The good reactivity of lithium with nanostructured copper phosphide

In Li-ion battery technology, Li diffusion in the electrode is mainly limited by the quality of the interfaces. To take advantage of the large capacity gain offered by the transition metal phosphides (TMP) as negative electrode, a new self-supported TMP/Cu nanoarchitectured electrode concept is proposed. This specific design allows one to fine-tune control of both (TMP)/current collector and (TMP)/electrolyte interfaces of the electrode. This new electrode preparation process is based on an electrochemical templated synthesis of copper nanorods followed by a phosphorus vaporization. The P vapour reacts with the Cu nanorods leading to Cu3P nanorods. Preliminary electrochemical tests of the as-obtained Cu3P nanorods/Li half cell show the great interest of using such a nanostructured TMP electrode in a Li battery. These nanoarchitectured phosphide electrodes can sustain a C-rate (a full discharge in 1h) cycling without exhibiting any important reversible capacity loss for 20 cycles

Snapshot on Negative Electrode Materials for Potassium-Ion Batteries

Potassium-based batteries have recently emerged as a promising alternative to lithium-ion batteries. The very low potential of the K+/K redox couple together with the high mobility of K+ in electrolytes resulting from its weak Lewis acidity should provide high energy density systems operating with fast kinetics. However, potassium metal cannot be implemented in commercial batteries due to its high reactivity. As safety is one of the major concerns when developing new types of batteries, it is therefore crucial to look for materials alternative to potassium metal that electrochemically insert K+ at low potential. Here, the different types of negative electrode materials highlighted in many recent reports will be presented in detail. As a cornerstone of viable potassium-ion batteries, the choice of the electrolyte will be addressed as it directly impacts the cycling performance. Lastly, guidelines to a rational design of sustainable and efficient negative electrode materials will be proposed as open perspectives

Effects of Relaxation on Conversion Negative Electrode Materials for Li-Ion Batteries: A Study of TiSnSb Using 119Sn Mössbauer and 7Li MAS NMR Spectroscopies

Conversion materials were recently considered as plausible alternatives to conventional insertion negative electrode materials in lithium-ion batteries due to their large gravimetric and volumetric energy densities. The ternary alloy TiSnSb was recently proposed as a suitable negative electrode material due to its large capacity (550 mA h g–1) and rate capability over many cycles. TiSnSb has been investigated at the end of lithiation (discharge) using 119Sn Mössbauer and 7Li magic-angle spinning (MAS) NMR spectroscopies to determine the species formed, their relative stabilities and their behavior during relaxation. During discharge, TiSnSb undergoes a conversion reaction to produce a mixture of phases believed to consist of lithium antimonides, lithium stannides, and titanium metal. In situ 119Sn Mössbauer spectroscopy indicates the presence of Li7Sn2 at the end of discharge, while 7Li NMR experiments suggest the formation of two distinct Sn-containing species (tentatively assigned to Li7Sn2 and Li7Sn3), in addition to two Sb-containing species (tentatively assigned as Li3Sb and a non-stoichiometric phase of Li2Sb, Li2–xSb). To gain insight into the relative stabilities of the species formed, experiments have been completed under open circuit voltage conditions. A new Sn-based species has been identified via 119Sn Mössbauer spectroscopy at the end of relaxation. Similar changes are observed in the 7Li NMR spectra obtained during relaxation. The species created at the end of discharge are extremely unstable and spontaneously evolve towards delithiated phases. Surprisingly, it is possible to resume electrochemical cycling after relaxation. It is likely that this behavior can be extended to this family of electrode materials that undergo the conversion reaction

Double-walled carbon nanotubes, a performing additive to enhance capacity retention of antimony anode in potassium-ion batteries

The effect of carbon additives on electrode formulation of bulk antimony was investigated in potassium-ion batteries. Several types of carbon including conventional carbon black, graphite and double-walled carbon nanotubes (DWCNT), employed as conductive agents, were found to play a non-negligible role on the electrochemical performance of antimony. While DWCNT alone show no reversible K+ storage compared to the other carbons, the Sb/DWCNT electrode exhibits better capacity retention and rate capability than Sb formulated with usual carbon additives or even with graphite. This can be ascribed to the specific structure of DWCNT acting not only as conductive additive but also as a mechanical reinforcement for the whole electrode, which has to withstand the large volume change of antimony during potassiation/depotassiation cycles

Pitch-based carbon/nano-silicon composite, an efficient anode for Li-ion batteries

International audienc

Dehydration of Alginic Acid Cryogel by TiCl4 vapor : Direct Access to Mesoporous TiO2@C Nanocomposites and Their Performance in Lithium-Ion Batteries

A new strategy for the synthesis of mesoporous TiO2@C nanocomposites through the direct mineralization of seaweed-derived alginic acid cryogel by TiCl4 through a solid/vapor reaction pathway is presented. In this synthesis, alginic acid cryogel can have multiple roles; i) mesoporous template, ii) carbon source, and iii) oxygen source for the TiO2 precursor, TiCl4. The resulting TiO2@alginic acid composite was transformed either into pure mesoporous TiO2 by calcination or into mesoporous TiO2@C nanocomposites by pyrolysis. By comparing with a nonporous TiO2@C composite, the importance of the mesopores on the performance of electrodes for lithium-ion batteries based on mesoporous TiO2@C composite was clearly evidenced. In addition, the carbon matrix in the mesoporous TiO2@C nanocomposite also showed electrochemical activity versus lithium ions, providing twice the capacity of pure mesoporous TiO2 or alginic acid-derived mesoporous carbon (A600). Given the simplicity and environmental friendliness of the process, the mesoporous TiO2@C nanocomposite could satisfy the main prerequisites of green and sustainable chemistry while showing improved electrochemical performance as a negative electrode for lithium-ion batteries

