The Interaction in Electrolyte Additives Accelerates Ion Transport to Achieve High-Energy Non-Aqueous Lithium Metal Batteries.

Electrolyte engineering is a feasible strategy to realize high energy density lithium metal batteries. However, stabilizing both lithium metal anodes and nickel-rich layered cathodes is extremely challenging. To break through this bottleneck, a dual-additives electrolyte containing fluoroethylene carbonate (10 vol.%) and 1-methoxy-2-propylamine (1 vol.%) in conventional LiPF6 -containing carbonate-based electrolyte is reported. The two additives can polymerize and thus generate dense and uniform LiF and Li3 N-containing interphases on both electrodes' surfaces. Such robust ionic conductive interphases not only prevent lithium dendrite formation in lithium metal anode but also suppress stress-corrosion cracking and phase transformation in nickel-rich layered cathode. The advanced electrolyte enables Li||LiNi0.8 Co0.1 Mn0.1 O2 stably cycle for 80 cycles at 60 mA g-1 with a specific discharge capacity retention of 91.2% under harsh conditions.

Interface Density Engineering on Heterogeneous Molybdenum Dichalcogenides Enabling Highly Efficient Hydrogen Evolution Catalysis and Sodium Ion Storage.

Constructing active heterointerfaces is powerful to enhance the electrochemical performances of transition metal dichalcogenides, but the interface density regulation remains a huge challenge. Herein, MoO2 /MoS2 heterogeneous nanorods are encapsulated in nitrogen and sulfur co-doped carbon matrix (MoO2 /MoS2 @NSC) by controllable sulfidation. MoO2 and MoS2 are coupled intimately at atomic level, forming the MoO2 /MoS2 heterointerfaces with different distribution density. Strong electronic interactions are triggered at these MoO2 /MoS2 heterointerfaces for enhancing electron transfer. In alkaline media, the optimal material exhibits outstanding hydrogen evolution reaction (HER) performances that significantly surpass carbon-covered MoS2 nanorods counterpart (η10 : 156 mV vs 232 mV) and most of the MoS2 -based heterostructures reported recently. First-principles calculation deciphers that MoO2 /MoS2 heterointerfaces greatly promote water dissociation and hydrogen atom adsorption via the O-Mo-S electronic bridges during HER process. Moreover, benefited from the high pseudocapacitance contribution, abundant "ion reservoir"-like channels, and low Na+ diffusion barrier appended by high-density MoO2 /MoS2 heterointerfaces, the material delivers high specific capacity of 888 mAh g-1 , remarkable rate capability and cycling stability of 390 cycles at 0.1 A g-1 as the anode of sodium ion battery. This work will undoubtedly light the way of interface density engineering for high-performance electrochemical energy conversion and storage systems.

Directional Ion Transport Enabled by Self-Luminous Framework for High-Performance Quasi-Solid-State Lithium Metal Batteries.

Composite gel polymer electrolyte (CGPE), derived from ceramic fillers has emerged as one of the most promising candidates to improve the safety and cycling stability of lithium metal batteries. However, the poor interface compatibility between the ceramic phase and polymer phase in CGPE severely deteriorates lithium-ion pathways and cell performances. In this work, a fluorescent ceramic nanowire network that can palliate the energy barrier of photoinitiators and contribute to preferential nucleation and growth of polymer monomers is developed, thus inducing polymer segment orderly arrangement and tightly combination. A proof-of-concept study lies on fabrications of poly(ethylene oxide) closely coating on the ceramic nanowires, thus dividing the matrix into mesh units that contribute to directional lithium-ion flux and dendrite-free deposition on the metallic anode. The CGPE, based on the state-of-the-art self-luminous framework, facilitates high-performance quasi-solid-state Li||LiFePO4 cell, registering a high capacity of 143.3 mAh g-1 after 120 cycles at a mass loading of 12 mg cm-2 . X-ray computed tomography provides an insight into the relationship between directional lithium-ion diffusion and lithium deposition behavior over the electrochemical processes. The results open a door to improve the electrochemical performances of composite electrolytes in various applications.

