Interface Design Enabling Stable Polymer/Thiophosphate Electrolyte Separators for Dendrite-Free Lithium Metal Batteries.

Organic/inorganic interfaces greatly affect Li+ transport in composite solid electrolytes (SEs), while SE/electrode interfacial stability plays a critical role in the cycling performance of solid-state batteries (SSBs). However, incomplete understanding of interfacial (in)stability hinders the practical application of composite SEs in SSBs. Herein, chemical degradation between Li6 PS5 Cl (LPSCl) and poly(ethylene glycol) (PEG) is revealed. The high polarity of PEG changes the electronic state and structural bonding of the PS4 3- tetrahedra, thus triggering a series of side reactions. A substituted terminal group of PEG not only stabilizes the inner interfaces but also extends the electrochemical window of the composite SE. Moreover, a LiF-rich layer can effectively prevent side reactions at the Li/SE interface. The results provide insights into the chemical stability of polymer/sulfide composites and demonstrate an interface design to achieve dendrite-free lithium metal batteries.

Impact of the Chlorination of Lithium Argyrodites on the Electrolyte/Cathode Interface in Solid-State Batteries.

Lithium argyrodite-type electrolytes are regarded as promising electrolytes due to their high ionic conductivity and good processability. Chemical modifications to increase ionic conductivity have already been demonstrated, but the influence of these modifications on interfacial stability remains so far unknown. In this work, we study Li6 PS5 Cl and Li5.5 PS4.5 Cl1.5 to investigate the influence of halogenation on the electrochemical decomposition of the solid electrolyte and the chemical degradation mechanism at the cathode interface in depth. Electrochemical measurements, gas analysis and time-of-flight secondary ion mass spectrometry indicate that the Li5.5 PS4.5 Cl1.5 shows pronounced electrochemical decomposition at lower potentials. The chemical reaction at higher voltages leads to more gaseous degradation products, but a lower fraction of solid oxygenated phosphorous and sulfur species. This in turn leads to a decreased interfacial resistance and thus a higher cell performance.

A mechanistic investigation of the Li10GeP2S12|LiNi1-x-yCoxMnyO2 interface stability in all-solid-state lithium batteries.

All-solid-state batteries are intensively investigated, although their performance is not yet satisfactory for large-scale applications. In this context, the combination of Li10GeP2S12 solid electrolyte and LiNi1-x-yCoxMnyO2 positive electrode active materials is considered promising despite the yet unsatisfactory battery performance induced by the thermodynamically unstable electrode|electrolyte interface. Here, we report electrochemical and spectrometric studies to monitor the interface evolution during cycling and understand the reactivity and degradation kinetics. We found that the Wagner-type model for diffusion-controlled reactions describes the degradation kinetics very well, suggesting that electronic transport limits the growth of the degradation layer formed at the electrode|electrolyte interface. Furthermore, we demonstrate that the rate of interfacial degradation increases with the state of charge and the presence of two oxidation mechanisms at medium (3.7 V vs. Li+/Li < E < 4.2 V vs. Li+/Li) and high (E ≥ 4.2 V vs. Li+/Li) potentials. A high state of charge (>80%) triggers the structural instability and oxygen release at the positive electrode and leads to more severe degradation.

Interfacial Evolution of Lithium Dendrites and Their Solid Electrolyte Interphase Shells of Quasi-Solid-State Lithium-Metal Batteries.

Unstable electrode/solid-state electrolyte interfaces and internal lithium dendrite penetration hamper the applications of solid-state lithium-metal batteries (SSLMBs), and the underlying mechanisms are not well understood. Herein, in situ optical microscopy provides insights into the lithium plating/stripping processes in a gel polymer electrolyte and reveals its dynamic evolution. Spherical lithium deposits evolve into moss-like and branch-shaped lithium dendrites with increasing current densities. Remarkably, the on-site-formed solid electrolyte interphase (SEI) shell on the lithium dendrite is distinctly captured after lithium stripping. Inducing an on-site-formed SEI shell with an enhanced modulus to wrap the lithium precipitation densely and uniformly can regulate dendrite-free behaviors. An in-depth understanding of lithium dendrite evolution and its functional SEI shell will aid in the optimization of SSLMBs.

Tuning wettability of molten lithium via a chemical strategy for lithium metal anodes.

