Covalent vs. non-covalent redox functionalization of C-LiFePO4 based electrodes

During high rate utilization of porous Li battery, Li+ refuelling from the electrolyte limits the discharge kinetics of positive electrodes. In the case of thick electrodes a strategy to buffer the resulting sharp drop of Li+ concentration gradient would be to functionalize the electrode with anionic based redox molecules (RMR) that would be therefore able to relay intercalation process. The occurrence of these RMR in the electrode should not however, induce adverse effect on Li intercalation processes. In this respect, this work studies the effect of functionalizing LFPC based electrodes by either covalent or non-covalent chemistry, on Li intercalation kinetics. To do so, model molecules containing a nitro group were introduced at the surface of both carbon conducting additives and active material (C-LiFePO4). It is shown that presumably due to formation of sp(3) defects, covalent anchoring using diazonium chemistry inhibits the intercalation kinetics in C-FePO4. On the contrary, if molecules such as pyrene derivatives are immobilized by pi-staking interactions, Li intercalation is not impeded. Therefore non-covalent functionalization of pyrene based RMR appears as a promising route to relay Li intercalation reaction during high power demand. The framework for future development of this strategy is discussed. (C) 2013 Elsevier B.V. All rights reserved

New Concept to Boost Energy and Power Peformance of Practical Electrochemical Devices

International audienc

In situ redox functionalization of composite electrodes for high power-high energy electrochemical storage systems via a non-covalent approach

The growing demand for new global resources of clean and sustainable energy emerges as the greatest challenge in today\u27s society. For numerous applications such as hybrid vehicles, electrochemical storage systems simultaneously require high energy and high power. For this reason, intensive researches focus on proposing alternative devices to conventional Li battery and supercapacitors. Here, we report a proof of concept based on non-covalent redox functionalization of composite electrodes that may occur either during the calendar life or during the device functioning. The active material, a multi-redox pyrene derivative, is initially contained in the electrolyte. No additional benchmarking step is therefore required, and it can, in principle, be readily applied to any type of composite electrode (supercapacitors, battery, semi-solid flow cell etc.). Accordingly, a practical carbon fiber electrode that is 10 mg cm(-2) loaded can deliver up to 130 kW kg(electrode)(-1) and 130 Wh kg(electrode)(-1) with negligible capacity loss over the first 60 000 charge/discharge cycles

New concept and electrochemistry of in situ non-covalent immobilization of redox molecules for energy storage applications

International audienc

EU agriculture and innovation: what role for the cap?

One of the current European public debates concerns the future of the Common Agricultural Policy (CAP), the most integrated European policy created over the last 60 years. Given the challenges of sustainable food and nutrition security, innovation should be an important aspect of that debate. Our organisations, Wageningen University & Research (Wageningen UR) and Institut National de la Recherche Agronomique (INRA), believe that a broad dissemination of results from our research contributes to creating benefit. This benefit is created not only through novel applications of technologies but also by working on societal challenges through dialogue with society and contributing to government policy and legislation. We are both concerned and thrilled about the future of the CAP. Concerned because of the need to take the right science-based decisions to ensure the long-term future of European agriculture as one of the most innovative, socially responsible and sustainable sectors in the world. And thrilled, because contributing to this promising long-term future provides our institutions with great challenges for partnerships with governments, farmers, consumers, private business, NGOs and scientific peers. The authors of this policy brief, experts in European research and innovation policy as well as in agricultural policy, have tried to take a critical look at the current CAP and more specifically how it supports innovation for European agriculture, food and rural areas. They have come up with suggestions to take on board in the public debate on the future CAP. Even it is not easy to have à clear picture of the total amount of regional, national and European public funds made available for innovation in agriculture, food and rural areas, we think that the share of the CAP budget specifically devoted to innovation (today, at best a few percentage points of Pillar II expenditure) is too limited. It should at least be doubled in the next CAP. The authors want to thank policy officers in the Dutch and French Ministries, as well as in the European Commission, for stimulating discussions. They very warmly thank Professor Alan Matthews for his very careful review of an earlier draft of the paper and his very useful remarks and suggestions. The Dutch authors thank the Dutch Ministry of Agriculture, Nature and Food Quality for financing part of this study and their travel expenses. We look forward to the responses in the public debate on the thoughts reflected in in the public debate on the thoughts reflected in this policy brief

Identification of the master sex determining gene in Northern pike (Esox lucius) reveals restricted sex chromosome differentiation.