Zero-Strain Insertion Anode Material of Lithium-Ion Batteries.

The insertion type materials are the most important anode materials for lithium-ion batteries, but their insufficient capacity is the bottleneck of practical application. Here, LiAl5 O8 nanowires with high theoretical capacity and Li-ions diffusion coefficient are prepared and studied as an insertion anode material, which exhibits zero-strain properties upon electrochemical cycling. However, the poor electronic conductivity of LiAl5 O8 definitely sacrifices the capacity and limits the rate performance. Therefore, compact LiAl5 O8 and carbon composite are further synthesized, in which nanosized LiAl5 O8 particles are uniformly embedded in an amorphous carbon matrix. It displays a reversible capacity of 490.9 mAh g-1 at 1 A g-1 , and the capacity rises continuously to 996.8 mAh g-1 after 1000 cycles due to the interfacial storage mechanism, that the excess Li+ ions can be accommodated in the grain boundaries and C/LiAl5 O8 interfaces.

A dual-function liquid electrolyte additive for high-energy non-aqueous lithium metal batteries.

Engineering the formulation of non-aqueous liquid electrolytes is a viable strategy to produce high-energy lithium metal batteries. However, when the lithium metal anode is combined with a Ni-rich layered cathode, the (electro)chemical stability of both electrodes could be compromised. To circumvent this issue, we report a combination of aluminum ethoxide (0.4 wt.%) and fluoroethylene carbonate (5 vol.%) as additives in a conventional LiPF6-containing carbonate-based electrolyte solution. This electrolyte formulation enables the formation of mechanically robust and ionically conductive interphases on both electrodes' surfaces. In particular, the alumina formed at the interphases prevents the formation of dendritic structures on the lithium metal anode and mitigate the stress-induced cracking and phase transformation in the Ni-rich layered cathode. By coupling a thin (i.e., about 40 µm) lithium metal anode with a high-loading (i.e., 21.5 mg cm-2) LiNi0.8Co0.1Mn0.1O2-based cathode in coin cell configuration and lean electrolyte conditions, the engineered electrolyte allows a specific discharge capacity retention of 80.3% after 130 cycles at 60 mA g-1 and 30 °C which results in calculated specific cell energy of about 350 Wh kg-1.

Cross-linked beta alumina nanowires with compact gel polymer electrolyte coating for ultra-stable sodium metal battery.

Sodium metal batteries have potentially high energy densities, but severe sodium-dendrite growth and side reactions prevent their practical applications, especially at high temperatures. Herein, we design an inorganic ionic conductor/gel polymer electrolyte composite, where uniformly cross-linked beta alumina nanowires are compactly coated by a poly(vinylidene fluoride-co-hexafluoropropylene)-based gel polymer electrolyte through their strong molecular interactions. These  beta alumina nanowires combined with the gel polymer layer create dense and homogeneous solid-liquid hybrid sodium-ion transportation channels through and along the nanowires, which promote uniform sodium deposition and formation of a stable and flat solid electrolyte interface on the sodium metal anode. Side reactions between the sodium metal and liquid electrolyte, as well as sodium dendrite formation, are successfully suppressed, especially at 60 °C. The sodium vanadium phosphate/sodium full cells with composite electrolyte exhibit 95.3% and 78.8% capacity retention after 1000 cycles at 1 C at 25 °C and 60 °C, respectively.

Interconnected Ultrasmall V2O3 and Li4Ti5O12 Particles Construct Robust Interfaces for Long-Cycling Anodes of Lithium-Ion Batteries.

