation for different charge cutoff potentials. The Li/SC-NCM65 cells showed >77 % capacity retention below 4.6 V vs. Li+ /Li after 400 cycles and revealed a significant decay to 56 % for 4.7 V cutoff. We demonstrate that the SC-NCM65 degradation is due to accumulation of rock-salt (NiO) species at the particle surface rather than intragranular cracking or side reactions with the electrolyte. The NiO-type layer formation is also responsible for the strongly increased impedance and transition-metal dissolution. Notably, the capacity loss is found to have a linear relationship with the thickness of the rock-salt surface layer. Density functional theory and COMSOL Multiphysics modeling analysis further indicate that the charge-transfer kinetics is decisive, as the lower lithium diffusivity of the NiO phase hinders charge transport from the surface to the bulk.

Novel electrolyte additive of graphene oxide for prolonging the lifespan of zinc-ion batteries.

Aqueous zinc-ion batteries have attracted the attention of the industry due to their low cost, good environmental friendliness, and competitive gravimetric energy density. However, zinc anodes, similar to lithium, sodium and other alkali metal anodes, are also plagued by dendrite problems. Zinc dendrites can penetrate through polymer membranes, and even glass fiber membranes which seriously hinders the development and application of aqueous zinc-ion batteries. To resolve this issue, certain additives are required. Here we have synthesized an electrochemical graphene oxide with novel electrolyte based on tryptophan, which allows to obtain few-layered sheets with a remarkably uniform morphology, good aqueous solution dispersion, easy preparation and environmental friendliness. We used this electrochemical graphene oxide as an additive to the electrolyte for aqueous zinc-ion batteries. The results of phase-field model combined with experimental characterization revealed that the addition of this material effectively promotes the uniform distribution of the electric field and the Zn-ion concentration field, reduces the nucleation overpotential of Zn metal, and provides a more uniform deposition process on the metal surface and improved cyclability of the aqueous Zn-ion battery. The resultant Zn∣Zn symmetric battery with the electrochemical graphene oxide additive affords a stable Zn anode, which provided service for more than 500 h at 0.2 mA cm-2and even more than 250 h at 1.0 mA cm-2. The Coulombic efficiency (98.7%) of Zn∣Cu half-cells and thus cyclability of aqueous Zn-ion batteries using electrochemical graphene oxide is significantly better compared to the additive-free electrolyte system. Therefore, our approach paves a promising avenue to foster the practical application of aqueous Zn-ion batteries for energy storage.

MRAC Control with Prior Model Knowledge for Asymmetric Damaged Aircraft.

This paper develops a novel state-tracking multivariable model reference adaptive control (MRAC) technique utilizing prior knowledge of plant models to recover control performance of an asymmetric structural damaged aircraft. A modification of linear model representation is given. With prior knowledge on structural damage, a polytope linear parameter varying (LPV) model is derived to cover all concerned damage conditions. An MRAC method is developed for the polytope model, of which the stability and asymptotic error convergence are theoretically proved. The proposed technique reduces the number of parameters to be adapted and thus decreases computational cost and requires less input information. The method is validated by simulations on NASA generic transport model (GTM) with damage.

Covalent Organic Framework with 3D Ordered Channel and Multi-Functional Groups Endows Zn Anode with Superior Stability.

Achieving a highly robust zinc (Zn) metal anode is extremely important for improving the performance of aqueous Zn-ion batteries (AZIBs) for advancing "carbon neutrality" society, which is hampered by the uncontrollable growth of Zn dendrite and severe side reactions including hydrogen evolution reaction, corrosion, and passivation, etc. Herein, an interlayer containing fluorinated zincophilic covalent organic framework with sulfonic acid groups (COF-S-F) is developed on Zn metal (Zn@COF-S-F) as the artificial solid electrolyte interface (SEI). Sulfonic acid group (- SO3H) in COF-S-F can effectively ameliorate the desolvation process of hydrated Zn ions, and the three-dimensional channel with fluoride group (-F) can provide interconnected channels for the favorable transport of Zn ions with ion-confinement effects, endowing Zn@COF-S-F with dendrite-free morphology and suppressed side reactions. Consequently, Zn@COF-S-F symmetric cell can stably cycle for 1,000 h with low average hysteresis voltage (50.5 mV) at the current density of 1.5 mA cm-2. Zn@COF-S-F|MnO2 cell delivers the discharge specific capacity of 206.8 mAh g-1 at the current density of 1.2 A g-1 after 800 cycles with high-capacity retention (87.9%). Enlightening, building artificial SEI on metallic Zn surface with targeted design has been proved as the effective strategy to foster the practical application of high-performance AZIBs.

