Materials for Energy Storage and Conversion

The development of new accumulators and/or batteries requires the design of innovative ionically conductive polymer materials to meet emerging challenges. Depending on the type of electrochemical device used (batteries such as metal-air, redox flow, lithium-ion, etc.; fuel cells; electrolyzers), the polymer membrane separating the electrodes plays a crucial role. Its functionalities (ionic conductivity, ion diffusion, and selectivity) are key to ensuring long-term durability.
We are developing new membranes that combine polymers, each contributing key properties of interest. To achieve this, two approaches are considered:

• The synthesis of (semi-)interpenetrating polymer networks combining a polyelectrolyte and a hydrophobic polymer.
• Dip-coating deposition of a polyelectrolyte onto a hydrophobic microporous support.

Once the membranes are developed, their mechanical, thermal, and ionic properties are characterized, and their chemical stability assessed under operating conditions. After that they are tested in real devices to evaluate their performances.

Device for Nickel/Zinc Battery Testing

Device for redox-flow battery tests

Keywords : membrane, polyelectrolyte, (semi-)IPN, ionic conduction, chemical aging

Selection of recent papers (or patents)

A. Naboulsi, G. Nguyen, S. Franger, O.Fichet, C. Laberty-Robert, Characterization of Li+ Transport through the Organic-Inorganic Interface by Using Electrochemical Impedance Spectroscopy, Journal of The Electrochemical Society 171 (2024) 020523; https://iopscience.iop.org/article/10.1149/1945-7111/ad2595/pdf
K. Dembélé, L. Chikh, S. Alfonsi , O. Fichet , Effect of polyelectrolyte architecture on chemical stability in alkaline medium of anion exchange membranes, Polymer Degradation and Stability 215 (2023) 110462. https://doi.org/10.1016/j.polymdegradstab.2023.110462
N. Festin, S. Magana, M. Fumagalli, L. Chikh, F. Gouanvé, V.H. Mareau, L. Gonon, S. Lyonnard, E. Espuche, O. Fichet, A. Morin, Morphology-induced percolation in crosslinked AMPS/Fluorolink for fuel cell membrane application, Journal of Membrane Science 534 (2017) 59–67. https://doi.org/10.1016/j.memsci.2017.04.004

Electrochemical capacitors or supercapacitors are becoming a promising alternative storage devices for rechargeable batteries thanks to their high power/energy density. Such devices have been emerged in a wide spectrum of applications, ranging from transportation (e.g. tramways, personal vehicles) to portable and wearable electronics. We develop at LPPI two key components of supercapacitor devices (electrode materials and electrolytes). Altogether, the materials are conceived and design with specific functionalities to tackle critical parameters for real life applications, including energy density, power density, stability, safety, flexibility, stretchability and self-healing ability.

For electrode, electrical conducting and controlled architectural materials are intensively been developed to enlarge the specific surface area as well as the electrochemical active surface area, including organic frameworks (COF/MOF), hierarchical porous carbon (HPC), multiwalled carbon nanotubes (MWCTs, vertically aligned/entangled), transition metal oxides/chalcogenides, and electrically conducting polymers. Typically, specific surface areas ranging from hundreds to ca. 3000 m2 g-1, depending on the material’s nature, had been obtained at LPPI.

For electrolyte, in parallel with conventional liquid electrolyte, we have strong activities in developing gelled polymer electrolytes (GPEs) for quasi-solid-state supercapacitors. One of our key expertise relies on the elaboration of ionic liquid contained gelled electrolytes and ionogel owning high operation voltage (> 2.5 V) and high ionic conductivity reaching ~ 10 mS cm-1 alongside with possibilities to combine with self-standing properties, self-healing ability, flexibility and stretchability.

 

Keywords: Ultrahigh porous materials, gelled polymer electrolytes, synthesis, characterizations, electrochemistry, devices

Selection of recent papers (or patents)

Lavillunière, H., Pham-Truong, T.N., Nguyen T.K.L, Vancaeyzeele, C., Aubert P-H., Controlled microwave-assisted synthesis of Covalent Organic Frameworks opens the way towards more suitable porous supercapacitors electrodes, ACS Appl. Energy Mater., 2024, 7, 5, 1723–1734 (Front cover), DOI : 10.1021/acsaem.3c02484
Pham-Truong, T.N., Lavillunière, H., Guemiza, H., Vancaeyzeele, C., Aubert, P-H., Electrochemical behavior of in-situ electrosynthetized 3D metal-organic framework (MOF) as ultra-stable thin film on nickel foam, Electrochim. Acta, 2023, 441, 141792, DOI: 10.1016/j.electacta.2022.141792
Querne, C., Vignal, T., Pinault, M., Banet, P., Mayne-L’Hermite, M., Aubert, P-H., A comparative study of high density Vertically Aligned Carbon Nanotubes grown onto different grades of aluminum – Application to supercapacitors, J. Power Sources, 2023, 553, 232258, DOI: 10.1016/j.jpowsour.2022.232258
Rogier, C., Pognon, G., Galindo, C., Nguyen, T.M.G., Vancaeyzeele, C., Aubert, P-H., MoO3–Carbon Nanotube Negative Electrode Designed for a Fully Hybrid Asymmetric Metal Oxide-Based Pseudocapacitor Operating in an Organic Electrolyte, ACS Appl. Energy Mater., 2022, 5, 8, 9361-9372, DOI : 10.1021/acsaem.2c00632
Aubert, P-H., Banet, P., Boisset, A., Darchy, L., Desparpentries, J., Ghamouss, F., Hauf, H., Mayne-L’Hermite, M., Pinault, M., Tran-Van, F., Method for growing carbon nanotubes on the surface and in the body of a porous carbonaceous substrate and use for preparing an electrode, US Patent App. 17/269,082, 2021

