Overcoming the Interfacial Limitations Imposed by the Solid-Solid Interface in Solid-State Batteries Using Ionic Liquid-Based Interlayers.

Li-garnets are promising inorganic ceramic solid electrolytes for lithium metal batteries, showing good electrochemical stability with Li anode. However, their brittle and stiff nature restricts their intimate contact with both the electrodes, hence presenting high interfacial resistance to the ionic mobility. To address this issue, a strategy employing ionic liquid electrolyte (ILE) thin interlayers at the electrodes/electrolyte interfaces is adopted, which helps overcome the barrier for ion transport. The chemically stable ILE improves the electrodes-solid electrolyte contact, significantly reducing the interfacial resistance at both the positive and negative electrodes interfaces. This results in the more homogeneous deposition of metallic lithium at the negative electrode, suppressing the dendrite growth across the solid electrolyte even at high current densities of 0.3 mA cm-2 . Further, the improved interface Li/electrolyte interface results in decreasing the overpotential of symmetric Li/Li cells from 1.35 to 0.35 V. The ILE modified Li/LLZO/LFP cells stacked either in monopolar or bipolar configurations show excellent electrochemical performance. In particular, the bipolar cell operates at a high voltage (≈8 V) and delivers specific capacity as high as 145 mAh g-1 with a coulombic efficiency greater than 99%.

Coupling Particle Ordering and Spherulitic Growth for Long-Term Performance of Nanocellulose/Poly(ethylene oxide) Electrolytes.

Development of lithium-ion batteries with composite solid polymer electrolytes (CPSEs) has attracted attention due to their higher energy density and improved safety compared to systems utilizing liquid electrolytes. While it is well known that the microstructure of CPSEs affects the ionic conductivity, thermal stability, and mechanical integrity/long-term stability, the bridge between the microscopic and macroscopic scales is still unclear. Herein, we present a systematic investigation of the distribution of TEMPO-oxidized cellulose nanofibrils (t-CNFs) in two different molecular weights of poly(ethylene oxide) (PEO) and its effect on Li+ ion mobility, bulk conductivity, and long-term stability. For the first time, we link local Li-ion mobility at the nanoscale level to the morphology of CPSEs defined by PEO spherulitic growth in the presence of t-CNF. In a low-MW PEO system, spherulites occupy a whole volume of the derived CPSE with t-CNF being incorporated in between lamellas, while their nuclei remain particle-free. In a high-MW PEO system, spherulites are scarce and their growth is arrested in a non-equilibrium cubic shape due to the strong t-CNF network surrounding them. Electrochemical strain microscopy and solid-state 7Li nuclear magnetic resonance spectroscopy confirm that t-CNF does not partake in Li+ ion transport regardless of its distribution within the polymer matrix. Free-standing CSPE films with low-MW PEO have higher conductivity but lack long-term stability due to the existence of uniformly distributed, particle-free, spherulite nuclei, which have very little resistance to Li dendrite growth. On the other hand, high-MW PEO has lower conductivity but demonstrates a highly stable Li cycling response for more than 1000 h at 0.2 mA/cm2 and 65 °C and more than 100 h at 85 °C. The study provides a direct link between the microscopic dynamic, Li-ion transport, bulk mechanical properties and long-term stability of the derived CPSE and, and as such, offers a pathway towards design of robust all-solid-state Li-metal batteries.

Graphene in Solid-State Batteries: An Overview.

Solid-state batteries (SSBs) have emerged as a potential alternative to conventional Li-ion batteries (LIBs) since they are safer and offer higher energy density. Despite the hype, SSBs are yet to surpass their liquid counterparts in terms of electrochemical performance. This is mainly due to challenges at both the materials and cell integration levels. Various strategies have been devised to address the issue of SSBs. In this review, we have explored the role of graphene-based materials (GBM) in enhancing the electrochemical performance of SSBs. We have covered each individual component of an SSB (electrolyte, cathode, anode, and interface) and highlighted the approaches using GBMs to achieve stable and better performance. The recent literature shows that GBMs impart stability to SSBs by improving Li+ ion kinetics in the electrodes, electrolyte and at the interfaces. Furthermore, they improve the mechanical and thermal properties of the polymer and ceramic solid-state electrolytes (SSEs). Overall, the enhancements endowed by GBMs will address the challenges that are stunting the proliferation of SSBs.

