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  • 1
    In: Advanced Energy Materials, Wiley, Vol. 7, No. 2 ( 2017-01)
    Abstract: Nowadays, millimeter scale power sources are key devices for providing autonomy to smart, connected, and miniaturized sensors. However, until now, planar solid state microbatteries do not yet exhibit a sufficient surface energy density. In that context, architectured 3D microbatteries appear therefore to be a good solution to improve the material mass loading while keeping small the footprint area. Beside the design itself of the 3D microbaterry, one important technological barrier to address is the conformal deposition of thin films (lithiated or not) on 3D structures. For that purpose, atomic layer deposition (ALD) technology is a powerful technique that enables conformal coatings of thin film on complex substrate. An original, robust, and highly efficient 3D scaffold is proposed to significantly improve the geometrical surface of miniaturized 3D microbattery. Four functional layers composing the 3D lithium ion microbattery stacking has been successfully deposited on simple and double microtubes 3D templates. In depth synchrotron X‐ray nanotomography and high angle annular dark field transmission electron microscope analyses are used to study the interface between each layer. For the first time, using ALD, anatase TiO 2 negative electrode is coated on 3D tubes with Li 3 PO 4 lithium phosphate as electrolyte, opening the way to all solid‐state 3D microbatteries. The surface capacity is significantly increased by the proposed topology (high area enlargement factor – “thick” 3D layer), from 3.5 μA h cm −2 for a planar layer up to 0.37 mA h cm −2 for a 3D thin film (105 times higher).
    Type of Medium: Online Resource
    ISSN: 1614-6832 , 1614-6840
    URL: Issue
    Language: English
    Publisher: Wiley
    Publication Date: 2017
    detail.hit.zdb_id: 2594556-7
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  • 2
    Online Resource
    Online Resource
    The Electrochemical Society ; 2017
    In:  ECS Meeting Abstracts Vol. MA2017-02, No. 6 ( 2017-09-01), p. 582-582
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2017-02, No. 6 ( 2017-09-01), p. 582-582
    Abstract: An increasingly number of studies is dedicated to the development of miniaturized sensors (“smartdust”), either for industrial purposes or for health monitoring. The requested power to get autonomous such miniaturized sensors led researchers to design efficient power sources. Microbatteries and microsupercapacitors have to be combined to fulfill such requirements. Our approach aims at miniaturizing metal-air batteries which can drastically boost the energy density available for smartdust sensors. In the frame of this study, the common thread is to design and to produce a full 3D microdevice in which energy is stored in the same way as in a metal-air battery. To address this task, the fabrication and characterization of miniaturized 3D metal anode and 3D macro-porous air cathode are proposed, each of those electrodes having a footprint area close to several mm 2 . First, a strategy for designing a 3D metal anode has been drawn, using CMOS compatible process. 3D zinc electrode (Zn micropillars) has already been electroplated through a porous membrane [1]. Despite an interesting technology, the 3D zinc scaffold is totally consumed after the first discharge (primary battery). The aim of our project is to produce a secondary metal-air microbattery by keeping safe the 3D template after the first discharge. A 3D metal electrode is then electroplated onto an inert 3D scaffold. To reach this goal, a 3D silicon template, consisting in an array of microtubes (Φ = 3 µm / depth = 50 µm) is fabricated. The lateral surface providing by the 3D scaffold allows the enhancement of the material mass loading while keeping constant the footprint area [2] . Once the geometry has been optimized by pushing back the limits of the silicon etching, the 3D scaffold is coated with a conformal deposit of metals. Zinc electroplated thin films has been deposited from an aqueous bath, and a similar approach for the electrodeposition of aluminum thin films was carried out from ionic liquids. Then, a micro-structured air cathode has been engineered using similar microelectronics processes. Air cathodes are composed of a conductive mesh, a catalyst and carbon material [3]. The project aims at reproducing the behavior of such air cathodes but at the millimeter scale: silicon wafer is double side etched with a tuned porosity. The top side of this topology acts as gas diffusion layer allowing the diffusion of oxygen into the miniaturized device. The bottom side of this electrode is composed of a large cavity, allowing the contact between the aqueous electrolyte, the catalytic sites and the oxygen. Conformal deposition of a platinum