Metallic lithium affords the highest theoretical capacity and lowest electrochemical potential and is viewed as a leading contender as an anode for high-energy-density rechargeable batteries. However, the poor wettability of molten lithium does not allow it to spread across the surface of lithiophobic substrates, hindering the production and application of this anode. Here we report a general chemical strategy to overcome this dilemma by reacting molten lithium with functional organic coatings or elemental additives. The Gibbs formation energy and newly formed chemical bonds are found to be the governing factor for the wetting behavior. As a result of the improved wettability, a series of ultrathin lithium of 10-20 µm thick is obtained together with impressive electrochemical performance in lithium metal batteries. These findings provide an overall guide for tuning the wettability of molten lithium and offer an affordable strategy for the large-scale production of ultrathin lithium, and could be further extended to other alkali metals, such as sodium and potassium.

Engineering Janus Interfaces of Ceramic Electrolyte via Distinct Functional Polymers for Stable High-Voltage Li-Metal Batteries.

The fast-ionic-conducting ceramic electrolyte is promising for next-generation high-energy-density Li-metal batteries, yet its application suffers from the high interfacial resistance and poor interfacial stability. In this study, the compatible solid-state electrolyte was designed by coating Li1.4Al0.4Ti1.6(PO4)3 (LATP) with polyacrylonitrile (PAN) and polyethylene oxide (PEO) oppositely to satisfy deliberately the disparate interface demands. Wherein, the upper PAN constructs soft-contact with LiNi0.6Mn0.2Co0.2O2, and the lower PEO protects LATP from being reduced, guaranteeing high-voltage tolerance and improved stability toward Li-metal anode performed in one ceramic. Moreover, the core function of LATP is amplified to guide homogeneous ions distribution and hence suppresses the formation of a space-charge layer across interfaces, uncovered by the COMSOL Multiphysics concentration field simulation. Thus, such a bifunctional modified ceramic electrolyte integrates the respective superiority to render Li-metal batteries with excellent cycling stability (89% after 120 cycles), high Coulombic efficiency (exceeding 99.5% per cycle), and a dendrite-free Li anode at 60 °C, which represents an overall design of ceramic interface engineering for future practical solid battery systems.

Nitriding-Interface-Regulated Lithium Plating Enables Flame-Retardant Electrolytes for High-Voltage Lithium Metal Batteries.

Safety concerns are impeding the applications of lithium metal batteries. Flame-retardant electrolytes, such as organic phosphates electrolytes (OPEs), could intrinsically eliminate fire hazards and improve battery safety. However, OPEs show poor compatibility with Li metal though the exact reason has yet to be identified. Here, the lithium plating process in OPEs and Li/OPEs interface chemistry were investigated through ex situ and in situ techniques, and the cause for this incompatibility was revealed to be the highly resistive and inhomogeneous interfaces. Further, a nitriding interface strategy was proposed to ameliorate this issue and a Li metal anode with an improved Li cycling stability (300 h) and dendrite-free morphology is achieved. Meanwhile, the full batteries coupled with nickel-rich cathodes, such as LiNi0.8 Co0.1 Mn0.1 O2 , show excellent cycling stability and outstanding safety (passed the nail penetration test). This successful nitriding-interface strategy paves a new way to handle the incompatibility between electrode and electrolyte.

Guiding Uniform Li Plating/Stripping through Lithium-Aluminum Alloying Medium for Long-Life Li Metal Batteries.

The uncontrolled growth of Li dendrites upon cycling might result in low coulombic efficiency and severe safety hazards. Herein, a lithiophilic binary lithium-aluminum alloy layer, which was generated through an in situ electrochemical process, was utilized to guide the uniform metallic Li nucleation and growth, free from the formation of dendrites. Moreover, the formed LiAl alloy layer can function as a Li reservoir to compensate the irreversible Li loss, enabling long-term stability. The protected Li electrode shows superior cycling over 1700 h in a Li|Li symmetric cell.

Constructing a Stable Lithium Metal-Gel Electrolyte Interface for Quasi-Solid-State Lithium Batteries.

Interfacial problems, including interfacial stability and contact issues, severely plague the practical application of Li metal anodes. Here we report an interfacial regulation strategy that stabilizes the Li metal-gel electrolyte interface through in situ constructing a stable solid electrolyte interphase (SEI) layer. By stabilizing the interface of Li metal anodes, the gel electrolyte enables dendrite-free morphology and high plating/stripping efficiency. A systematic analysis further confirms that the formed SEI layer is responsible for homogeneous deposition and stable cycling performance. Benefiting from the interfacial stability between electrodes and electrolytes, the lifespan of Li metal batteries is extended.

