Autonomous self-healing functionalities for next generation batterie (UTMOST)
1. Description of the project
Grand challenge and Objectives: The ambitious goal of the UTMOST project is to develop two different autonomous self-healing functionalities from bio-based materials that remain active within the chemical and electrochemical environment of the targeted battery chemistry, preserve its performance and significantly improve the batteries’ QRL. This can be obtained by designing smart biomimetic or biosourced membranes with controlled functionalities and porosity, thus enabling selective conductivity for working cations. The objective of the first self-healing functionality is the use of biological pores with engineered functionalities as channels for selective transport of working cation. Pores embedded into biomimetic membranes can serve as an artificial Cathode Electrolyte Interface (aCEI), artificial solid electrolyte interface (aSEI) or as a self-standing layer in all cases, controlling transport between active materials and the rest of the electrochemical cell. An alternative approach is the use of biosourced interphases with high selectivity and embedded functionalities for autonomous self-healing properties.
Methodology: UTMOST is extending knowledge within material science, electrochemistry, biology, and engineering with a grand challenge to design self-healing functionalities in the battery environment using biosourced materials. Biomimetic or biobased materials will be used for the development of ionoselective interfaces/interphases with a function of preventing unwanted cross communication between two electrodes caused by degradation products (dissolved metals, reduction products from electrolyte, dissolved binder, …). Ionic transport can be controlled by introducing artificial interfaces (aCEI or aSEI) specially designed for conducting the selected ionic species. Such interfaces have already been developed in nature and are ready to be adopted and used in novel applications. As a good example, biomimetic membranes prepared from biological pores with high selectivity for cations can transport small cations based on size and charge selectivity. Selectivity will be possible through protein and pore engineering. Proof of concept is expected to be developed within this complementary scheme. An alternative approach is based on the modification of separators with biosourced molecules, such as chitosan, starch, lignin, cellulose, cyclodextrin, guar gum, and xanthan gum, each of them possessing distinct functionalities supporting ion selective separation. Proof of concept will be shown by using cellulose as the starting point. Modifications will be performed thereafter to enable self-healing functionalities of the introduced biomaterial.
Feasibility: Two different self-healing functionalities known from nature or other applications will be developed during the project duration for modern battery systems (predominantly for lithium and if feasible also for magnesium rechargeable batteries). Use of biomimetic membranes with pores for selective cation transport has up until now not been exemplified in batteries, however, it has been demonstrated in other applications. Pores obtained from lysenin as well as other biosourced polymers have been shown to be stable in the harsh environment of Li-ion batteries. These materials therefore represent a suitable starting point for developing ion selective interphases/interfaces. This makes the project feasible from a methodological point of view. As the experimental equipment is available, the project is also feasible from the equipment accessibility perspective.
Impact: Breakthrough research in the project offers a paradigm shift in battery research that will lead to the development of more effective battery systems in terms of quality, reliability and lifetime.
Financial Support: The project is financed from Slovenian research agency (ARRS) under the code N2-0214. The duration is of the project is 01.06.2021―31.05.2024.
2. Members of the project
Prof. dr. Robert Dominko (Sicris): The project leader and contractor is also one of the world's leading researchers in the field of modern battery systems, materials for energy storage and conversion and the introduction of advanced characterization methodologies in the field of batteries. Sabina Kolar, a doctoral student with an excellent background in the field of biochemistry, is working on the project.
3. Project timeline and realization
WP1 (M1-M36): Biomimetic interfaces prepared from biological pores embedded into a membrane will serve as a self-standing separator or will be coated on the active particles. These membranes will have a functionality to control transport between the two electrodes or between the active material and the bulk electrolyte with a selectivity for the working cation. Biological pores like lysenin exhibit chemical and electrochemical stability in electrolytes based on aprotic solvents. Engineered pores will be integrated into the solid-state membrane for study of ionic transport through the pores and their selectivity. Progressively larger quantities of pores will be isolated for further studies. Optimisation in terms of the number of pores per surface area, their pore size and length will provide hybrid membranes that can be used as separator layers or membranes that can cover active cathode particles, i.e. forming protective layer (aCEI or aSEI) and with that directly control the transport from / to active material. Their electrochemical and physiochemical properties will be tested in WP3 with a focus on thermodynamic stability (chemical and electrochemical) and kinetics.
WP2 (M7-M36): Biosourced interfaces offer immense possibilities for tuning of their properties. Different biosourced polymers like cellulose, cyclodextrine, gelatine and others are known to be stable in the battery environment. These polymers will be used as a starting point for exploration of their potential use as self-healing agents in advanced battery systems. Biosourced polymers will be prepared with various nanostructured modifications which can offer different functionalities, like anisotropic assemble, channels and layers. These functionalities can be additionally decorated with chelating molecules that can trap cationic or/and anionic species. Processing of separators with biosourced polymers allows embedment of different functionalities which would enable integrity and stability as well as a controlled ionic transport.