A stable TiO2-graphene nanocomposite anode with high rate capability for lithium-ion batteries.

A rapid microwave hydrothermal process is adopted for the synthesis of titanium dioxide and reduced graphene oxide nanocomposites as high-performance anode materials for Li-ion batteries. With the assistance of hydrazine hydrate as a reducing agent, graphene oxide was reduced while TiO2 nanoparticles were grown in situ on the nanosheets to obtain the nanocomposite material. The morphology of the nanocomposite obtained consisted of TiO2 particles with a size of ∼100 nm, uniformly distributed on the reduced graphene oxide nanosheets. The as-prepared TiO2-graphene nanocomposite was able to deliver a capacity of 250 mA h g-1 ± 5% at 0.2C for more than 200 cycles with remarkably stable cycle life during the Li+ insertion/extraction process. In terms of high rate capability performance, the nanocomposite delivered discharge capacity of ca. 100 mA h g-1 with >99% coulombic efficiency at C-rates of up to 20C. The enhanced electrochemical performance of the material in terms of high rate capability and cycling stability indicates that the as-developed TiO2-rGO nanocomposites are promising electrode materials for future Li-ion batteries.

Interface in Solid-State Lithium Battery: Challenges, Progress, and Outlook.

All-solid-state batteries (ASSBs) based on inorganic solid electrolytes promise improved safety, higher energy density, longer cycle life, and lower cost than conventional Li-ion batteries. However, their practical application is hampered by the high resistance arising at the solid-solid electrode-electrolyte interface. Although the exact mechanism of this interface resistance has not been fully understood, various chemical, electrochemical, and chemo-mechanical processes govern the charge transfer phenomenon at the interface. This paper reports the interfacial behavior of the lithium and the cathode in oxide and sulfide inorganic solid-electrolytes and how that affects the overall battery performance. An overview of the recent reports dealing with high resistance at the anodic and cathodic interfaces is presented and the scientific and engineering aspects of the approaches adopted to solve the issue are summarized.

Design and Tuning of the Electrochemical Properties of Vanadium-Based Cation-Disordered Rock-Salt Oxide Positive Electrode Material for Lithium-Ion Batteries.

Disordered rock-salt compounds are becoming increasingly important due to their potential as high-capacity positive electrode materials for lithium-ion batteries. Thereby, a significant number of studies have focused on increasing the accessible Li capacity, but studies to manipulate the electrochemical potential are limited. This work explores the effect of transition-metal substitution on the electrochemistry of ternary disordered rock-salt-type compounds with LiM2+0.5V0.54+O2 stoichiometry (M = Mn, Fe, Co) directly synthesized through mechanochemistry. Rietveld refinements of synchrotron X-ray diffraction patterns confirm the disordered rock-salt structures. First-principles density functional theory study is used to predict the impact of the cation substitution on the expected average voltage and the electronic structures of these materials are used to analyze the underlying redox processes. For LiM2+0.5V4+0.5O2 (M = Mn, Fe, Co), discharge voltages increase in the order of Mn < Fe < Co with 2.28, 2.41, and 2.51 V, exhibiting discharge capacities of 219, 207, and 234 mAh g-1, respectively. In comparison, for the disordered rock-salt Li2VO3, an average discharge voltage of ∼2.2 V with V5+/4+ redox couple has been reported. However, detrimental electrode-electrolyte interactions manifested as transition-metal dissolution has been found to result in severe capacity fading. Thereto, the use of a concentrated 5.5 M LiFSI increased the cycling stability significantly, effectively reducing transition-metal dissolution. The underlying reasons for the capacity fading of disordered rock salts are yet unclear. We stress the importance of cathode-electrolyte interactions, thus opening new directions for the improvement of cation-disordered materials.

Revealing of Core Shell Effect on Frequency-Dependent Properties of Bi-based Relaxor/Ferroelectric Ceramic Composites.