Designing High-Performance Composite Electrodes for Vanadium Redox Flow Batteries: Experimental and Computational Investigation.

Highly catalytic electrodes play a vital role in exploiting the capability of vanadium redox flow batteries (VRFBs), but they suffer from a tedious synthesis process and ambiguous interaction mechanisms for catalytic sites. Herein, a facile urea pyrolysis process was applied to prepare graphitic carbon nitride-modified graphite felt (GF@CN), and by the virtue of a density functional theory-assisted calculation, the electron-rich pyridinic nitrogen atom of CN granules is demonstrated as the adsorption center for redox species and plays the key role in improving the performance of VRFBs, with 800 cycles and an energy efficiency of 75% at 150 mA cm-2. Such experimental and computational collaborative investigations guide a realizable and cost-effective solution for other high-power flow batteries.

An Abnormal 3.7†Volt O3-Type Sodium-Ion Battery Cathode.

Layered O3-type sodium oxides (NaMO2 , M=transition metal) commonly exhibit an O3-P3 phase transition, which occurs at a low redox voltage of about 3 V (vs. Na+ /Na) during sodium extraction and insertion, with the result that almost 50 % of their total capacity lies at this low voltage region, and they possess insufficient energy density as cathode materials for sodium-ion batteries (NIBs). Therefore, development of high-voltage O3-type cathodes remains challenging because it is difficult to raise the phase-transition voltage by reasonable structure modulation. A new example of O3-type sodium insertion materials is presented for use in NIBs. The designed O3-type Na0.7 Ni0.35 Sn0.65 O2 material displays a highest redox potential of 3.7 V (vs. Na+ /Na) among the reported O3-type materials based on the Ni2+ /Ni3+ couple, by virtue of its increased Ni-O bond ionicity through reduced orbital overlap between transition metals and oxygen within the MO2 slabs. This study provides an orbital-level understanding of the operating potentials of the nominal redox couples for O3-NaMO2 cathodes. The strategy described could be used to tailor electrodes for improved performance.

Trapping Lithium into Hollow Silica Microspheres with a Carbon Nanotube Core for Dendrite-Free Lithium Metal Anodes.

Li metal anodes, which have attracted much attention for their high specific capacity and low redox potential, face a great challenge in realizing their practical application. The fatal issue of dendrite formation gives rise to internal short circuit and safety hazards and needs to be addressed. Here we propose a rational strategy of trapping Li within microcages to confine the deposition morphology and suppress dendrite growth. Microcages with a carbon nanotube core and porous silica sheath were prepared and proved to be effective for controlling the electrodeposition behavior. In addition, the insulative coating layer prevents concentrated electron flow and decreases the possibility of "hot spots" formation. Because of the Li trapper and uniform electron distribution, the electrode with delicate structure exhibits a dendrite-free morphology after plating 2 mA h cm-2 of Li. As the dendrite growth is suppressed, the as-obtained electrode maintains a high plating/stripping efficiency of 99% over 200 cycles. This work delivers new insights into the design of rational Li metal anodes and hastens the practical application of Li metal batteries.

A novel bismuth-based anode material with a stable alloying process by the space confinement of an in situ conversion reaction for a rechargeable magnesium ion battery.

A novel Bi-based anode material with a stable alloy reaction is prepared by a solvothermal method. The Mg storage mechanism is elucidated for the first time. Owing to the space confinement of in situ conversion, the anode material shows superior magnesium storage performance, especially the cycling stability (capacity retention >96% after 100 cycles).

Stable Li Metal Anodes via Regulating Lithium Plating/Stripping in Vertically Aligned Microchannels.

Li anodes have been rapidly developed in recent years owing to the rising demand for higher-energy-density batteries. However, the safety issues induced by dendrites hinder the practical applications of Li anodes. Here, Li metal anodes stabilized by regulating lithium plating/stripping in vertically aligned microchannels are reported. The current density distribution and morphology evolution of the Li deposits on porous Cu current collectors are systematically analyzed. Based on simulations in COMSOL Multiphysics, the tip effect leads to preferential deposition on the microchannel walls, thus taking full advantage of the lightening rod theory of classical electromagnetism for restraining growth of Li dendrites. The Li anode with a porous Cu current collector achieves an enhanced cycle stability and a higher average Coulombic efficiency of 98.5% within 200 cycles. In addition, the resultant LiFePO4 /Li full battery demonstrates excellent rate capability and stable cycling performance, thus demonstrating promise as a current collector for high-energy-density, safe rechargeable Li batteries.

