Tony Jaumann

High Area Capacity Lithium-Sulfur Full-cell Battery with Prelitiathed Silicon Nanowire-Carbon Anodes for Long Cycling Stability

We show full Li/S cells with the use of balanced and high capacity electrodes to address high power electro-mobile applications. The anode is made of an assembly comprising of silicon nanowires as active material densely and conformally grown on a 3D carbon mesh as a light-weight current collector, offering extremely high areal capacity for reversible Li storage of up to 9 mAh/cm2. The dense growth is guaranteed by a versatile Au precursor developed for homogenous Au layer deposition on 3D substrates. In contrast to metallic Li, the presented system exhibits superior characteristics as an anode in Li/S batteries such as safe operation, long cycle life and easy handling. These anodes are combined with high area density S/C composite cathodes into a Li/S full-cell with an ether- and lithium triflate-based electrolyte for high ionic conductivity. The result is a highly cyclable full-cell with an areal capacity of 2.3 mAh/cm2, a cyclability surpassing 450 cycles and capacity retention of 80% after 150 cycles (capacity loss <0.4% per cycle). A detailed physical and electrochemical investigation of the SiNW Li/S full-cell including in-operando synchrotron X-ray diffraction measurements reveals that the lower degradation is due to a lower self-reduction of polysulfides after continuous charging/discharging.

Anodically fabricated TiO2–SnO2 nanotubes and their application in lithium ion batteries

Developing novel electrode materials is a substantial issue to improve the performance of lithium ion batteries. In the present study, single phase Ti–Sn alloys with different Sn contents of 1 to 10 at% were used to fabricate Ti–Sn–O nanotubes via a straight-forward anodic oxidation step in an ethylene glycol-based solution containing NH4F. Various characterization tools such as SEM, EDXS, TEM, XPS and Raman spectroscopy were used to characterize the grown nanotube films. Our results reveal the successful formation of mixed TiO2/SnO2 nanotubes in the applied voltage range of 10–40 V. The as-formed nanotubes are amorphous and their dimensions are precisely controlled by tuning the formation voltage which turns Ti–Sn–O nanotubes into highly attractive materials for various applications. As an example, the Ti–Sn–O nanotubes offer promising properties as anode materials in lithium ion batteries. The electrochemical performance of the grown nanotubes was evaluated against a Li/Li+ electrode at a current density of 504 μA cm−2. The results demonstrate that TiO2/SnO2 nanotubes prepared at 40 V on a TiSn1 alloy substrate display an average 1.4 fold increase in areal capacity with excellent cycling stability over more than 400 cycles compared to the pure TiO2 nanotubes fabricated and tested under identical conditions. This electrode was tested at current densities of 50, 100, 252, 504 and 1008 μA cm−2 exhibiting average capacities of 780, 660, 490, and 405 μA cm−2 (i.e. 410, 345, 305 and 212 mA h g−1), respectively. The remarkably improved electrochemical performance is attributed to enhanced lithium ion diffusion which originates from the presence of SnO2 nanotubes and the high surface area of the mixed oxide tubes. The TiO2/SnO2 electrodes retain their original tubular structure after electrochemical cycling with only slight changes in their morphology.

Dichlorosilane-derived nano-silicon inside hollow carbon spheres as a high-performance anode for Li-ion batteries

A novel and cost-effective synthesis of silicon nanocrystallites (<10 nm) sealed in hollow carbon spheres (nc-Si@HCS) is developed as a promising anode material for high-performance Li-ion batteries (LIBs). The preparation method involves dichlorosilane (H2SiCl2) as widely available feedstock, to form a hydrogen-rich polysiloxane as a precursor for the production of large quantities of silicon nanoparticles. The final electrode material is composed of agglomerated 5 nm sized silicon nanoparticles encapsulated within hollow micro-sized carbon structures. A high specific capacity of 1570 mA h gelectrode−1 at 0.25 A g−1 with a capacity retention of 65% after 250 deep discharge cycles and a reversible high areal capacity of up to 4 mA h cm−2 at a total mass loading of 3.2 mg cm−2 impressively demonstrate the excellent features of this novel anode material. We performed a detailed structural as well as electrochemical characterization in different electrolytes. Post mortem investigations help to understand the degradation mechanism in our material. The study herein heralds a new approach to structurally design advanced negative electrode materials with the potential to increase the specific energy of LIBs and to boost future electro-mobility technology.

Surface and Electrochemical Studies on Silicon Diphosphide as Easy-to-Handle Anode Material for Lithium-Based Batteries-the Phosphorus Path.