Relaxation of Stress Propagation in Alloying-Type Sn Anodes for K-Ion Batteries.

Alloying-type metallic tin is perceived as a potential anode material for K-ion batteries owing to its high theoretical capacity and reasonable working potential. However, pure Sn still face intractable issues of inferior K+ storage capability owing to the mechanical degradation of electrode against large volume changes and formation of intermediary insulating phases K4 Sn9 and KSn during alloying reaction. Herein, the TiC/C-carbon nanotubes (CNTs) is prepared as an effective buffer matrix and composited with Sn particles (Sn-TiC/C-CNTs) through the high-energy ball-milling method. Owing to the conductive and rigid properties, the TiC/C-CNTs matrix enhances the electrical conductivity as well as mechanical integrity of Sn in the composite material and thus ultimately contributes to performance supremacy in terms of electrochemical K+ storage properties. During potassiation process, the TiC/C-CNTs matrix not only dissipates the internal stress toward random radial orientations within the Sn particle but also provides electrical pathways for the intermediate insulating phases; this tends to reduce microcracking and prevent considerable electrode degradation.

Role of Interfacial Defects on Electro-Chemo-Mechanical Failure of Solid-State Electrolyte.

High-stress field generated by electroplating of lithium (Li) in pre-existing defects is the main reason for mechanical failure of solid-state electrolyte because it drives crack propagation in electrolyte, followed by Li filament growth inside and even internal short-circuit if the filament reaches another electrode. To understand the role of interfacial defects on mechanical failure of solid-state electrolyte, an electro-chemo-mechanical model is built to visualize distribution of stress, relative damage, and crack formation during electrochemical plating of Li in defects. Geometry of interfacial defect is found as dominating factor for concentration of local stress field while semi-sphere defect delivers less accumulation of damage at initial stage and the longest failure time for disintegration of electrolyte. Aspect ratio, as a key geometric parameter of defect, is investigated to reveal its impact on failure of electrolyte. Pyramidic defect with low aspect ratio of 0.2-0.5 shows branched region of damage near interface, probably causing surface pulverization of solid-state electrolyte, whereas high aspect ratio over 3.0 will trigger accumulation of damage in bulk electrolyte. The correction between interfacial defect and electro-chemo-mechanical failure of solid-state electrolyte is expected to provide insightful guidelines for interface design in high-power-density solid-state Li metal batteries.

Regulating the Solvation Structure of Electrolyte via Dual-Salt Combination for Stable Potassium Metal Batteries.

Batteries using potassium metal (K-metal) anode are considered a new type of low-cost and high-energy storage device. However, the thermodynamic instability of the K-metal anode in organic electrolyte solutions causes uncontrolled dendritic growth and parasitic reactions, leading to rapid capacity loss and low Coulombic efficiency of K-metal batteries. Herein, an advanced electrolyte comprising 1 M potassium bis(fluorosulfonyl)imide (KFSI) + 0.05 M potassium hexafluorophosphate (KPF6 ) dissolved in dimethoxyethane (DME) is introduced as a simple and effective strategy of regulated solvation chemistry, showing an enhanced interfacial stability of the K-metal anode. Incorporating 0.05 M KPF6 into the 1 M KFSI in DME electrolyte solution decreases the number of solvent molecules surrounding the K ion and simultaneously leads to facile K+ de-solvation. During the electrodeposition process, these unique features can lower the exchange current density between the electrolyte and K-metal anode, thereby improving the uniformity of K electrodeposition, as well as potentially suppressing dendritic growth. Even under a high current density of 4 mA cm-2 , the K-metal anode in 0.05 M KPF6 -containing electrolyte ensures high areal capacity and an unprecedented lifespan with stable Coulombic efficiency in both symmetrical half-cells and full-cells employing a sulfurized polyacrylonitrile cathode.

Electro-Chemo-Mechanical Failure of Solid Electrolytes Induced by Growth of Internal Lithium Filaments.