WP3 (M12-M36): Characterisation and testing of self-healing functionalities is required in order to determine the (i) stability, (ii) operating mechanism, (iii) kinetics of self-healing process and (iv) possible side-effects of the most promising self-healing agents developed in WP1-WP2. Outcome from work in this WP will be a gain in scientific knowledge enabling further adaption of experimental conditions in WP1-WP2 and with that development of subsequent generations of self-healing agents. Our focus is on the most promising tools in terms of capability, adaptability, and usability, for example ex situ elemental analysis tools, such as inductively coupled plasma mass spectrometry (ICP-MS), ICP coupled with laser ablation; solid state in situ NMR; ex situ cryo-TEM and different operando mode spectroscopies.
4. Bibliography produced during the project
/
High Energy Organic Batteries (HEOBAT)
1. Description of the project
Development of cheaper, more energy-dense, safer, durable and sustainable battery technology will unlock innovation within transport and facilitate transition to renewables by providing flexibility in how we produce and consume energy. Within the HEOBAT project we aim to bring about this change. The project is designed to achieve this through the development of a fundamental platform of a completely new battery technology based on Redox-active Polymer Nanoparticles (RPN). This project is basic knowledge oriented. The possible future benefits of this new battery technology:
• A lower price of RPN- batteries compared to inorganic (350-600 $/kWh) as they will be produced from abundant materials.
• An improved sustainability profile as RPN can be produced by organic synthesis using renewable sources, organic waste or CO2.
• A lower energy cost for production as RPN can be prepared at low temperatures <100 °C vs. inorganics, which need temperatures >700 °C.
• Higher theoretical energy density (1100–1600 Wh/kg), vs. traditional inorganic based battery materials (500–700 Wh/kg).
• Higher power output as they can be discharged in less than 6 minutes (>10C rate) where most useful inorganics need above 30 min.
The project is innovative and interdisciplinary, integrating polymer science, electrochemistry, and modelling. It is ambitious in its scope, high risk and high gain. Our experiences in polymer nanoparticles, emulsion polymerization, academic and industrial networks mean we are uniquely placed to achieve this ambition.
The first novelty that this project brings is the preparation of completely new redox-active material based on poly(2,3,4,5-tetrahydroxystyrene) with a theoretical density of 1600 Wh/kg. The second novelty is the use of very small redox polymer nanoparticles, which will enable faster charging/discharging. The third novelty is the complete suppression of the active material dissolution by crosslinking.
Impact on batteries in general: If we reach all novelties listed above, this will have a profound influence on the battery research. In this case RPN-batteries will outperform most state-of-the-art batteries and will become the main research area. Moreover, as organic materials are flexible, they are very promising for the use with other bigger and more abundant cations such as Na+, K+, Mg2+, Ca2+, Al3+, Zn2+ – where most of rigid inorganic materials fail.
Impact on energy storage: Climate changes and decreasing reserves of fossil fuels are inciting our society for a shift toward renewable energy resources, i.e., wind, solar, hydropower, tidal, etc. While the latter can provide sustainable energy to meet our demands, energy production from renewable sources is often time-dependent. Thus, energy storage devices will be a necessary piece of the energy supply chain to balance the energy production and demand. Currently, energy storage solutions rely mainly on pumped hydro storage, but this type of energy storage has low energy density and requires a suitable geographical configuration. Batteries offer a more energy dense alternative and are expected to play an increasingly important role in the future electrical energy storage. When considering batteries for energy storage, price and sustainability are among the most important factors. RPN based batteries, especially the ones with lithium being replaced with other more abundant elements (Na, K, Mg, Ca, Al, Zn), will have all the desired properties for energy storage.
Financial Support: The project is financed from Slovenian research agency (ARRS) under the code N2-0165. The duration is of the project is 1.10.2020―30.9.2022.
2. Members of the project
Dr. Klemen Pirnat (Sicris): Leader and main worker is experienced researcher from the field of Organic batteries, organic synthesis and electrochemistry. On this topic he is already working since 2008, when Li-Organic batteries started to gain attraction.
3. Project timeline and realization
1st year:
Task 1 - Synthesis of monomers: First monomers will be synthesised from substituted benzaldehydes, which will be reduced to styrenes using methyltriphenylphosphonium bromide and n-butyllithium in tetrahydrofuran (Wittig reaction). 1,2,3,4-tetramethoxybenzaldehyde is not commercially available and will be prepared in three-step reaction from 1,2,3-trimethoxybenzene.
Task 2 - Emulsion polymerisation: Corresponding monomers will be polymerized in water dispersion to get polymer nanoparticles (RPN) from 40–400 nm particle size. Redox-active nanoparticles to be used in batteries will be prepared by copolymerisation with divinylbenzene crosslinker.
