Loïc Baggetto

Lithium-Ion (De)Insertion Reaction of Germanium Thin-Film Electrodes: An Electrochemical and In Situ XRD Study

Germanium is a promising negative electrode candidate for lithium-ion thin-film batteries because of its very high theoretical storage capacity. When assuming full conversion of the material into the room-temperature equilibrium lithium saturated germanium phase Li 22 Ge 5 , a theoretical capacity of 1625 mAh g -1 or 8643 mAh cm -3 of germanium starting material is expected. However, the lithium-ion (de)insertion reaction of pure germanium thin films and the resulting electrochemical thermodynamic and kinetic properties are not yet fully understood. To address some of these questions, a combined electrochemical and in situ X-ray diffraction (XRD) study is presented. Results on the crystallographic phase transitions, occurring upon Li-(de)insertion of evaporated and sputtered germanium thin films are discussed. Moreover, the difference in reaction between evaporated and sputtered films is addressed. In addition, a detailed electrochemical investigation (cyclic voltammetry, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy) of evaporated germanium is conducted. The results reveal that evaporated and sputtered germanium crystallizes into Li 15 Ge 4 when fully inserted with Li ions. This composition corresponds to a maximum storage capacity of 1385 mAh g -1 or 7366 mAh cm -3 of germanium starting material.

In Situ Ambient Pressure X-ray Photoelectron Spectroscopy Studies of Lithium-Oxygen Redox Reactions

The lack of fundamental understanding of the oxygen reduction and oxygen evolution in nonaqueous electrolytes significantly hinders the development of rechargeable lithium-air batteries. Here we employ a solid-state Li4+xTi5O12/LiPON/LixV2O5 cell and examine in situ the chemistry of Li-O2 reaction products on LixV2O5 as a function of applied voltage under ultra high vacuum (UHV) and at 500 mtorr of oxygen pressure using ambient pressure X-ray photoelectron spectroscopy (APXPS). Under UHV, lithium intercalated into LixV2O5 while molecular oxygen was reduced to form lithium peroxide on LixV2O5 in the presence of oxygen upon discharge. Interestingly, the oxidation of Li2O2 began at much lower overpotentials (~240 mV) than the charge overpotentials of conventional Li-O2 cells with aprotic electrolytes (~1000 mV). Our study provides the first evidence of reversible lithium peroxide formation and decomposition in situ on an oxide surface using a solid-state cell, and new insights into the reaction mechanism of Li-O2 chemistry.

Intrinsic thermodynamic and kinetic properties of Sb electrodes for Li-ion and Na-ion batteries: experiment and theory

A detailed comparative study between the electrochemical lithiation and sodiation of pure antimony (Sb), relating changes in structural, thermodynamic, kinetic and electrochemical properties has been carried out. For this purpose, a wide range of measurements using electrochemical (galvanostatic cycling, GITT, PITT), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) methods as well as density functional theory (DFT) based investigations have been undertaken. Assessment of the thermodynamics reveals that the reaction proceeds identically during the first and second cycles for Li whereas it differs between the first and subsequent cycles for Na as the reaction with Na proceeds through a different pathway associated with the formation of amorphous NaxSb phases. For the first time we rationalize the amorphization of NaxSb phases by the long ranged strain propagation due to Na-vacancy compared to Li–Sb. At full discharge, our XRD results show for the first time that a minor fraction of hexagonal Li3Sb forms concomitantly with cubic Li3Sb. The XRD results confirm that Sb crystallizes into hexagonal Na3Sb at full sodiation. The kinetics of the reaction is assessed by rate performance tests which highlight that both Li and Na can diffuse rapidly throughout micron thick films at room temperature. However, it is found that the (de)insertion of Li provides lower overpotentials and larger storage capacities compared to Na. The difference in rate performance is complemented by diffusion coefficient determinations near the 0 V region where both materials are crystallized into M3Sb (M = Li, Na). Interestingly, calculations show that the energy barrier for near-neighbor vacancy migration, predominant in these close-packed phases, is about twice for Na than for Li. Our analysis tries to relate the lower intrinsic diffusivity of Na compared to Li with the long-range strain propagation induced by the former, thereby leading to an intrinsic origin of differences in rates, mechanical properties and amorphization. Finally, the surface chemistry of Sb electrodes cycled in NaClO4 dissolved in pure PC with(out) the addition of 5 wt% EC or FEC shows presence of ethers and NaF for the EC- and FEC-based electrolytes, respectively, and SEI films rich in Na-based carbonates.