Growth of lithium (Li) filaments within solid electrolytes, leading to mechanical degradation of the electrolyte and even short circuit of the cell under high current density, is a great barrier to commercialization of solid-state Li-metal batteries. Understanding of this electro-chemo-mechanical phenomenon is hindered by the challenge of tracking local fields inside the solid electrolyte. Here, a multiphysics simulation aiming to investigate evolution of the mechanical failure of the solid electrolyte induced by the internal growth of Li is reported. Visualization of local stress, damage, and crack propagation within the solid electrolyte enables examination of factors dominating the degradation process, including the geometry, number, and size of Li filaments and voids in the electrolyte. Relative damage induced by locally high stress is found to preferentially occur in the region of the electrolyte/Li interface having great fluctuations. A high number density of Li filaments or voids triggers integration of damage and crack networks by enhanced propagation. This model is built on coupling of mechanical and electrochemical processes for internal plating of Li, revealing evolution of multiphysical fields that can barely be captured by the state-of-the-art experimental techniques. Understanding mechanical degradation of solid electrolytes with the presence of Li filaments paves the way to design advanced solid electrolytes for future solid-state Li-metal batteries.

Two Birds with One Stone: Using Indium Oxide Surficial Modification to Tune Inner Helmholtz Plane and Regulate Nucleation for Dendrite-free Lithium Anode.

Lithium metal has been considered as the most promising anode material due to its distinguished specific capacity of 3860 mAh g-1 and the lowest reduction potential of -3.04 V versus the Standard Hydrogen Electrode. However, the practicalization of Li-metal batteries (LMBs) is still challenged by the dendritic growth of Li during cycling, which is governed by the surface properties of the electrodepositing substrate. Herein, a surface modification with indium oxide on the copper current collector via magnetron sputtering, which can be spontaneously lithiated to form a composite of lithium indium oxide and Li-In alloy, is proposed. Thus, the growth of Li dendrites is effectively suppressed via regulating the inner Helmholtz plane modified with LiInO2 to foster the desolvation of Li-ion and induce the nucleation of Li-metal in two-dimensions through electro-crystallization with Li-In alloy. Using the In2 O3 modification, the Li-metal anode exhibits outstanding cyclic stability, and LMBs with lithium cobalt oxide cathode present excellent capacity retention (above 80% over 600 cycles). Enlightening, the scalable magnetron sputtering method reported here paves a novel way to accelerate the practical application of the Li anode in LMBs to pursue higher energy density.

Insight into the Critical Role of Exchange Current Density on Electrodeposition Behavior of Lithium Metal.

Due to an ultrahigh theoretical specific capacity of 3860 mAh g-1, lithium (Li) is regarded as the ultimate anode for high-energy-density batteries. However, the practical application of Li metal anode is hindered by safety concerns and low Coulombic efficiency both of which are resulted fromunavoidable dendrite growth during electrodeposition. This study focuses on a critical parameter for electrodeposition, the exchange current density, which has attracted only little attention in research on Li metal batteries. A phase-field model is presented to show the effect of exchange current density on electrodeposition behavior of Li. The results show that a uniform distribution of cathodic current density, hence uniform electrodeposition, on electrode is obtained with lower exchange current density. Furthermore, it is demonstrated that lower exchange current density contributes to form a larger critical radius of nucleation in the initial electrocrystallization that results in a dense deposition of Li, which is a foundation for improved Coulombic efficiency and dendrite-free morphology. The findings not only pave the way to practical rechargeable Li metal batteries but can also be translated to the design of stable metal anodes, e.g., for sodium (Na), magnesium (Mg), and zinc (Zn) batteries.

Crumpled Nitrogen-Doped Graphene-Wrapped Phosphorus Composite as a Promising Anode for Lithium-Ion Batteries.

Red phosphorus (P) has recently gained wide attention because of the high theoretical capacity of 2596 mA h/g, which has been regarded as promising anode material for lithium-ion batteries (LIBs). However, the actual application of red P in LIBs is hampered by the huge expansion of volume and low electronic conductivity. Herein, we design a kind of red phosphorus/crumpled nitrogen-doped graphene (P/CNG) nanocomposites with high capacity density and great rate performance as anode material for LIBs. This anode material was rationally fabricated through the scalable ball-milling method. The nanocomposite structure of P/CNG improves the electron conductivity and alleviates volume change of raw red P because of the three-dimension (3D) framework, massive defects and active sites of CNG sheets. As expected, the P/CNG composite shows excellent electrochemical performances, including high capacity (2522.6 mA h/g at 130 mA/g), remarkable rate capability (1340.5 mA h/g at 3900 mA/g), and great cyclability (1470.1 mA h/g at 1300 mA/g for 300 cycles). This work may provide a broad prospect for a great rate performance of P-based anode material for LIBs.