We are developing electroactive polymer materials able to change their shape or volume under electrical stimulation and to generate a mechanical work. These soft actuators, often considered as precursors of artificial muscles, present numerous advantages over « convential » bulky and stiff actuators such electrical engines or piezoelectric actuators. They are soft and silent, can present large deformations, operate under low voltage (~1V) and can be biocompatibles.
The materials and devices developed at LPPI are most of the time based on electronic conducting polymers, such as poly(3,4-éthylènedioxythiophène) (PEDOT), able to present reversible volume variations when electrochemically oxidized or reduced in the presence of an electrolyte. During this redox process, ions from the surrounding electrolyte will swell or be expelled from the material to insure its electroneutrality and consequently will promote its volume expansion or shrinking. Our activities are turned toward the synthesis and the characterization of electroactive polymers but also of stretchable and highly conducting ionic membranes (ionogels or ionoelastomers) acting as ion source/sink. The challenges often rely on obtaining an ideal combination of mechanical, electrical, electrochemical and electromechanical properties.

microactionneur tricouche ionique

matériaux « tricouche » électrostimulables flexibles, matériau tricouche intégré avec une aile artificielle d’insecte, Microscopie à balayage d’un microactionneur (collab. IEMN)

Keywords : electronic conducting polymers, PEDOT, ionogels, polymeric ionic liquids, ionoelastomers, vitrimers, electroactive textiles, biomedical, soft robotics.

Selection of recent papers

Bin Ni, Loris Gelas, Gabriela Ananieva, Cédric Vancaeyzeele, Giao T. M. Nguyen, Frédéric Vidal, Cédric Plesse, Artificial muscle based on coiled CNT yarns and biofriendly ionogels, Sensors and Actuators B: Chemical, 2024, 403, 135227, https://doi.org/10.1016/j.snb.2023.135227
Frédéric Braz Ribeiro, Bin Ni, Giao T. M. Nguyen, Eric Cattan, Alexander S. Shaplov, Frédéric Vidal, Cédric Plesse, Highly Stretchable and Ionically Conductive Membranes with Semi-Interpenetrating Network Architecture for Truly All-Solid-State Microactuators and Microsensors, Advanced Materials Interfaces, 2023, 10, 10, 2202381, https://doi.org/10.1002/admi.202202381
Bin Ni, Frédéric Braz Ribeiro, Cédric Vancaeyzeele, Giao T.M. Nguyen, Edwin W.H. Jager, Frédéric Vidal, Cédric Plesse, Linear contracting and air-stable electrochemical artificial muscles based on commercially available CNT yarns and ionically selective ionogel coatings, Applied Materials Today, 2023, 31, 101756, https://doi.org/10.1016/j.apmt.2023.101756
A. Ferrandez-Montero, B. Carlier, R. Agniel, J. Leroy-Dudal,C. Vancaeyzeele, C. Plesse, 4D smart porous scaffolds based on the polyHIPE architecture and electroactive PEDOT, J. Mater. Chem. C, 2021, 9, 12388-12398 https://doi.org/10.1039/D1TC01846A
Kätlin Rohtlaid, Giao T. M. Nguyen, Caroline Soyer, Eric Cattan, Frédéric Vidal, Cédric Plesse, Poly(3,4-ethylenedioxythiophene):Poly(styrene sulfonate)/Polyethylene Oxide Electrodes with Improved Electrical and Electrochemical Properties for Soft Microactuators and Microsensors, Adv. Electron. Mater., 2019, 5, 1800948, https://doi.org/10.1002/aelm.201800948
 

 

Selection of recent papers (or patents)

The laboratory is working on the development of adaptative optical systems (screens) able to changing color on command. Among the available technologies, electrochromic materials are particularly interesting. The LPPI is thus developing displays based on electrochromic conductive polymers (ECP) capable of change from a colored state to am achromatic state by the application of an electric potential. This color change is induced by a redox reaction involving the ECP occurring when it’s integrated into an electrochemical device consisting of the ECP as a working electrode, an electrolyte medium (in our case, an ionic liquid) and a counter electrode. Operational displays using cyan,¹ magenta and yellow (CMY) polymers and developed on glass substrates are obtained by the superposition of 3 CMY layers.² Selective control of one or more colors makes it possible to display all the visible colors, here for example yellow, red, black and green represented on 4 pixels. By adjusting the applied potentials, it’s possible to reproduce a set of 75 discernible colors. The LPPI has also carried out the integration of the display technology on thin and flexible substrates (based on PET) allowing a significant reduction in their mass and the creation of conformable systems. The design of scleral contact lenses with two cyan and yellow electrochromic polymers, capable of reversibly changing from green to blue, was this carried out.³

Keywords: Synthesis, conductive polymers, colorimetry, electrochemical control, multi-component optical devices.

