Periodic Reporting for period 1 - ROCHE (“Multilayer approach for solid-state batteries” - (ROCHE))
Période du rapport: 2022-09-01 au 2024-08-31
Solid electrolytes represent a significant advancement in battery technology, primarily due to their potential to address the key challenges faced by liquid electrolytes, such as safety risks associated with flammability, leakage, and thermal instability. Additionally, solid electrolytes can improve battery performance by enabling higher energy densities, longer life cycles, and better thermal management. The development of solid-state batteries, which utilize solid electrolytes, is considered one of the most promising approaches to meeting the growing global demand for safe, high-performance, and sustainable energy storage solutions.
ROCHE project will use a novel multilayer approach to fabricate solid-state batteries, in which solid inorganic material will be intercalated with MOFs layers. As novelty, three synergetic approaches of metal-organic frameworks (MOF) will be designed to improve and favour the ionic transport. It is expected that the use of the multilayer approach will increase the mechanical resistance compared to an individual one. Also the synergistic effect of the high ionic conductivity and nanowetted interface between the MOF and the cathode will entail a high-capacity and good dendrite suppression capability, allowing its implementation in next-generation solid-state batteries. The combined database and machine learning approach have been applied to design and predict material properties of electrodes such as voltage, crystallinity and chemical stability, from atomic scale to mesoscale.[5] Bearing this in mind, it can been applied to design new SSEs with fast Li-ion transport and mechanical properties. Providing an opportunity for exploring material properties at a lower cost and accelerating the material discovery processes.
Once aims have been established, the specific scientific objectives of the project are:
(1) The synthesis and optimization of materials with the objective to develop a multi-layer structure of SSEs.
(2) The assembly of SSEs in a battery structure and characterize their behaviour under long-test cycling.
(3) The understanding of the role of interfaces in the ionic transport in order to unravel a possible kinetic mechanism in solid-state batteries.
ROCHE project will use a novel multilayer approach to fabricate solid-state batteries, in which solid inorganic material will be intercalated with MOFs layers. As novelty, three synergetic approaches of metal-organic frameworks (MOF) will be designed to improve and favour the ionic transport. It is expected that the use of the multilayer approach will increase the mechanical resistance compared to an individual one. Also the synergistic effect of the high ionic conductivity and nanowetted interface between the MOF and the cathode will entail a high-capacity and good dendrite suppression capability, allowing its implementation in next-generation solid-state batteries. The combined database and machine learning approach have been applied to design and predict material properties of electrodes such as voltage, crystallinity and chemical stability, from atomic scale to mesoscale.[5] Bearing this in mind, it can been applied to design new SSEs with fast Li-ion transport and mechanical properties. Providing an opportunity for exploring material properties at a lower cost and accelerating the material discovery processes.
Once aims have been established, the specific scientific objectives of the project are:
(1) The synthesis and optimization of materials with the objective to develop a multi-layer structure of SSEs.
(2) The assembly of SSEs in a battery structure and characterize their behaviour under long-test cycling.
(3) The understanding of the role of interfaces in the ionic transport in order to unravel a possible kinetic mechanism in solid-state batteries.
The scope of our work during this period has involved both theoretical research and experimental validation. The key objectives include synthesizing new solid electrolyte materials, evaluating their electrochemical performance, and optimizing their integration into next-generation battery systems. We have been particularly focused on two classes of solid electrolytes: three-components materials and organic ionic plastic crystals materials (OIPC). Each of these materials offers distinct advantages and challenges, and our goal has been to explore their properties in-depth to identify the most promising candidates for further development.
The study of three-components materials was focused on the incorporation of an ionic liquid doped with lithium salt into a metal-organic framework. More specifically, this work set out to study the incorporation of an ionic liquid doped with a lithium salt into an archetype Ti-based Metal Organic Framework (MOF) to create a solid to quasi-solid (depending on the amount of IL in the system), and how this affects not only ionic transport but also the structural properties of the IL/MOF electrolyte. Remarkably high ionic conductivity values as well as a lithium transference number were achieved, supported by pulsed field gradient (PFG) NMR experiments. Electrochemical characterization revealed reversible plating-stripping of lithium and lower overpotential after 750 h at 50 ºC. Additionally, a proof-of-concept solid state battery was fabricated resulting in a discharge capacity of 160 mAh·g-1 at 50 ºC and 0.1C rate after 50 cycles. This work presents a suitable strategy to dendrite suppression capability, allowing its implementation as interface modifiers in next-generation solid-state batteries.
On the other hand, OIPCs are innovative hybrid materials that merge the characteristics of ionic liquids with those of plastic crystals. Composed of organic ions, these materials exhibit a unique combination of fluidity and crystalline order, allowing the ions to move freely within the crystal lattice while maintaining structural integrity. This duality results in exceptional ionic conductivity and flexibility, making OIPCs ideal for use in solid-state electrolytes, energy storage devices, and other electrochemical applications. Furthermore, the chemical composition of OIPCs can be tailored to enhance specific properties, providing a versatile platform for the development of advanced functional materials. In particular, we have use a tetramethylammonium-based OIPC that, upon the incorporation of lithium and sodium salts presents impressive characteristics as high ionic conductivity, high diffusion coefficient, high Li transference number with only one phase change at 78 ⁰C. We believe that this is the first time that true solid-state behaviour with Li+ transport decoupled from the motion of the host structure.
