Fabrication and advanced caracterizations of all-solid state micro-supercapacitors for pulsed regimes in severe environments – ARTEMIS

The proposed work takes a multi-faceted approach. Firstly, capacitive storage materials in thin-film technology will be synthesized (Vanadium and Ruthenium oxides, nitrides and oxynitrides) by magnetron sputtering. Structure/property relationships will be finely analyzed (XRD, XRR, XAS, XPS, X-ray fluorescence, EIS etc.) to determine the best synthesis conditions for using these materials as MSCs electrodes. MSCs will then be fabricated in both symmetrical and asymmetrical configurations, in order to increase the potential range of the micro-devices and thus multiply their energy densities. In parallel, the team will synthesize a LiOH solid electrolyte deposited by Atomic Layer Deposition (ALD) and demonstrate its electrochemical properties, in particular the mechanisms enabling charge transfer in the all-solid state configuration with the electrode materials developed upstream. Then, all-solid-state MSCs will be fabricated using processes from the microelectronics industry, with the aim of demonstrating collective fabrication (several hundred components on a single Silicon wafer). A wafer-scale mapping approach (chemical, electrochemical, structural, electrical, etc.) will be developed to verify the homogeneity of the various deposits/devices on several scales. Finally, advanced in-situ/operando characterizations will also be carried out as part of the ARTEMIS project on our materials and components to understand the storage mechanisms of our MSCs. As part of the ARTEMIS project, new all-solid-state MSCs will be developed to power the miniaturized Internet of Things. Binary or ternary thin films of transition metal oxides, nitrides or oxynitrides will be studied as new pseudo-capacitive electrodes and solid electrolytes. These thin films will be deposited by magnetron sputtering, where the deposition atmosphere (Ar, N2, O2) will be modulated to meet the required needs and adjust the electrode composition, and by atomic layer deposition (ALD) for solid electrolyte deposition.

- A combinatorial sputtering methodology has been implemented on the mixed Vanadium/Tungsten nitride system by playing on the possibility of co-sputtering in an Ar/N2 plasma two metal targets on a silicon substrate, either rotating or fixed. By not rotating the substrate, we can create a gradient of composition and therefore of properties. Depending on the zone under consideration, the composition will vary from vanadium-rich to tungsten-rich. In parallel, we have developed wafer-scale mapping to highlight these variations in composition and therefore properties: microdiffraction, microX-ray fluorescence, electronic conductivity and electrochemical mapping. For this last part, we have fully designed an automated measurement bench that enables us to carry out measurements on a complete wafer without the need to cut it into pieces, as is customary.
This work was published in the journal Chemistry of Materials in 2023

- Exceptional performance was achieved on Ruthenium nitride nanoplates, previously electrochemically oxidized. Over and above these performances, by coupling numerous characterization methods (ex situ, in situ and operando), the storage mechanisms were revealed. It has been shown that the «secret« of these performances lies in the control of a thin layer of hydrated ruthenium oxide material on the ruthenium nitride support, which is a very good electronic conductor.
This work has been published in Nature Materials and in Small in 2024

- Optimization of the deposition conditions for vanadium nitride electrodes has been launched, and has enabled us to push back the limits of cycling stability for these materials in liquid KOH. 150,000 charge/discharge cycles were achieved with no significant loss (< 80%) in coulombic efficiency and retention capacity.
This work was published in the journal Advanced Energy Materials in 2023.

- In addition to these already-published highlights, we have also launched work that is, for the moment, very promising... For example, we have launched work on MoN molybdenum nitrides, which are materials that can be «faced« with ruthenium nitride to make asymmetrical devices, promising in KOH liquid media.

- Trials to fabricate a solid electrolyte, not in LiOH as hoped at the time the project was written (subject abandoned...), using a hydrogel approach are promising, with a proof of concept well on the way to validation for a symmetrical RuN / RuN MSC - Finally, we recently received/designed electrochemical cells that will enable us to monitor, in situ and operando, the behavior of electrodes and/or devices using Raman spectroscopy and X-ray diffraction.

Bukola Jolayemi, Gaëtan Buvat, Pascal Roussel, Christophe Lethien. [Review] Emerging Capacitive Materials for On-Chip Electronics Energy Storage Technologies. Batteries, 2024, 10, 65 p. ?10.3390/batteries10090317?. ?hal-04723253?
Khac Huy Dinh, Grace Whang, Antonella Iadecola, Houssine Makhlouf, Antoine Barnabé, et al.. Nanofeather ruthenium nitride electrodes for electrochemical capacitors. Nature Materials, 2024, Nature Materials, ?10.1038/s41563-024-01816-0?. ?hal-04495652?
Khac Huy Dinh, Grace Whang, Marielle Huve, David Troadec, Antoine Barnabé, et al.. High Capacitance Porous Ruthenium Nitride Films with High Rate Capability for Micro-Supercapacitors. Small, In press, ?10.1002/smll.202402607?. ?hal-04610328?
Aiman Jrondi, Gaëtan Buvat, Francisco de La Pena, Maya Marinova, Marielle Huvé, et al.. Major Improvement in the Cycling Ability of Pseudocapacitive Vanadium Nitride Films for Micro-Supercapacitor. Advanced Energy Materials, 2023, 13 (9), ?10.1002/aenm.202203462?. ?hal-03959151?
Khac Huy Dinh, Kevin Robert, Joelle Thuriot-Roukos, Marielle Huvé, Pardis Simon, et al.. Wafer-Scale Performance Mapping of Magnetron-Sputtered Ternary Vanadium Tungsten Nitride for Microsupercapacitors. Chemistry of Materials, 2023, ?10.1021/acs.chemmater.3c01803?. ?hal-04241602?

ARTEMIS is part of an ambitious valorisation project around micro-energy storage devices for for autonomous and connected objects, forming what is called now Internet of Things (IoT). For about ten years, thie preset consortium is involved in the field of powering millimeter network nodes by developing thin-films materials and micro-devices such as all-solid-state micro-batteries, dielectric micro-capacitors and electrochemical micro-supercapacitors. These devices are designed with the aim of fulfilling the requirements of current hardware IoT key challenges such as high areal energy and power density (from 1 to 10 mWh/cm-2), low on-board mass (from 0.2 to 20 mg) at millimeter to micrometer scale in terms of surface area. Indeed, the bottleneck of micro-sensors network nodes is the autonomy when deployed in restricted access to any source of energy. One way to increase the lifespan of such applications is to complete the array of present micro-devices (micro-batteries and micro-capacitors) with all-solid-state micro-supercapacitors for pulsed modes where the time constant is significantly different from few hours (micro-batteries) to few seconds (micro-supercapacitors) to few milliseconds (micro-capacitors). For this purpose, a multi-disciplinary approach will be conducted with on one side solid-state chemistry specialists (UCCS, coordinator of this project) and on the other side by micro and nano-electronic profiles (IEMN). There are several objectives within this project, answering to the 1st topic of this call, and more precisely around micro-energy storage devices for high power densities applications (pulsed modes) with very low loading mass and surface area (lightering, ergonomy and autonomy). This paves the way for numerous applications for IoTs such as wireless sensor networks nodes, wireless telecommunication systems, Defense and civil ones (micro-drones, micro-robots, embedded sensors).