Selection of recent papers (or patents)

(1) S. Fagour, D. Thirion, A. Vacher, X. Sallenave, G. Sini, P.-H. Aubert, F.Vidal, C. Chevrot. Understanding the Colorimetric Properties of Quinoxaline-based Pi-conjugated Copolymers by Tuning Their Acceptor Strength: a Joint Theoretical and Experimental Approach. RSC Adv. 2017, 7, 22311. https://doi.org/10.1039/C7RA02535A
(2) C. Ernest, S. Fagour, X. Sallenave, P.-H. Aubert, F. Vidal. An Electrochromic Displays Comprising the Three Primary Cyan Magenta and Yellow Colors Under Juxtaposed and Stacked Architectures. Advanced Materials Technologies 2024, 9, 2301654. https://doi.org/10.1002/admt.202301654
(3) A. Khaldi, H. Menez, Q. Murat, X. Sallenave, F. Vidal, P-H. Aubert, L. Dupont, J-L. de Bougrenet de la Tocnaye. Development of Multi-layer Electrochromic Polymer Display for Remotely Tunable Green-cyan Contact Lens. AIP Advances 2024, 14, 065125. https://doi.org/10.1063/5.0201708

Electronically conductive polymers offer very interesting potential as materials with modulable infrared emissivity. They can be used for thermal control of buildings and satellites, as well as for infrared stealth technologies. In fact, these polymers have the ability to switch from an IR reflecting state to an IR emitting state depending on their oxidation state. Our work has led to the development of self-supporting, flexible and electro-emissive devices that, when judiciously integrated into a satellite, can contribute to the active thermal regulation of the spacecraft. Simulations have shown that their presence can reduce the weight of the heaters currently used in satellites by about 30%.

   

Representation of the environments to which a satellite is exposed during the rotations around the Earth. In front of the sun, the environment is “hot”. In the shadow of the Earth, the environment is “cold”.

 

Image of a radiator with 16 electroemissive devices

Aluminum-doped zinc oxide nanoparticles also have interesting properties that can be exploited to develop devices that modulate infrared reflection. In fact, these nanoparticles are characterized by plasmonic resonances that make them absorbent in the IR. In collaboration with our partner at IMT Atlantique - Brest, we have patented the first electrophoretic device with IR modulation properties. The aim was to reproduce in the IR range a device similar to an e-reader (e.g. Amazon's Kindle or Fnac's Kobo).

 

Aluminum-doped zinc oxide colloidal nanocrystals.

LWIR thermographs and apparent temperatures accessible with the IR electrophoretic device.

Keywords:  electronically conductive polymers, nanoparticles and plasmonic resonances; thermal regulation, stealth, IR camouflage


Selection of recent papers (or patents)

Petroffe, G., Beouch, L., Cantin, S., Aubert, P.-H., Plesse, C., Dudon, J.-P., Vidal, F., Chevrot, C., 2018. Investigations of ionic liquids on the infrared electroreflective properties of poly(3,4-ethylenedioxythiophene). Solar Energy Materials and Solar Cells 177, 23–31. https://doi.org/10.1016/j.solmat.2017.07.018
Petroffe, G., Beouch, L., Cantin, S., Chevrot, C., Aubert, P.-H., Dudon, J.-P., Vidal, F., 2019. Thermal regulation of satellites using adaptive polymeric materials. Solar Energy Materials and Solar Cells 200, 110035. https://doi.org/10.1016/j.solmat.2019.110035
Vidal, F., Petroffe, G., Beouch, L., Cantin, S., Chevrot, C., Aubert, P.-H., Dudon, J.-P., 2022. Active Thermal Control of Satellites with Electroactive Materials, in: Rasmussen, L. (Ed.), Smart Materials. Springer International Publishing, Cham, pp. 221–254. https://doi.org/10.1007/978-3-030-70514-5_7
Chrun, J., Da Silva, A., Vancaeyzeele, C., Vidal, F., Aubert, P.-H., Dupont, L., 2023. Electrophoretic displays for IR emissivity modulation and temperature control. J. Mater. Chem. C 11, 141–150. https://doi.org/10.1039/D2TC04147B
Da Silva, A., Vancaeyzeele, C., Vidal, F., Dupont, L., Aubert, P.-H., 2024. Plasmonic Al, Ga and in-doped zinc oxide nanoparticles as key components for the design of electrophoretic inks with MWIR and LWIR absorbance properties. Chemical Engineering Journal 497, 154253. https://doi.org/10.1016/j.cej.2024.154253