In this study, electromechanical characteristics of (1-x) Bi0.5Na0.5TiO3-xSrTiO3 (ST26, x = 0.26)/(1-y) Bi0.5Na0.5TiO3-ySrTiO3 (ST10, y = 0.1) (matrix/seed) composites were studied. The ST26 (high relaxor phase) and ST10 (a relaxor ferroelectric (RF), high ferroelectric phase) composite with large (r-ST26-ST10) and small (t-ST26-ST10) grains exhibited frequency-related dielectric properties and large strain response at a low triggering electric field (an incipient piezoelectricity). It is ascribed to a matrix-seed effect originating from the inhomogeneous composition due to the presence of two phases. The r-ST26-ST10 composite sintered at 4 h, prominent material, showed a high normalized dynamic strain (d33*) of ~700 pm/V (large grains) with stable frequency dependence properties at a low field of 40 kV/cm. The properties of the r-ST26-ST10 composite exhibit less decay with frequency-related polarization and strain compared to those of t-ST26-ST10 composite. The increase in soaking time promotes the diffusion and homogenization of the microstructure in composites, leading to changes in the core-shell structure in the solid solution. The polarization and strain of the ST26-ST10 composites with the frequency are linked to the stability of the internal random fields created by non-ergodic relaxor phase of seed and the amount of phase change in the ergodic relaxor matrix.

Anodic WO3 mesosponge @ carbon: a novel binder-less electrode for advanced energy storage devices.

A novel design for an anodic WO3 mesosponge @ carbon has been introduced as a highly stable and long cyclic life Li-ion battery electrode. The nanocomposite was successfully synthesized via single-step electrochemical anodization and subsequent heat treatment in an acetylene and argon gas environment. Morphological and compositional characterization of the resultant materials revealed that the composite consisted of a three-dimensional interconnected network of WO3 mesosponge layers conformally coated with a 5 nm thick carbon layer and grown directly on top of tungsten metal. The results demonstrated that the carbon-coated mesosponge WO3 layers exhibit a capacity retention of 87% after completion of 100 charge/discharge cycles, which is significantly higher than the values of 25% for the crystalline (without carbon coating) or 40% for the as-prepared mesosponge WO3 layers. The improved electrochemical response was attributed to the higher stability and enhanced electrical conductivity offered by the carbon coating layer.

Comparative electrochemical analysis of crystalline and amorphous anodized iron oxide nanotube layers as negative electrode for LIB.

This work is a comparative study of the electrochemical performance of crystalline and amorphous anodic iron oxide nanotube layers. These nanotube layers were grown directly on top of an iron current collector with a vertical orientation via a simple one-step synthesis. The crystalline structures were obtained by heat treating the as-prepared (amorphous) iron oxide nanotube layers in ambient air environment. A detailed morphological and compositional characterization of the resultant materials was performed via transmission electron microscopy (TEM), field-emission scanning electron microscopy (FE-SEM), X-ray diffraction (XRD), and Raman spectroscopy. The XRD patterns were further analyzed using Rietveld refinements to gain in-depth information on their quantitative phase and crystal structures after heat treatment. The results demonstrated that the crystalline iron oxide nanotube layers exhibit better electrochemical properties than the amorphous iron oxide nanotube layers when evaluated in terms of the areal capacity, rate capability, and cycling performance. Such an improved electrochemical response was attributed to the morphology and three-dimensional framework of the crystalline nanotube layers offering short, multidirectional transport lengths, which favor rapid Li(+) ions diffusivity and electron transport.

Electrically exploded silicon/carbon nanocomposite as anode material for lithium-ion batteries.

In this work, silicon (Si) containing carbon coated core-shell nanostructures were synthesized by electrical explosion of Si wires in ethanol solution followed by high energy mechanical milling (HEMM) process. Material characterization was carried-out using transmission electron microscopy (TEM), field-emission scanning electron microscopy (FESEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD) analysis. HEMM led to very fine and amorphous Si particles in the presence of carbon and inactive Silicon-Carbide (SiC) matrix. These Si based nanocomposites, obtained through electrical explosion followed by HEMM (milled sample), exhibited enhanced electrochemical performance than unmilled nanocomposites, when evaluated as anode material for lithium-ion batteries (LIBs). On completion of (the) 1st cycle, milled and unmilled sample(s) showed specific discharge capacities around 825 mAh/g and 717 mAh/g, respectively. Interestingly, the coulombic efficiencies of milled and unmilled samples were 98.5% and 97% after 60th cycle respectively. The enhanced electrochemical performance is attributed to fine and amorphous Si based nanocomposite obtained through HEMM process.