The electrochemical characteristics of silicon diphosphide (SiP2) as a new anode material for future lithium-ion batteries (LIBs) are evaluated. The high theoretical capacity of about 3900 mA h g-1 (fully lithiated state: Li15Si4 + Li3P) renders silicon diphosphide as a highly promising candidate to replace graphite (372 mA h g-1) as the standard anode to significantly increase the specific energy density of LIBs. The proposed mechanism of SiP2 is divided into a conversion reaction of phosphorus species, followed by an alloying reaction forming lithium silicide phases. In this study, we focus on the conversion mechanism during cycling and report on the phase transitions of SiP2 during lithiation and delithiation. By using ex situ analysis techniques such as X-ray powder diffraction, formed reaction products are identified. Magic angle spinning nuclear magnetic resonance spectroscopy is applied for the characterization of long-range ordered compounds, whereas X-ray photoelectron spectroscopy gives information of the surface-layer species at the interface of active material and electrolyte. Our SiP2 anode material shows a high initial capacity of about 2700 mA h g-1, whereas a fast capacity fading during the first few cycles occurs which is not necessarily expected. On the basis of our results, we conclude that besides other degradation effects, such as electrolyte decomposition and electrical contact loss, the rapid capacity fading originates from the formation of a low ion-conductive layer of LiP. This insulating layer hinders lithium-ion diffusion during lithiation and thereby mainly contributes to fast capacity fading.

Metal-derived nanostructured materials for advanced lithium–sulfur batteries

Since the resurgence of interest in lithium–sulfur (Li–S) batteries at the end of the 2000s, research in the field has grown rapidly. Li–S batteries hold great promise as the upcoming post-lithium-ion batteries owing to their notably high theoretical specific energy density of 2600 W h kg−1, nearly five-fold larger than that of current lithium-ion batteries. However, one of their major technical problems is found in the shuttling of soluble polysulfides between the electrodes, resulting in rapid capacity fading and poor cycling stability. This review spotlights the foremost findings and the recent progress in enhancing the electrochemical performance of Li–S batteries by using nanoscaled metal compounds and metals. Based on an overview of reported functional metal-based materials and their specific employment in certain parts of Li–S batteries, the underlying mechanisms of enhanced adsorption and improved reaction kinetics are critically discussed involving both experimental and computational research findings. Thus, material design principles and possible interdisciplinary research approaches providing the chance to jointly advance with related fields such as electrocatalysis are identified. Particularly, we elucidate additives, sulfur hosts, current collectors and functional interlayers/hybrid separators containing metal oxides, hydroxides and sulfides as well as metal–organic frameworks, bare metal and further metal nitrides, metal carbides and MXenes. Throughout this review article, we emphasize the close relationship between the intrinsic properties of metal-based nanostructured materials, the (electro)chemical interaction with lithium (poly)sulfides and the subsequent effect on the battery performance. Concluding the review, prospects for the future development of practical Li–S batteries with metal-based nanomaterials are discussed.

Synthetic and Catalytic Potential of Amorphous Mesoporous Aluminosilicates Prepared by Postsynthetic Aluminations of Silica in Aqueous Media

Amorphous aluminosilicate catalysts have been used industrially on a large scale for almost a century. However, the influence of the pH on the alumination of silica in aqueous solutions has remained largely unclear. Herein, room temperature aluminations of different mesoporous amorphous silicas (fumed silica, dried silica gel, SBA‐15, MCM‐41, and COK‐12) with aqueous solutions of various pH (3–13) are explored. The aqueous solutions are prepared using different aluminum sources (Al(NO3)3 or NaAlO2) and alkaline additives (NaOH or NH4OH). The decoupling of pH and Al source using alkaline additives results in a vast experimental potential to prepare unique aluminosilicates, whereby an important role is played by the pH development during the treatment. The bulk and surface composition, acidity, aluminum coordination, morphology, hydrothermal stability, and porosity of the obtained materials are characterized. Optimal samples possess large surface areas and superior acidities (up to 50 % higher) and outstanding stabilities compared to aluminosilicates prepared with state‐of‐the‐art methods. The obtained materials are evaluated in a series of acid‐catalyzed model reactions involving substrates of various chemical reactivity and size, enabling insight in the catalytic functionality of the introduced Brønsted and Lewis sites. The potential of the obtained materials is emphasized by the similar or superior acidity and catalytic performance compared to several benchmark industrial silica–alumina‐based catalysts.