Designing composite structures of active materials is critical for high-performance lithium-ion batteries, as it determines the reversibility of lithium-ion insertion and extraction of the electrodes. The V2O3 anode has a high specific capacity but presents poor cycling stability due to a large volume change. Herein, a novel C@V2O3-Li4Ti5O12 composite with ultrastable cycling stability is constructed. In this composite structure, the interconnected ultrasmall V2O3 and Li4Ti5O12 nanoparticles (5-10 nm) construct robust interfaces in the carbon matrix. The Li4Ti5O12 nanoparticles with excellent cycling stability and a minor volume change act as fixtures that effectively restrict the volume change of V2O3 nanoparticles and improve the cycling stability of the C@V2O3-Li4Ti5O12 composite. The C@V2O3-Li4Ti5O12 composite maintains no degradation during 500 cycles under a current density of 100 mA g-1. The results demonstrate that constructing a highly stable interface between the active nanoparticles with smaller and larger volume changes is of great significance to suppress their pulverization and achieve high reversibility. This work contributes to a new strategy to design the structure of long-cycling anode materials for highly stable lithium-ion batteries.

Spherical Li Deposited inside 3D Cu Skeleton as Anode with Ultrastable Performance.

Porous current collectors are conducive to enhance the property of Li metal anode. Unfortunately, congestion in diffusion path during plating process damages the effects of current collectors. Herein, we developed a 3D Cu skeleton with open micrometer-sized pores by NaCl-assisted powder-sintering method. The unobstructed pores of 3D Cu skeleton help to reduce congestion during plating, thus most of Li deposited inside the current collector. Besides, the large smooth surface promotes the deposition of Li with smooth spherical shape, which mitigating Li dendrite growth. As a result, better safety and rechargeability of Li metal anode were achieved in this design.

Transformation of bulk alloys to oxide nanowires.

One dimensional (1D) nanostructures offer prospects for enhancing the electrical, thermal, and mechanical properties of a broad range of functional materials and composites, but their synthesis methods are typically elaborate and expensive. We demonstrate a direct transformation of bulk materials into nanowires under ambient conditions without the use of catalysts or any external stimuli. The nanowires form via minimization of strain energy at the boundary of a chemical reaction front. We show the transformation of multimicrometer-sized particles of aluminum or magnesium alloys into alkoxide nanowires of tunable dimensions, which are converted into oxide nanowires upon heating in air. Fabricated separators based on aluminum oxide nanowires enhanced the safety and rate capabilities of lithium-ion batteries. The reported approach allows ultralow-cost scalable synthesis of 1D materials and membranes.

Influence of Binders, Carbons, and Solvents on the Stability of Phosphorus Anodes for Li-ion Batteries.

Phosphorus (P) is an abundant element that exhibits one of the highest gravimetric and volumetric capacities for Li storage, making it a potentially attractive anode material for high capacity Li-ion batteries. However, while phosphorus carbon composite anodes have been previously explored, the influence of the inactive materials on electrode cycle performance is still poorly understood. Here, we report and explain the significant impacts of polymer binder chemistry, carbon conductive additives, and an under-layer between the Al current collector and ball milled P electrodes on cell stability. We focused our study on the commonly used polyvinylidene fluoride (PVDF) and poly(acrylic acid) (PAA) binders as well as exfoliated graphite (ExG) and carbon nanotube (CNT) additives. The mechanical properties of the binders were found to change drastically because of interactions with both the slurry and electrolyte solvents, significantly effecting the electrochemical cycle stability of the electrodes. Binder adhesion was also found to be critical in achieving stable electrochemical cycling. The best anodes demonstrated ∼1400 mAh/g-P gravimetric capacity after 200 cycles at C/2 rates in Li half cells.

Performance Enhancement and Side Reactions in Rechargeable Nickel-Iron Batteries with Nanostructured Electrodes.

We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni-Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe(-1) at 200 mA g(-1) current density), which exceed that of commercial Ni-Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20-50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized [such as Fe(OH)2 or Fe3O4] states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction-oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH(-) anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability.

Carbon and graphene double protection strategy to improve the SnO(x) electrode performance anodes for lithium-ion batteries.