Atomic layer fluorination of 5 V class positive electrode material LiCoPO4 for enhanced electrochemical performance

EJK would like to thank the Alistore ERI for the award of a studentship. The authors thank EPSRC Capital for Great Technologies Grant EP/L017008/1. The authors want to thank the French Research Network on the Electrochemical Energy Storage (RS2E) for YCB’s PhD grant. MD and NL are indebted to the IR-RMN-THC FR3050 CNRS for the spectrometer time access and the financial support of the NMR experiments.The surface fluorination of lithium cobalt phosphate (LiCoPO4, LCP) using a one‐step, room temperature processable, easily up‐scalable and dry surface modification method with XeF2 as fluorine source was developed. After fluorination, fluorine‐rich nanoparticles were observed mainly on the particle surface, which facilitates the improvement of surface stability and electrochemical performance such as cycling stability and rate capability, as the fluorinated LCP can be protected against side reactions with electrolyte or by‐products of electrolyte decomposition at high voltage (5 V). More importantly, the direct surface fluorination proved more efficient than adding a fluorinated electrolyte additive (i. e., FEC). These results suggest that surface fluorination using XeF2 is of great promise for practical applications of high voltage positive materials for lithium‐ion batteries.PostprintPeer reviewe

In-Depth Analysis of the Conversion Mechanism of TiSnSb vs Li by Operando Triple-Edge X-ray Absorption Spectroscopy: a Chemometric Approach

The electrochemical cycling mechanism of the ternary intermetallic TiSnSb, a promising conversion-type negative electrode material for lithium batteries, was thoroughly studied by operando X-ray absorption spectroscopy (XAS) at three different absorption edges, i.e., Ti, Sn, and Sb K-edge. Chemometric tools such as principal component analysis and multivariate curve resolution-alternating least squares were applied on the extensive data set to extract the maximum contained information in the whole set of operando data. The evolution of the near-edge (XANES) fingerprint and of the extended fine-structure (EXAFS) of the XAS spectra confirms the reversibility of the conversion mechanism, revealing that Ti forms metallic nanoparticles upon lithiation and binds back to both Sn and Sb upon the following delithiation. The formation of both Li7Sn2 and Li3Sb upon lithiation was also clearly confirmed. The application of chemometric tools allowed the identification of a time shift between the reaction processes of Sn and Sb lithiation, indicating that the two metals do not react at the same time, in spite of a certain overlap between their respective reaction. Furthermore, XANES and EXAFS fingerprint show that the Ti–Sn–Sb species formed after one complete lithiation/delithiation cycle is distinct from the starting material TiSnSb

Alginic acid-derived mesoporous carbonaceous materials (Starbon®) as negative electrodes for lithium ion batteries : Importance of porosity and electronic conductivity

Alginic acid-derived mesoporous carbonaceous materials (Starbon® A800 series) were investigated as negative electrodes for lithium ion batteries. To this extent, a set of mesoporous carbons with different pore volume and electronic conductivity was tested. The best electrochemical performance was obtained for A800 with High Pore Volume (A800HPV), which displays both the highest pore volume (0.9 cm3 g−1) and the highest electronic conductivity (84 S m−1) of the tested materials. When compared to a commercial mesoporous carbon, A800HPV was found to exhibit both better long-term stability, and a markedly improved rate capability. The presence of a hierarchical interconnected pore network in A800HPV, accounting for a high electrolyte accessibility, could lay at the origin of the good electrochemical performance. Overall, the electronic conductivity and the mesopore size appear to be the most important parameters, much more than the specific surface area. Finally, A800HPV electrodes display similar electrochemical performance when formulated with or without added conductive additive, which could make for a simpler and more eco-friendly electrode processing

Sustainable polysaccharide-derived mesoporous carbons (Starbon®) as additives in lithium-ion batteries negative electrodes

For the first time, polysaccharide-derived mesoporous carbonaceous materials (Starbon®) are used as carbon additives in Li-ion battery negative electrodes. A set of samples with pore volumes ranging from ≈0 to 0.91 cm3 g-1 was prepared to evidence the role of porosity in such sustainable carbon additives. Both pore volume and pore diameter have been found crucial parameters for improving the electrodes performance e.g. reversible capacity. Mesoporous carbons with large pore volumes and pore diameters provide efficient pathways for both lithium ions and electrons as proven by the improved electrochemical performances of Li4Ti5O12 (LTO) and TiO2 based electrodes compared to conventional carbon additives. The mesopores provide easy access for the electrolyte to the active material surface, and the fibrous morphology favors the connection of active materials particles. These results suggest that polysaccharide-derived mesoporous carbonaceous materials are promising, sustainable carbon additives for Li-ion batteries