Graphitized Carbon Fibers as Multifunctional 3D Current Collectors for High Areal Capacity Li Anodes.

The Li metal anode has long been considered as one of the most ideal anodes due to its high energy density. However, safety concerns, low efficiency, and huge volume change are severe hurdles to the practical application of Li metal anodes, especially in the case of high areal capacity. Here it is shown that that graphitized carbon fibers (GCF) electrode can serve as a multifunctional 3D current collector to enhance the Li storage capacity. The GCF electrode can store a huge amount of Li via intercalation and electrodeposition reactions. The as-obtained anode can deliver an areal capacity as high as 8 mA h cm-2 and exhibits no obvious dendritic formation. In addition, the enlarged surface area and porous framework of the GCF electrode result in lower local current density and mitigate high volume change during cycling. Thus, the Li composite anode displays low voltage hysteresis, high plating/stripping efficiency, and long lifespan. The multifunctional 3D current collector promisingly provides a new strategy for promoting the cycling lifespan of high areal capacity Li anodes.

Novel P2-type Na2/3Ni1/6Mg1/6Ti2/3O2 as an anode material for sodium-ion batteries.

A novel P2-type Na2/3Ni1/6Mg1/6Ti2/3O2 material is explored as an anode for sodium-ion batteries (SIBs) for the first time. It delivers a reversible capacity of 92 mA h g-1 with a safe average storage voltage of approximately 0.7 V in a sodium half-cell, and exhibits good cycle stability (ca. 87.4% capacity retention for 100 cycles) at a cut-off voltage of 0.2-2.5 V, indicating its superiority as a promising candidate anode material for SIBs.

Subzero-Temperature Cathode for a Sodium-Ion Battery.

A subzero-temperature cathode material is obtained by nucleating cubic prussian blue crystals at inhomogeneities in carbon nanotubes. Due to fast ionic/electronic transport kinetics even at -25 °C, the cathode shows an outstanding low-temperature performance in terms of specific energy, high-rate capability, and cycle life, providing a practical sodium-ion battery powering an electric vehicle in frigid regions.

[Responses of Arma chinensis cold tolerance to rapid cold hardening and underlying physiological mechanisms].

Rapid cold hardening can enhance the cold tolerance of some insects. To explore the effects of different cold hardening induction temperature on the cold tolerance of Arma chinensis and related physiological mechanisms, the 3rd generation A. chinensis adults reared indoor were treated with cooling at 15, 10, and 4 degrees C for 4 h, respectively, or with gradual cooling from 15 degrees C for 4 h to 10 degrees C for 4 h, and finally to 4 degrees C for 4 h. The super-cooling point, water content, and the contents of low molecular carbohydrates, glycerol, and amino acids of the adults after cooling and the adults cold tolerance at 0, -5, and -10 degrees C were measured by thermocouple, high performance liquid chromatography, and other analytical techniques. When exposed at -10 degrees C after cooling, the survival rate of the adults treated with gradual cooling or treated with cooling at 4 degrees C for 4 h was averagely 58.3%, while that of the adults reared at room temperature (25 degrees C +/- 2 degrees C) or treated with cooling at 15 degrees C or 10 degrees C for 4 h decreased significantly, with an average of 8.9%. The super-cooling point of the adults treated with gradual cooling or with cooling at 4 degrees C for 4 h was -15.6 degrees C, which was averagely 1.3 degrees C lower than that of the other treatments. The water content of the adults had no significant difference among all treatments, with an average of 61.8%, but the glucose, sorbitolum, glycerol, Ala, and Glu contents in treatments gradual cooling and cooling at 4 degrees C for 4 h increased by 2.82-fold, 2.65-fold, 3.49-fold, 51.3%, and 80.2%, while the fucose, mannose, and Pro contents decreased by 68.4%, 52.2%, and 30.2%, respectively, as compared with the other treatments. The fructose content showed no significant difference among all treatments. It was suggested that rapid cool hardening had a critical temperature to induce the physiological metabolism process of adult A. chinensis, and gradual cooling hardening could not further increase the cold tolerance of adult A. chinensis on the basis of rapid cool hardening.