Task 3 – Deprotection: Methyl group from polymers will be removed using BBr3 to get electroactive –OH groups.
Task 4 - RPN/rGO composite: Graphene (rGO) is a wonder material due to its spectacular physical properties. It has very good electronic and thermal conductivity and is mechanically very strong. Incorporation of rGO will improve electronic and ionic conductivity due to an enhanced porosity of the composite. This will result in improved battery performance.
2nd year:
Task 5 - RPN electrochemistry: Three electrode measurements will be performed in a beaker cell with a reference electrode. Electroactivity of RPN materials will be tested in several types of electrolytes to find the optimal one.
Task 6 - RPN battery: We will prepare full battery cell. If possible Li-RPN battery will be developed with high voltage in the range 3.0–2.5 V. In case this will not be possible, we will develop full organic or zinc-organic batteries with lower voltages.
Task 7 - Operando FTIR and modelling: In order to monitor redox reaction during charge/discharge, ex situ or operando IR will be supported by DFT modelling. This will allow for monitoring the switching between reduced C-O- and oxidized carbonyl C=O groups as well as other changes inside the polymer structure during battery cycling.
4. Bibliography produced during the project
/
Model system-based interface design for enhancement of the electrochemical performance of Ni-rich NMC for Li-ion batteries
1. Description of the project
The ambitious goal of the proposed project is to achieve improved capacity stability of Ni-rich LiNixMnyCozO2 (NR-NMC, x+y+z=1, x > 0.6) cathode-based Li-ion battery cells via application of carefully designed protective interface coatings at the NR-NMC/electrolyte interface. To accomplish the proposed project goal, the design, deposition, and characterization of known and newly developed interfacial coatings will be approached systematically via the establishment of a comprehensive research platform for interfacial coating design and characterization. Within this platform, an NR-NMC811 thin-film model system with well-defined composition and surface crystallography will be designed and produced by pulsed laser deposition (PLD). Produced battery model system will be chemically and electrochemically aged to study the correlation of the interface structure with the electrochemical properties. The outcomes of this comprehensive approach will provide us with a knowledge matrix outlining the impact of the interface coatings on the NR-NMC/electrolyte electrochemistry. The knowledge matrix will serve for controlled transfer of the successful model system strategy to the commercial NR-NMC powder material.
Financial Support: The project is financed from Slovenian research agency (ARRS) under the code J2-3050 (C). Duration of the project is 1.10.2021 - 30.9.2024.
2. Members of the project
National Institute of Chemistry (NIC):
prof. dr. Robert Dominko (SICRIS): the project leader is an experienced and internationally recognized researcher on the field of modern battery systems. He is leading the electrochemical characterization part of the project;
dr. Jože Moškon (SICRIS) is working on designing setups for model system electrochemical testing;
dr. Elena Chernyshova (SICRIS) is in charge of the structural and compositional characterization of the materials and interfaces at the atomic level by means of advanced transmission electron microscopy methods;
Alenka Križan (SICRIS) is working on the development of the characterization techniques for battery interfaces.
Jozef Stefan Institute (IJS):
izr. prof. dr. Matjaž Spreitzer (SICRIS) is coordinating PLD related activities;
dr. Tjaša Parkelj Potočnik (SICRIS) is covering PLD targets preparation and films’ structural characterization;
dr. Jamal Belhadi (SICRIS) is performing PLD growth of thin films;
prof. dr. Gertjan Koster (SICRIS) is an expert in structure-property relation of atomically engineered complex (nano)materials and is contributing with the scientific discussions as well as for supervision of PLD related activities.
3. Project timeline and realization
WP 1 (JSI): This work package will focus on preparing PLD targets and on choosing suitable substrates (defined orientations and morphology) for depositing NR-NMC811 thin films.
WP 2 (NIC, JSI): Inorganic and organic protective coatings will be deposited onto NR-NMC811 thin film model systems prepared within WP1. Coating methods comprising PLD, sol-gel technique and wet coating process will be applied in the inert Ar atmosphere.
WP 3 (NIC, JSI): Cathode/electrolyte and cathode/coating/electrolyte interfacial phenomena will be investigated to the finest detail within the simplified experimental environment using advanced characterization methods and instrumentation available in the partnering groups. Comprehensive and interlinked characterization will help us to clarify the influence of the terminating plain on the cathode surface on the mechanisms of the battery capacity decay as well as to gather more thorough understanding of the coating protective function upon long-term battery cycling.
WP 4 (NIC): Well-performing model system coatings will be coated onto commercial NR-NMC811 (TARGRAY, Canada) powder. Special attention will be paid to the coating homogeneity and its distribution over the secondary particles due to the heterogeneous crystallography of the secondary particle surface.
WP 5 (NIC, JSI): This work package will be dealing with project management, data management, and communication, dissemination and exploitation of the project results.
4. Bibliography produced during the project
/