PILLAR 2 - ADVANCING THE MANUFACTURE OF HIGH-PERFORMANCE ENERGY STORAGE MICRODEVICES FOR FUTURE CONNECTED OBJECTS
The central focus of this pillar is to address the entire value chain enabling the mass production of Energy Storage Microdevices (ESMs) to ensure the energy autonomy of future miniaturized electronics.
These ESMs, including complementary performance micro-batteries, capacitors, micro-capacitors, supercapacitors, and micro-supercapacitors, will be studied and manufactured.
The goal is to elevate these ESMs to a Technology Readiness Level (TRL) of 5 or 6 (prototypes) by addressing fundamental needs such as understanding material growth mechanisms, charge storage mechanisms, and technological challenges in manufacturing currently unavailable components.
To successfully carry out this initiative, the IEMN and UCCS laboratories will join forces, leveraging the accredited platforms of the University of Lille such as the CHEVREUL characterization platform, the Central MicroNanoFabrication (CMNF), and the Multi-Physical Characterization Platform (PCMP) of the IEMN.
This pillar will be dedicated to the manufacturing of high-performance lithium-ion micro-batteries, asymmetric micro-supercapacitors, and hybrid micro-devices integrating faradaic and capacitive charge storage processes.
For microelectronics applications, the devices will be all-solid-state and will not incorporate liquid electrolytes. On a more exploratory aspect, other chemistries such as Zn-ion, Al-ion, etc., may be investigated to offer an alternative to the currently studied Li-ion technology by the involved laboratories.
This pillar will also rely on the technological capabilities of the equipeX (LEAF and Excelsior) and the equipeX+ NANOFUTUR at IEMN. On a more fundamental aspect, national discussions will be conducted with partners from the Labex Store-Ex and the Electrochemical Energy Storage Research Federation (RS2E), in which IEMN has been a historical partner for the past 10 years.
Objectives and scientific challenges
Connected objects are playing an increasingly important role in our daily lives. They are becoming smaller and more energy-demanding (with a surface footprint on the order of a few hundred mm2). Therefore, their energy autonomy has become a significant societal challenge.
Our generic strategy, applicable to all Energy Storage Modules (ESMs), will enable a progression in TRL up to an industrial stage to meet the needs of future miniaturized mobile electronics. This strategy is based on our expertise and achievements (RS2E Network, Labex STOREX) (De Andrade et al., 2021; Huang et al., 2016; Lethien et al., 2019; Létiche et al., 2017; Robert et al., 2020).
ESMs consist of a stack of nano/micrometer-thick film layers of different materials, overlaid and supported by a mechanical substrate.
Task description
Task 1 – Synthesis of "ULILLE" material targets by Spark Plasma Sintering (SPS)
The materials used in our ESMs are typically ternary or quaternary, meaning they consist of 3 to 4 elements, and it is important to control their proportions.
Let's take the example of a thin film of LiNi0.5Mn1.5O4 (positive electrode of a lithium-ion microbattery). To form this thin layer (thickness ~ 1 µm), a target (diameter ~ 10 cm, thickness ~ 10 mm) of the bulk material is sputtered under vacuum. The different elements do not have the "same deposition rates," making it challenging to obtain a stoichiometric thin film. Since these targets are commercially available, finding the right proportions and controlling the initial composition of the bulk material are costly and labor-intensive steps to implement.
We could start with several commercially available elemental powders, carefully controlling their quantities to obtain the desired ternary or quaternary compound (e.g., adjusting the amount of Li in LNMO). From this powder mixture, we propose to create material targets with controlled composition at either UCCS or the SPS CNRS platform at CIRIMAT using Spark Plasma Sintering (3D animation). These targets are then brazed onto a copper substrate to be integrated into a vacuum deposition reactor using magnetron sputtering (CMNF IEMN = RENATECH+ network).
Task 2 - Coating of thin films of materials using ULILLE targets
These targets are installed in a magnetron sputtering reactor, and deposition parameters are modulated to obtain thin films with controlled composition.
On the fundamental aspect, the growth modes of these thin films will be studied using in situ characterization techniques during the growth process in the reactor (in situ ellipsometry, in situ stress, in situ resistivity) to better control the structure/ electrical, electrochemical, mechanical, and morphological properties relationships of these films (EquipeX+ NANOFUTUR). Ex situ analysis techniques using high-resolution scanning probe microscopy (AFM / STM, equipeX EXCELSIOR, PCMP IEMN) will also be employed to distinguish between island growth modes and layer-by-layer growth modes, which will govern the performance of our materials integrated into our ESMs.
Task 3 - Characterization of thin films at the substrate scale (mapping) and coupled in situ/operando characterization.