Sonochemical functionalization of mesoporous carbon for uranium extraction from seawater

Extracting uranium from seawater is challenging due to its low concentration (3.3 ppb) and the myriad of competing ions. Mesoporous carbon materials provide a high surface area alternative to the traditional polymeric fiber braids developed for seawater extractions, specifically uranium extraction. In this work, sonochemical grafting of acrylonitrile onto the pores of soft-templated mesoporous carbons followed by its conversion to amidoxime functionalities was used to prepare an effective sorbent material with a high density of binding sites. Pore blockage, often observed for free radical polymerization, leads to poor adsorbent performance but can be easily overcome by the use of ultrasound during polymerization. Parameters such as surface area and surface pre-treatment, sonication intensity, solvent system, and monomer/initiator ratios were varied to optimize the polymerization and uranium adsorption capacity while not blocking the porosity, a significant hurdle in the utilization of functionalized porous materials. The results show that neither the surface oxidation with nitric acid nor CO2 activation alone is sufficient to cause significant improvement in grafting and uranium uptake. However, when coupled together, a greatly enhanced performance of the adsorbent materials was observed.

Probing the electrode/electrolyte interface in the lithium excess layered oxide Li1.2Ni0.2Mn0.6O2

A detailed surface investigation of the lithium-excess nickel manganese layered oxide Li1.2Ni0.2Mn0.6O2 structure was carried out using X-ray photoelectron spectroscopy (XPS), total electron yield and transmission X-ray absorption spectroscopy (XAS), and electron energy loss spectroscopy (EELS) during the first two electrochemical cycles. All spectroscopy techniques consistently showed the presence of Mn(4+) in the pristine material and a surprising reduction of Mn at the voltage plateau during the first charge. The Mn reduction is accompanied by the oxygen loss revealed using EELS. Upon the first discharge, the Mn at the surface never fully recovers back to Mn(4+). The electrode/electrolyte interface of this compound consists of the reduced Mn at the crystalline defect-spinel inner layer and an oxidized Mn species simultaneously with the presence of a superoxide species in the amorphous outer layer. This proposed model signifies that oxygen vacancy formation and lithium removal result in electrolyte decomposition and superoxide formation, leading to Mn activation/dissolution and surface layer-spinel phase transformation. The results also indicate that the role of oxygen is complex and significant in contributing to the extra capacity of this class of high energy density cathode materials.

Honeycomb-structured silicon: remarkable morphological changes induced by electrochemical (de)lithiation.

Arrays of silicon honeycombs are evaluated as a negative electrode material for lithium-ion microbatteries. The morphological changes of the structure are investigated by means of scanning electron microscopy (SEM) and it is revealed that the honeycomb structure can reversibly withstand huge mechanical deformations. Free-standing structures are envisioned to serve advanced future applications, such as switchable sieves and microelectromechanical systems.

Deposition of TiN and TaN by Remote Plasma ALD for Cu and Li Diffusion Barrier Applications

TaN and TiN films were deposited by remote plasma atomic layer deposition (ALD) using the combinations of Ta[N(CH 3 ) 2 ] 5 precursor with H 2 plasma and TiCl 4 precursor with H 2 -N 2 plasma, respectively. Both the TaN and TiN films had a cubic phase composition with a relatively low resistivity (TaN: 380 μΩ cm; TiN: 150 μΩ cm). Dissimilar from the TiN properties, the material properties of the TaN films were found to depend strongly on the plasma exposure time. Preliminary tests on planar substrates were carried out revealing the potential of the TaN and TiN films as Cu and Li diffusion barriers in through-silicon via and silicon-integrated thin-film battery applications, respectively. For the specific films studied, it was found that TiN showed better barrier properties than TaN for both application areas. The TiN films were an effective barrier to Cu diffusion and had no Cu diffusion for anneal temperatures up to 700°C. The TiN films showed low Li intercalation during electrochemical charging and discharging.