SnOx is a promising high-capacity anode material for lithium-ion batteries (LIBs), but it usually exhibits poor cycling stability because of its huge volume variation during the lithium uptake and release process. In this paper, SnOx carbon nanofibers (SnOx@CNFs) are firstly obtained in the form of a nonwoven mat by electrospinning followed by calcination in a 0.02 Mpa environment at 500 °C. Then we use a simple mixing method for the synthesis of SnOx@CNF@graphene (SnOx@C@G) nanocomposite. By this technique, the SnOx@CNFs can be homogeneously deposited in graphene nanosheets (GNSs). The highly scattered SnOx@C@G composite exhibits enhanced electrochemical performance as anode material for LIBs. The double protection strategy to improve the electrode performance through producing SnOx@C@G composites is versatile. In addition, the double protection strategy can be extended to the fabrication of various types of composites between metal oxides and graphene nanomaterials, possessing promising applications in catalysis, sensing, supercapacitors and fuel cells.

ß-Cobalt sulfide nanoparticles decorated graphene composite electrodes for high capacity and power supercapacitors.

Electrochemical supercapacitors have drawn much attention because of their high power and reasonably high energy densities. However, their performances still do not reach the demand of energy storage. In this paper ß-cobalt sulfide nanoparticles were homogeneously distributed on a highly conductive graphene (CS-G) nanocomposite, which was confirmed by transmission electron microscopy analysis, and exhibit excellent electrochemical performances including extremely high values of specific capacitance (~1535 F g(-1)) at a current density of 2 A g(-1), high-power density (11.98 kW kg(-1)) at a discharge current density of 40 A g(-1) and excellent cyclic stability. The excellent electrochemical performances could be attributed to the graphene nanosheets (GNSs) which could maintain the mechanical integrity. Also the CS-G nanocomposite electrodes have high electrical conductivity. These results indicate that high electronic conductivity of graphene nanocomposite materials is crucial to achieving high power and energy density for supercapacitors.

Small quantities of cobalt deposited on tin oxide as anode material to improve performance of lithium-ion batteries.

In this report, we present a hybrid structure involving a small quantity of Co element uniformly deposited on porous SnO(2) spheres as stable and high capacity anode materials for lithium-ion batteries. Specifically, Co element deposited on SnO(2) nanomaterials exhibited an exceptional reversible capacity of 810 mA h g(-1) after 50 cycles which is higher than the pure SnO(2) electrode. Based on the experiments results, a possible mechanism for the change of this structure during lithium ion insertion/extraction was proposed. The minute quantity of Co element uniformly deposited on SnO(2) spherical structure could prevent Sn aggregation during charging-discharging, and high porosity of the spherical structure allowed the volume expansion during lithium ion alloying/dealloying. The SnO(2) deposited with small quantities of Co element as electrode facilitated improved performance of lithium ion batteries with higher energy densities.

α-Fe2O3 nanowall arrays: hydrothermal preparation, growth mechanism and excellent rate performances for lithium ion batteries.

α-Fe(2)O(3) nanowall arrays (NWAs) were grown directly on Ni foam by a facile hydrothermal method. Based on time-dependent experiment results, a possible formation mechanism for this structure was proposed. The as-prepared α-Fe(2)O(3) samples have an open network structure constituted of interconnected nanowalls and can be directly used as integrated electrodes for lithium-ion batteries (LIBs). The unique nanostructural feature is advantageous in electron transport and electrolyte diffusion efficiency, which can accelerate the electrochemical reaction. Thus, compared to a traditional electrode, the unique assembly reduces polarization of the electrode and results in excellent rate performances (440 mA h g(-1) at 5 C).

Facile solvothermal synthesis of mesoporous Cu2SnS3 spheres and their application in lithium-ion batteries.

Three dimensional (3D) mesoporous Cu(2)SnS(3) spheres composed of nanoparticles were synthesized by a simple solvothermal route. As anode materials for lithium-ion batteries, they delivered remarkably enhanced cycling performances. This could be attributed to the 3D mesoporous structure which may be propitious to the accommodation of volume expansion. Besides, a possible electrochemical reaction mechanism was proposed based on cyclic voltammetry (CV) testing results and confirmed by subsequent ex situ XRD studies. In addition, the influence of testing temperature on cycling performance has also been investigated.