thin film is achieved by atomic layer deposition (ALD) to add the conductive contribution to the porous silicon scaffold. This platinum layer acts as the current collector and as the seed layer for catalysts electrodeposition process. These two electrodes have been separately characterized. Concerning the 3D metallic anode, various Zn-air prototypes have been assembled in KOH electrolyte using a homemade electrochemical cell with a commercially available air cathode. In the best configuration tested so far, this 3D Zn electrode can deliver a discharge capacity close to 1 mAh.cm - ² with a flat discharge plateau at 1.2 V (fig. 1C). This value is three times higher than the one reported for state-of-art 3D Li-ion microbattery capacity using material thickness in the same order of magnitude [4]. Similarly, various Zn-air prototypes have been assembled using a Zn foil and the silicon micromachined air cathode in KOH electrolyte. A discharge plateau around 1.3V has been observed (fig. 1D). Finally, both components have been assembled to demonstrate the feasibility of a 3D metal-air primary microbattery with improved performance which will be reported in this communication. Acknowledgment: The RS2E and the DGA financially support this work. The French RENATECH network is greatly acknowledged for the microfabrication facilities. References [1] Chamran, F. et al. (2007), Zinc-Air Microbattery with Electrode Array of Zinc Microposts, MEMS 2007, Kobe, Japan, 21-25 January 2007 [2] Eustache, E. et al. (2014), Silicon-Microtube Scaffold Decorated with Anatase TiO2 as a Negative Electrode for a 3D Litium-Ion Microbattery, Adv. Energy Mater. 1301612 [3] Xiaoming, G. et al. (2015), Oxygen Reduction in Alkaline Media: From Mechanisms to Recent Advances of Catalysts, ACS Catal., 5, 4643-4667 [4] Létiche, M et al. (2016), Atomic layer deposition of functional layers for on Chip 3D Li-ion all solid state microbattery, Adv. Energy Mater. 1601402 Figure 1
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2017
    detail.hit.zdb_id: 2438749-6
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  • 3
    Online Resource
    Online Resource
    American Chemical Society (ACS) ; 2023
    In:  Journal of the American Chemical Society Vol. 145, No. 38 ( 2023-09-27), p. 21012-21019
    In: Journal of the American Chemical Society, American Chemical Society (ACS), Vol. 145, No. 38 ( 2023-09-27), p. 21012-21019
    Type of Medium: Online Resource
    ISSN: 0002-7863 , 1520-5126
    RVK:
    Language: English
    Publisher: American Chemical Society (ACS)
    Publication Date: 2023
    detail.hit.zdb_id: 1472210-0
    detail.hit.zdb_id: 3155-0
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  • 4
    Online Resource
    Online Resource
    The Electrochemical Society ; 2015
    In:  Journal of The Electrochemical Society Vol. 162, No. 4 ( 2015), p. A493-A500
    In: Journal of The Electrochemical Society, The Electrochemical Society, Vol. 162, No. 4 ( 2015), p. A493-A500
    Type of Medium: Online Resource
    ISSN: 0013-4651 , 1945-7111
    RVK:
    Language: English
    Publisher: The Electrochemical Society
    Publication Date: 2015
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  • 5
    In: Energy Storage Materials, Elsevier BV, Vol. 42 ( 2021-11), p. 259-267
    Type of Medium: Online Resource
    ISSN: 2405-8297
    Language: English
    Publisher: Elsevier BV
    Publication Date: 2021
    detail.hit.zdb_id: 2841602-8
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  • 6
    In: Lab on a Chip, Royal Society of Chemistry (RSC), Vol. 22, No. 10 ( 2022), p. 1929-1942
    Abstract: Organ-on-a-chip systems that recapitulate tissue-level functions have been proposed to improve in vitro – in vivo correlation in drug development. Significant progress has been made to control the cellular microenvironment with mechanical stimulation and fluid flow. However, it has been challenging to introduce complex 3D tissue structures due to the physical constraints of microfluidic channels or membranes in organ-on-a-chip systems. Inspired by 4D bioprinting, we develop a subtractive manufacturing technique where a flexible sacrificial material can be patterned on a 2D surface, swell and shape change when exposed to aqueous hydrogel, and subsequently degrade to produce perfusable networks in a natural hydrogel matrix that can be populated with cells. The technique is applied to fabricate organ-specific vascular networks, vascularized kidney proximal tubules, and terminal lung alveoli in a customized 384-well plate and then further scaled to a 24-well plate format to make a large vascular network, vascularized liver tissues, and for integration with ultrasound imaging. This biofabrication method eliminates the physical constraints in organ-on-a-chip systems to incorporate complex ready-to-perfuse tissue structures in an open-well design.