Teleost fishes, thanks to their rapid evolution of sex determination mechanisms, provide remarkable opportunities to study the formation of sex chromosomes and the mechanisms driving the birth of new master sex determining (MSD) genes. However, the evolutionary interplay between the sex chromosomes and the MSD genes they harbor is rather unexplored. We characterized a male-specific duplicate of the anti-Müllerian hormone (amh) as the MSD gene in Northern Pike (Esox lucius), using genomic and expression evidence as well as by loss-of-function and gain-of-function experiments. Using RAD-Sequencing from a family panel, we identified Linkage Group (LG) 24 as the sex chromosome and positioned the sex locus in its sub-telomeric region. Furthermore, we demonstrated that this MSD originated from an ancient duplication of the autosomal amh gene, which was subsequently translocated to LG24. Using sex-specific pooled genome sequencing and a new male genome sequence assembled using Nanopore long reads, we also characterized the differentiation of the X and Y chromosomes, revealing a small male-specific insertion containing the MSD gene and a limited region with reduced recombination. Our study reveals an unexpectedly low level of differentiation between a pair of sex chromosomes harboring an old MSD gene in a wild teleost fish population, and highlights both the pivotal role of genes from the amh pathway in sex determination, as well as the importance of gene duplication as a mechanism driving the turnover of sex chromosomes in this clade

First principles electronic structure of spinel LiCr2O4: A possible half-metal?

We have employed first-principles electronic structure calculations to examine the hypothetical (but plausible) oxide spinel, LiCr2O4 with the d^{2.5} electronic configuration. The cell (cubic) and internal (oxygen position) structural parameters have been obtained for this compound through structural relaxation in the first-principles framework. Within the one-electron band picture, we find that LiCr2O4 is magnetic, and a candidate half-metal. The electronic structure is substantially different from the closely related and well known rutile half-metal CrO2. In particular, we find a smaller conduction band width in the spinel compound, perhaps as a result of the distinct topology of the spinel crystal structure, and the reduced oxidation state. The magnetism and half-metallicity of LiCr2O4 has been mapped in the parameter space of its cubic crystal structure. Comparisons with superconducting LiTi2O4 (d^{0.5}), heavy-fermion LiV2O4 (d^{1.5}) and charge-ordering LiMn2O4 (d^{3.5}) suggest the effectiveness of a nearly-rigid band picture involving simple shifts of the position of E_F in these very different materials. Comparisons are also made with the electronic structure of ZnV2O4 (d^{2}), a correlated insulator that undergoes a structural and antiferromagnetic phase transition.Comment: 9 pages, 7 Figures, version as published in PR

Some Directions for Performance Improvement of Li-Ion Batteries out of Usual Paths

Recent developments at IMN will be shared on several research directions out of usual paths for performance improvement of Li-ion batteries. We will focus on innovative surface modifications of electrode components, new electrode compositions and architectures, and failure mechanism upon cycling by in-depth characterization through coupled advanced spectroscopic techniques. A molecular grafting approach has been proposed as a way to modify the interfacial chemical reactivity of oxide materials, which is detrimental to their long-term energy storage properties as electrodes of Li-ion batteries. Surface derivatization of powder oxide materials such as Li1.2V3O8 and Li(Mn,Ni)2O4 was accomplished by in situ electrografting of a diazonium salt during Li-ion intercalation, leading to a covalently bonded organic multilayer. Charge transfer is not impeded, while electrolyte decomposition is inhibited thus increasing the cycle life and decreasing the self-discharge. Carbon additives of classical porous electrodes occupy a large volume fraction which is lost for charge storage. Redox functionalization of the surface of some carbon additives has been successfully achieved through non-covalent grafting chemistry using multi-redox pyrene molecules synthesized on purpose. Such functionalized carbon additives have been used to increase the stored energy and power of C-coated LFP porous electrodes. Thicker electrodes are needed for higher energy density Li-ion batteries. We evaluate different directions in order to design new innovative electrode architectures for such a purpose. Our grafting chemistry has been further developed to achieve molecular junctions between non-carbon-coated LFP and multiwall carbon nanotubes (MWCNT) using a designed thiophene-based conjugated molecule. The strategy enables original architecturing of the cathode of Li-ion batteries, with the individual MWCNT being electronically nanocontacted at the surface of LFP grains. This advancement leads to much higher specific capacity and better capacity retention for non calendared thick electrodes, for which the electronic wiring of the electroactive material grains is a critical issue. Another direction followed is the use of conducting polymer additives in porous electrodes, which are able to act as both conducting fillers and mechanical reinforcement materials. We have synthesized a new form of lithium doped PANI, the excellent properties of which in terms of specific capacity, stability on cycling and rate capability will be presented. The coating of bare LFP particles with thin layers of this new Li-doped PANI allows surpassing the performance of commercial carbon coated LFP thick electrodes. The role of this PANI additive into millimetric thick electrodes of NMC material will also be discussed. Future developments of higher energy density Si-based Li-ion batteries depend on the mastering of side reactions at the Si anode. We will compare the SEI composition and morphology at the Si surface upon cycling in half cell and full Li-ion cell configurations using a combination of 7Li, 19F MAS NMR, XPS, TOF-SIMS and STEM-EELS. The origin of the much faster aging of Si-based full cells versus half cells and future directions for improvement will be discusse