This task will be dedicated to advanced morphological, electrical, mechanical, and structural characterizations of thin films, initially focusing on the thin layers and subsequently on complete devices. We will employ a wide range of characterization techniques suitable for thin films, such as scanning electron microscopy, transmission electron microscopy, near-field microscopy (potentially in situ), and X-ray diffraction using a rotating anode apparatus (to significantly increase the power). For example, in the latter case, in addition to "standard" characterizations such as 2θ/ω scans or rocking curves to assess layer quality, we can also perform pole figures (texture evaluation), reciprocal lattice mapping (potential epitaxial evaluation), or large substrate mapping (~10 cm diameter) covered with the thin film using microdiffraction.
In this case, the entire power of the generator is concentrated, enabling the mapping of an entire large-sized substrate (~10 cm) to verify its diffraction homogeneity. Conductivity and mechanical stress mapping of thin films deposited on large substrates will be conducted at the CHEVREUL (UCCS) and PCMP platforms of the IEMN.
To study growth mechanisms (combined structural/electrochemical analysis), we will utilize the expertise and collaborative network we have developed, particularly through the ANR CASSIOPES project (in situ/operando XRD analysis, in situ/operando Raman analysis, in situ/operando TEM analysis, in situ/operando XAS analysis using large-scale instruments), where IEMN and UCCS are partners. Transmission electron microscopy in TEM/STEM mode (transmission electron microscopy and scanning transmission electron microscopy) coupled with EDS and EELS will be an important characterization tool (Robert et al., 2020). It will provide atomic-scale information about the morphology, crystallinity, composition, potential oxidation with spatial localization of oxidized regions, oxidation degrees of cations, and their localization. Tomographic reconstruction will allow visualization and quantification of porosity.
Task 4 - Production and characterization of ESMs (Li-ion micro-batteries, micro-supercapacitors, micro-hybrid devices)
Once the synthesis of high-performance thin films is successfully achieved on a large-area substrate (diameter = 10 cm), we will leverage the resources and techniques available in the microelectronics industry at the Central MicroNanoFabrication (CMNF) facility of IEMN to collectively produce ESMs (Eustache et al., 2017; Robert et al., 2018). Advanced etching techniques such as Atomic Layer Etching (ALE) (EquipeX+ NANOFUTUR) and laser etching (Equipex LEAF) will be employed to structure the stack of thin films and fabricate high-quality ESMs.
Task 5 - Maturation/upscale project
Once the ESMs are fabricated, we aim to investigate the encapsulation steps for these micro-devices to facilitate their industrial transfer and promote mass production. There is significant intellectual property potential associated with this technology. The idea is to capitalize on all the results to develop a portfolio of patents in the areas of "materials," "components," and "applications." Establishing a startup based in the Haut de France region will undoubtedly contribute to the regional ecosystem in terms of employment opportunities and technological expertise in the deeptech domain.
Impacts
Beyond the anticipated performance improvement within this pillar, we aim to capitalize on expertise in the fabrication of high-performance planar and 3D ESMs to power miniaturized components with surface areas of a few mm2. The idea is to work with silicon substrates ranging from 7.5 to 10 cm in diameter to enable mass production. The creation of a startup in the region is being considered in this field, following the recent example of TIAMAT on the southern side of the Hauts-de-France region. Energy storage is a strong focus in our region (TIAMAT, RS2E, LRCS, IEMN, UCCS, ACC - Li-ion Gigafactory in Douvrin). Thus, all the conditions are in place for the successful implementation of this initiative at the Lille site.
Moreover, IEMN has extensive experience in creating companies, with no less than 6 active startups in the region: WAVELY, a player in the industry 4.0 sector, combines audio signal processing and artificial intelligence to detect and diagnose malfunctions in industrial equipment based on their sound signature; ZYMOPTIQ, VMICRO, LITUUS, AXORUS, and CORDIAL IT. The success of MC2, a company stemming from the ideas and work of researchers/lecturers at IEMN, further highlights this entrepreneurial culture.
The field of micro-energy storage is gaining momentum in France, and academically, the IEMN/UCCS partnership is among the leaders in this domain. The Lille site possesses tremendous potential in the energy storage field, making it highly attractive at the regional level, particularly considering the various strategic initiatives supported by the region through structuring programs.
Training programs in the field of "micro-energy storage" are offered at Polytech Lille in the Materials and 2IA specialization. They are part of the ETECH (EEA) master's program and at Junia during a four-hour seminar focused on the energy autonomy of miniaturized connected objects.
The deliverable of Pillar 2 is the production of several thousand planar Li-ion micro-batteries on a 10 cm diameter silicon substrate.
This strategy will also be applied to 3D Li-ion micro-batteries, where the performance will be enhanced by a pre-created 3D framework in the substrate. The materials will be deposited using atomic layer deposition (ALD), a technique available at IEMN (Létiche et al., 2017; Ouendi et al., 2019).
These lithium-ion micro-batteries are devices capable of delivering a constant voltage for several minutes to hours but cannot withstand high current demands.
In this context, other ESMs will be investigated within this pillar to meet the need for fast charging, such as micro-capacitors and micro-super capacitors, where we aim to raise the technology readiness level (TRL) of these capacitive energy storage technologies.
References
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