    Type of Medium: Online Resource
    ISSN: 1473-0197 , 1473-0189
    Language: English
    Publisher: Royal Society of Chemistry (RSC)
    Publication Date: 2022
    detail.hit.zdb_id: 2056646-3
    SSG: 12
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  • 7
    In: ECS Meeting Abstracts, The Electrochemical Society, Vol. MA2014-02, No. 5 ( 2014-08-05), p. 448-448
    Abstract: With the development of energy autonomous systems (sensors, connected objects, active RFID…), the interest for energy storage devices as microbatteries is growing. Such batteries are based on lithium technologies. Classically, a thin film lithium microbattery consists of the deposition on a substrate of several functional layers such as 2 current collectors, a positive and a negative (lithium metal) electrodes separated by a solid electrolyte (fig. 1). Our study focuses on sputtered thin films deposited on a silicon substrate (figure 1). To prevent the lithium diffusion from the active layers to the silicon substrate, a diffusion barrier layer should be integrated in the structure. Titanium Nitride (TiN) is really developed in microelectronics and TiN could be used both as a current collector and as lithium diffusion barrier (1) for the negative electrode (2, 3). The purpose of this study is to understand the influence of deposition parameters on the titanium nitride characteristics in order to get low resistivity and low electrochemically active thin film against lithium ion insertion. To do so, experiments have been led to get resistivity and Li-capacity as function of the deposition parameters. Structural properties such as crystalline texture, roughness and microstructure have been also studied (figure 2). Prior to the thin film deposition of gold materials and their electrochemical characterization, in operando X ray diffraction measurement has been performed on a gold foil in order to clearly understand the structural evolution of the lithium-gold alloys (4). As in the lithium-silicon alloys, the understanding is really complicated and the number of publications is limited (5-7): ours conclusion and results will be presented. Then, a negative gold electrode has been deposited on the TiN current collector by sputtering means. It has been shown that the electrochemical study is quite difficult if the gold thin film is deposited directly on the silicon wafer owing to the lithium-silicon alloys. It has been demonstrated the benefit from the TiN layer by TOF-SIMS measurement where the lithium ion bas been blocked in the gold electrode due to the TiN barrier layer. Galvanostatic cycling tests has been carried out on the gold electrode and two plateaus have been highlighted corresponding to the lithium-poor and lithium-rich gold phases. The reversibility of these two plateaus have been studied in liquid (1M LITFSI/EC/DEC) as well as in solid (sputtered LIPON) electrolytes and will be presented. Finally, the C-LiFePO 4 positive electrode has been studied by RF and pulsed DC magnetron sputtering deposition means. The electrochemical (cyclic voltammetry, galvanostatic cycling) experiments on the thin films as a function of the deposition parameters (figure 3) will also be reported. Micro-patterning of the C-LiFePO 4 layer has been realized for the first time by deep reactive ion etching. All the building blocks mixing material deposition/characterization and microelectronic fabrication have been developed in this study and paves the ways to the technological fabrication of thin film lithium-ion microbattery based on this technology. Acknowledgments: The authors want to thank the French network of the electrochemical energy storage (RS2E) for this support. This research is financially supported by the ANR and the DGA within the MECANANO project (ANR-12-ASTR-0032-01). The French RENATECH network and the CPER CIA are greatly acknowledged. 1. L. Baggetto, R. A. H. Niessen, F. Roozeboom and P. H. L. Notten, Advanced Functional Materials , 18 , 1057 (2008). 2. S.-K. Rha, W.-J. Lee, D.-I. Kim, S.-Y. Lee, D.-W. Kim, Y.-S. Hwang, S.-S. Chun and C.-O. Park, Thin Solid Films , 320 , 134 (1998). 3. V. Chakrapani, F. Rusli, M. A. Filler and P. A. Kohl, Journal of Power Sources , 216 , 84 (2012). 4. A. D. Pelton, Bulletin of Alloy Phase Diagrams 7 , 228 (1986). 5. G. Taillades, N. Benjelloun, J. Sarradin and M. Ribes, Solid State Ionics 152–153 , 119 (2002). 6. T. L. Kulova, A. M. Skundin, V. M. Kozhevin, D. A. Yavsin and S. A. Gurevich, Russian Journal of Electrochemistry , 46 , 877 (2010). 7. A. Gohier, B. Laïk, J.-P. Pereira-Ramos, C. S. Cojocaru and P. Tran-Van, Journal of Power Sources , 203 , 135 (2012).
    Type of Medium: Online Resource
    ISSN: 2151-2043
    Language: Unknown
    Publisher: The Electrochemical Society
    Publication Date: 2014
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