In addition to material development, significant effort has been devoted to the characterization and testing of solid electrolytes under real-world conditions. In this secondment, has been employing advanced analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS) to gain insights into the structural, morphological, and electrochemical properties of these materials. These tools have been critical in identifying the strengths and weaknesses of different electrolyte candidates and guiding the optimization process.
Papers
- J.C. Barbosa, A. Fidalgo-Marijuan, J.C. Dias, R. Gonçalves, M. Salado, C.M. Costa, S. Lanceros-Méndez. Molecular design of functional polymers for organic radical batteries. Energy Storage Materials, Volume 60, June 2023, 102841
- Manuel Salado, Marco Amores, Cristina Pozo-Gonzalo, Maria Forsyth, Senentxu Lanceros-Méndez. Advanced and sustainable functional materials for potassium-ion Batteries. Energy Mater 2023;3:300037
- M. Salado, R. Fernández de Luis, T. H. Smith, M. Hasanpoor, S. Lanceros-Mendez, M. Forsyth. Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte (Q-SSEs) for Li−Metal Batteries. doi.org/10.1002/batt.202400134.
Conferences
- Oral presentation: 38th Australasian Polymer Symposium. “Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte (Q-SSEs)”
The study of three-components materials was focused on the incorporation of an ionic liquid doped with lithium salt into a metal-organic framework. More specifically, this work set out to study the incorporation of an ionic liquid doped with a lithium salt into an archetype Ti-based Metal Organic Framework (MOF) to create a solid to quasi-solid (depending on the amount of IL in the system), and how this affects not only ionic transport but also the structural properties of the IL/MOF electrolyte. Remarkably high ionic conductivity values as well as a lithium transference number were achieved, supported by pulsed field gradient (PFG) NMR experiments. Electrochemical characterization revealed reversible plating-stripping of lithium and lower overpotential after 750 h at 50 ºC. Additionally, a proof-of-concept solid state battery was fabricated resulting in a discharge capacity of 160 mAh·g-1 at 50 ºC and 0.1C rate after 50 cycles. This work presents a suitable strategy to dendrite suppression capability, allowing its implementation as interface modifiers in next-generation solid-state batteries.
On the other hand, OIPCs are innovative hybrid materials that merge the characteristics of ionic liquids with those of plastic crystals. Composed of organic ions, these materials exhibit a unique combination of fluidity and crystalline order, allowing the ions to move freely within the crystal lattice while maintaining structural integrity. This duality results in exceptional ionic conductivity and flexibility, making OIPCs ideal for use in solid-state electrolytes, energy storage devices, and other electrochemical applications. Furthermore, the chemical composition of OIPCs can be tailored to enhance specific properties, providing a versatile platform for the development of advanced functional materials. In particular, we have use a tetramethylammonium-based OIPC that, upon the incorporation of lithium and sodium salts presents impressive characteristics as high ionic conductivity, high diffusion coefficient, high Li transference number with only one phase change at 78 ⁰C. We believe that this is the first time that true solid-state behaviour with Li+ transport decoupled from the motion of the host structure.
In addition to material development, significant effort has been devoted to the characterization and testing of solid electrolytes under real-world conditions. In this secondment, has been employing advanced analytical techniques such as X-ray diffraction (XRD), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS) to gain insights into the structural, morphological, and electrochemical properties of these materials. These tools have been critical in identifying the strengths and weaknesses of different electrolyte candidates and guiding the optimization process.
Papers
- J.C. Barbosa, A. Fidalgo-Marijuan, J.C. Dias, R. Gonçalves, M. Salado, C.M. Costa, S. Lanceros-Méndez. Molecular design of functional polymers for organic radical batteries. Energy Storage Materials, Volume 60, June 2023, 102841
- Manuel Salado, Marco Amores, Cristina Pozo-Gonzalo, Maria Forsyth, Senentxu Lanceros-Méndez. Advanced and sustainable functional materials for potassium-ion Batteries. Energy Mater 2023;3:300037
- M. Salado, R. Fernández de Luis, T. H. Smith, M. Hasanpoor, S. Lanceros-Mendez, M. Forsyth. Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte (Q-SSEs) for Li−Metal Batteries. doi.org/10.1002/batt.202400134.
Conferences
- Oral presentation: 38th Australasian Polymer Symposium. “Dimensionality Control of Li Transport by MOFs Based Quasi-Solid to Solid Electrolyte (Q-SSEs)”
• Design easy-scalable solid-electrolytes: Considering the knowledge obtained during this period, the idea is to design electrolytes for use in larger battery systems, with the goal of testing in real-world applications by Q2 2025.
• Further Interface Studies: Conduct additional research on electrolyte-electrode interfaces to optimize contact and reduce resistance in metal-based systems.
• Simulation of electrolyte material: Modelling and simulations play an important role in understanding materials compositions and designing batteries. The optimal composition and nanostructure will be determined by the use of density functional theory (DFT) meanwhile the full battery behaviour will be simulated by finite element method (FE) modelling.
• Industrial Collaboration: Explore opportunities for collaboration with battery manufacturers to test solid electrolytes in commercial-scale applications.
• Further Interface Studies: Conduct additional research on electrolyte-electrode interfaces to optimize contact and reduce resistance in metal-based systems.
• Simulation of electrolyte material: Modelling and simulations play an important role in understanding materials compositions and designing batteries. The optimal composition and nanostructure will be determined by the use of density functional theory (DFT) meanwhile the full battery behaviour will be simulated by finite element method (FE) modelling.
• Industrial Collaboration: Explore opportunities for collaboration with battery manufacturers to test solid electrolytes in commercial-scale applications.