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新虫 (小有名气)

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[交流] 巴黎大学Benoit Limoges 课题组招2022 CSC 博士生 - Zn-Organic Battery

单位：University of Paris
实验室：Laboratoire d’Electrochimie Moléculaire分子电化学实验室(LEM)
要求：化学、材料或者物理背景，2022年7月份取得硕士学位，最好有托福或雅思成绩（英语B1水平），CSC（公派）项目留学生。

本课题研究方向为生命分析，Benoit Limoges 教授为ED388博士生院在巴黎大学的主要负责人，导师认真负责，关心留学生，不论在科研还是生活都给了大家很多帮助。并且该课题在组里进展良好，文章质量和数量一直不错，所以对想出国读博的同学是很好的机会。

The PhD candidate will be part of the team « MER » (Electroanalytical methodologies and reactivity). A strong expertise of the team is the understanding of the electron transfer/charge transport echanisms in mesoporous and/or nanostructured semiconductive metal oxide electrodes (TiO2, SnO2, MnO2, ITO, …). In the recent years, the team has progressively oriented its research activities towards the conception and characterization of innovative rechargeable aqueous batteries.

联系方式：Benoit Limoges limoges@u-paris.fr
Batiment Lavoisier - 7ème étage - Case 7107
15, rue Jean-Antoine de Baïf
75205 PARIS CEDEX 13 - FRANCE

研究计划如下，更详细的可以查阅附件或者邮件询问导师。
Title: Towards a rational and quantitative understanding of the charge storage mechanism in aqueous rechargeable zinc/organic batteries
Keywords: Physical sciences and Engineering
Description of subjet:
General Context:
An increasing concern regarding the global environment and energy sustainability is driving research and development of clean energy storage technologies. Currently, lithium-ion batteries (LIBs), which operate through the reversible insertion of Li ions into an oxide cathode and a graphite anode, are the most prominent candidate, being commercially used in numerous portable electronic devices and electric vehicles (EVs).1 It is expected that the number of LIBs used will exponentially rise as the EV market grows and the utility industry begins to adopt LIBs. Because of this, there is growing concern surrounding not only the availability of Li but also the accessibility of heavy metal ions (i.e., cobalt and nickel) included in the metal oxide cathodes, which would impact the sustainability and cost of LIBs.2 For this reason, other battery chemistries that utilize cheaper and earth abundant elements are sought after as “beyond Li-ion” technologies. Among those, rechargeable batteries based on the reversible insertion of multivalent ions such as Ca2+, Mg2+, Zn2+, Al3+ into organic electrode materials have attracted considerable attention in recent years.3 The main advantage of these hybrid battery chemistries is an access to low-cost and eco-sustainable electrochemical storage systems, made from abundant, non-toxic, and easily recyclable elements. In particular, aqueous zinc-ion batteries (ZIBs) pairing a zinc metal anode with an organic redox-active cathodes in an aqueous electrolyte are considered among the most promising candidates for the development of low-cost energy storages at the grid-scale level.3a,c The key advantages of a Zn metal anode is that it can deliver a high specific capacity (820 mAh g?1) as well as a high volumetric capacity (5851 mAh cm?3). In addition, zinc is abundant, cheap, nontoxic, and easy to process. Moreover, in contrast to other multivalent metal ions, its reducing potential is sufficiently high (E0 = ?0.76 V vs. NHE) for allowing its reversible electroplating in an aqueous electrolyte without significant interference of the hydrogen evolution reaction. In addition, water-based electrolytes are intrinsically safe and do not rely heavily on battery management systems, thereby providing robustness and cost advantages over competing lithium-ion batteries that use volatile and toxic organic electrolytes.3 For this reason, the coupling of zinc before these aqueous batteries become practically feasible. One major problem with MV ions is their sluggish diffusion kinetics in solid-state insertion hosts, which can translate into a lack of appreciable electrochemical activity. Another problem is that, similar to what has been reported for inorganic materials, many papers report a charge storage mechanism involving Zn2+ as the inserting species to compensate for the negative charges generated in the organic cathode material.3 However, an increasing number of studies, including our own,4 have recently reported that the observed promising electrochemical performance in aqueous Zn-ion systems, is in fact mostly due to the insertion of protons rather than MV ions into the cathode, making them technically a proton hybrid battery. This misidentification of the charge carrier ions imposes severe consequences on the research and development in the MIB field. Therefore, it calls for further research to definitely clarify the actual ionic species involved as charge carriers in rechargeable aqueous zinc/organic battery.

Research project:
The main objective of the present PhD project is to better understand the charge storage mechanism of aqueous rechargeable zinc/organic hybrid batteries and to elucidate the true nature of the charge carriers involved in the reversible insertion process at the positive organic electrode. It is thus by essence a fundamental research project. To do so, we will first investigate composite electrodes based on model redox-active compounds (quinones) that we will characterize not only by different electrochemical techniques (galvanometry, cyclic voltammetry, spectroelectrochemistry, etc...), but also by different material characterization techniques (XPS, XRD, in operando Raman spectroscopy, NMR, SEM, ...). In a second step, we will examine the charge storage mechanism with respect to organic redox-active polymers, which have the merit of being less subject to dissolution in aqueous electrolytes. In parallel, aqueous electrolytes of different nature, pH and concentration will be examined, up to so-called water-in-salt electrolytes.

Expected skills of the PhD candidate:

To have a good knowledge in electrochemistry, electrochemical charge storage systems, electrode materials, material chemistry and material characterization. To have also a strong interest for the field of battery.

References:
[1] Manthiram, A., Nat. Commun. 2020, 11, 1550.
[2]. Grey, C. P.; Tarascon, J. M. Nat. Mater., 2017, 16, 45?56.
[3] (a) K. Qin, J. Huang, K. Holguin, C. Luo, Energy Environ. Sci., 2020, 13, 3950-3992. (b) P. Poizot, J. Gaubicher, S. ven Renault, L. Dubois, Y. Liang, Y. Yao, Chem. Rev., 2020, 120, 14, 6490–6557. (c) J. Huang, X. Dong, Z. Guo, Y. Wang, Angew. Chem. Int., 2020, 59, 18322-18333.
[4] (a) V. Balland, M. Mateo, A. Singh, C. Laberty-Robert, K. D. Harris, B. Limoges. Small, 2021, 17, 2101515. (b) N. Makivic, J-Y. Cho, K. D. Harris, J-M. Tarascon, B. Limoges, V. Balland, Chem. Mater., 2021, 33, 3436–3448. (c) M. Mateos, N. Makivic, Y-S. Kim, B. Limoges, V. Balland, Adv. Energ. Mater., 2020, 3, 7610–7618. (d) Y-S. Kim, K. D. Harris, B. Limoges, V. Balland, Chem. Sci., 2019, 10, 8752–8763. (e) Mateos, K. D. Harris, B. Limoges, V. Balland, ACS Applied Energy Materials, 2020, 3, 8, 7610–7618

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