Elucidating the Phase Transformation of Li4Ti5O12 Lithiation at the Nanoscale

This work provides insight regarding the fundamental lithiation and delithiation mechanism of the popular lithium ion battery anode material, Li4Ti5O12 (LTO). Our results quantify the extent of reaction between Li4Ti5O12 and Li7Ti5O12 at the nanoscale, during the first cycle. Lithium titanates discharge (lithiation) and charge (delithiation) reactions are notoriously difficult to characterize due to the zero-strain transition occurring between the end members Li4Ti5O12 and Li7Ti5O12. Interestingly, however, the latter compound is electronically conductive, while the former is an insulator. We take advantage of this critical property difference by using conductive atomic force microscopy (c-AFM) to locally monitor the phase transition between the two structures at various states of charge. To do so, we perform ex situ characterization on electrochemically cycled LTO thin-films that are never exposed to air. We provide direct confirmation of the manner in which the reaction occurs, which proceeds via percolation channels within single grains. We complement scanning probe analyses with an X-ray photoelectron spectroscopy (XPS) study that identifies and explains changes in the LTO surface structure and composition. In addition, we provide a computational analysis to describe the unique electronic differences between LTO and its lithiated form.

Understanding the Role of NH4F and Al2O3 Surface Co-modification on Lithium-Excess Layered Oxide Li1.2Ni0.2Mn0.6O2

In this work we prepared Li1.2Ni0.2Mn0.6O2 (LNMO) using a hydroxide co-precipitation method and investigated the effect of co-modification with NH4F and Al2O3. After surface co-modification, the first cycle Coulombic efficiency of Li1.2Ni0.2Mn0.6O2 improved from 82.7% to 87.5%, and the reversible discharge capacity improved from 253 to 287 mAh g(-1) at C/20. Moreover, the rate capability also increased significantly. A combination of neutron diffraction (ND), high-resolution transmission electron microscopy (HRTEM), aberration-corrected scanning transmission electron microscopy (a-STEM)/electron energy loss spectroscopy (EELS), and X-ray photoelectron spectroscopy (XPS) revealed the changes of surface structure and chemistry after NH4F and Al2O3 surface co-modification while the bulk properties showed relatively no changes. These complex changes on the materials surface include the formation of an amorphous Al2O3 coating, the transformation of layered material to a spinel-like phase on the surface, the formation of nanoislands of active material, and the partial chemical reduction of surface Mn(4+). Such enhanced discharge capacity of the modified material can be primarily assigned to three aspects: decreased irreversible oxygen loss, the activation of cathode material facilitated with preactivated Mn(3+) on the surface, and stabilization of the Ni-redox pair. These insights will provide guidance for the surface modification in high-voltage-cathode battery materials of the future.

Effect of morphology and manganese valence on the voltage fade and capacity retention of Li[Li2/12Ni3/12Mn7/12]O2.

We have determined the electrochemical characteristics of the high voltage, high capacity Li-ion battery cathode material Li[Li2/12Ni3/12Mn7/12]O2 prepared using three different synthesis routes: sol-gel, hydroxide coprecipitation, and carbonate coprecipitation. Each route leads to distinct morphologies and surface areas while maintaining the same crystal structures. X-ray photoelectron spectroscopy (XPS) measurements reveal differences in their surface chemistries upon cycling, which correlate with voltage fading. Indeed, we observe the valence state of Mn on the surface to decrease upon lithiation, and this reduction is specifically correlated to discharging below 3.6 V. Furthermore, the data shows a correlation of the formation of Li2CO3 with the Mn oxidation state from the decomposition of electrolyte. These phenomena are related to each materials electrochemistry in order to expand upon the reaction mechanisms taking place-specifically in terms of the particle morphology produced by each synthetic approach.