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[交流] 巴黎西岱大学Prof. Benoit Limoges 课题组招2024CSC博士生，电化学，电池方向

PHD Project: Towards the development of an innovative concept of rechargeable aqueous hybrid zinc/Br2 battery with high performances

The management of electrical grids involves storing surplus electricity during periods of low demand so that it can be used during periods of high demand. While it is currently dominated by hydroelectric dams (96%), technologies such as batteries and supercapacitors are emerging. This shift is driven by the need to accommodate increasing intermittent renewable energy production in response to climate change. Currently, the main battery chemistry starting to be integrated into the stationary grid storage is the lithium-ion technology. However, it is hard to envision its massive
implementation due to the rising costs of required raw materials (e.g. Li, Co, Ni), competitive uses, and safety issues due to its inherent flammability. Future battery technologies thus have to meet several requirements, including production cost < 100 €/kWh, safety (non- flammability), lifespan
> 10 years or 5000 cycles, energy efficiency > 75%, energy density > 50 Wh/kg, self-discharge < 1% per day, enhanced recyclability, easier maintenance and larger operating temperature range (-30 to 50 °C).[1] To meet these requirements, several technologies based on electrochemical
storage approaches in aqueous electrolytes are currently under development, but their practical applications are often limited by complex architectures, the use of scarce metals, difficult maintenance or short service life. In this context, the Zn/Br2 aqueous system has been the subject of intensive researches as well as commercialization effort.[2] The use of zinc and bromine is attractive because both elements are earth-abundant and can lead to a high nominal cell voltage of 1.8 V. However, the formation of zinc dendrites at the anode and corrosive bromine at the cathode,
with the recurring problem of cross-reaction of soluble Br2/Br3-species with the anode, limit the
performances.

The proposed PhD project relies on innovative solutions to efficiently exploit the Zn2+/Zn and Br2/Brredox couples at the anode and cathode, respectively. The main objectives of the PhD work will be to overcome several of the current limitations of zinc-bromine batteries by notably playing with the nature and electrolyte composition in view to: (i) improve the Coulombic efficiency as well as to reduce the self-discharge, (ii) to avoid the need for an expensive anion selective membrane, (iii) tolimit the formation of Zn dendrites and inhibit zinc corrosion, (iv) to maximize the energy densities with the deployment of strategies allowing an access to the highest possible concentrations in species, (v) to take advantage of chemicals that are cheap, non-toxic and environmental friendly, and (vi) to develop a simple battery cell architecture that is technically easy to assemble
and to recycle.To achieve these objectives, all the different tested systems will be thoroughly investigated in order to fully understand their physiochemical properties and to extract the key parameters which lead to the best performances. Characterization technics will include galvanostatic charge/discharge, cyclic voltammetry, chronoamperometry, spectroelectrochemistry, XPS, XRD, MEB, UV-vis, Raman and IR spectroscopies.Based on the already promising preliminary results obtained by the group, we anticipate that the strategy we are developing will provide groundbreaking solutions for future stationary energy storage.

[1] Z. Zhu et al Rechargeable Batteries for Grid Scale Energy Storage, Chem. Rev., 2022, 122, 16610.
[2] Y. Yin et al. Rechargeable aqueous zinc–bromine batteries: an overview and future perspectives, Phys. Chem. Chem. Phys., 2021, 23, 26070.
[3] Accessing the two-electron charge storage capacity of MnO2 in mild aqueous electrolytes. M. Mateos, N. Makivic, Y-S. Kim, B. Limoges, V. Balland, Adv. Energ. Mater., 2020, 10, 2000332.
[4] On the Unsuspected Role of Multivalent Metal Ions on the Charge Storage of a Metal Oxide Electrode in Mild Aqueous Electrolytes. Y-S. Kim, K. D. Harris, B. Limoges, V. Balland, Chem. Sci., 2019, 10, 8752–8763
[5] The role of Al3+-based aqueous electrolytes in the charge storage mechanism of MnOx cathodes.V. Balland, M. Mateo, A. Singh, C. Laberty-Robert, K. D. Harris, B. Limoges. Small, 2021, 17, 2101515.
[6] Evidence of Bulk Proton Insertion in Nanostructured Anatase and Amorphous TiO2 Electrodes.N. Makivic, J-Y. Cho, K. D. Harris, J-M. Tarascon, B. Limoges, V. Balland, Chem. Mater., 2021, 33, 3436–3448.
[7] Impact of reversible proton insertion on the electrochemistry of electrode materials operating in mild aqueous electrolytes: a case study with TiO2. N. Makivić, K. D. Harris, J-M. Tarascon, B. Limoges, V. Balland, Adv. Energ. Mater., 2023, 3, 2203122.
[8] Tuning the valence of MnOx cathodes reveals the universality of the proton-coupled electrodissolution/electrodeposition mechanism in rechargeable aqueous Zn batteries. A. Singh, C. Laberty-Robert, V. Balland, B. Limoges, Adv. Energ. Mater., 2023, 2301745.

SCIENTIFIC ENVIRONNEMENT
The PhD candidate will be part of the team « MER » (Electroanalytical methodologies and reactivity) from the Laboratory of Molecular Electrochemistry (LEM). One of the team's key areas of expertise is understanding electron transfer and charge transport mechanisms in electrodes based on
mesoporous and/or nanostructured semiconducting metal oxides (TiO2, SnO2, MnO2, ITO, …).[3-8]In recent years, the team has progressively shifted its research activities towards the development and characterization of innovative rechargeable aqueous batteries.

EXPECTED SKILLS OF THE PHD CANDIDATE：
The candidate must have a strong interest in electrochemical energy storage systems and, in particular, rechargeable aqueous batteries. He/she should also have a good knowledge of the electrochemistry of electrode materials and material characterization, the chemistry of aqueous solutions and concentrated electrolytes, and if possible the chemistry of redox-active molecules.
最好有托福或雅思成绩，CSC（公派）项目留学生。

Prof. Benoit Limoges and Assistant Professor Dr. Mathieu Branca是个专注于科研的老师，平易近人，认真负责，关心留学生。科研成果较好，近年在Advance Energy Materials, Small 等高水平杂志上发表多篇文章，该课题进展良好，对想出国读博的同学是很好的机会。巴黎西岱大学是国际知名高校，全球排名US new 前50，软科前100， QS自然科学前100。

联系方式：E-MAILS: limoges@u-paris.fr ; mathieu.branca@u-paris.fr

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