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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

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Reaction and transport mechanism investigation for magnesium metal battery anode

1. Description of the project

The project’s objective is to study passive layer formation kinetics at open circuit voltage on magnesium metal anodes with impedance spectroscopy using (i) chloride containing electrolyte compositions and (ii) less corrosive electrolytes. We will employ advanced operando impedance spectroscopy measurement technique for the purpose of deeper understanding of mechanism of operation of magnesium metal anode by simultaneously varying cell parameters (separator thickness, electrolyte concentration, etc.) and measurement conditions (temperature, current density, extent of cycling). Both the OCV and operando impedance spectroscopy measurements will be coupled with morphology and chemical composition analysis of magnesium metal surfaces in order to provide more information on passive layer growth and supply input parameters (layer thicknesses, species concentration, porosity) for the development of impedance model simulations. Qualitative and quantitative analysis of modelled spectra will be used to identify physical processes behind each impedance contribution, how they change during cycling, as well as the bottle-neck of the mechanism of operation and provide targeted research paths for direct performance improvements.

Financial support: The project is financed from the Slovenian research agency (ARRS) under the code Z2-4465 with the starting date 30. 3. 2023.

2. Members of the project

Dr. Sara Drvarič Talian, project leader


3. Project timeline and realization

The work will be divided into four work packages (WP), according to the project objectives. The first WP will deal with following the passive layer growth on magnesium metal anodes at open circuit voltage conditions. In WP2, operando impedance spectroscopy measurements will be used to deepen the understanding of the mechanism of operation during charging and discharging (stripping and plating) of the studied metal anodes. In WP3, morphology and chemical composition analysis of magnesium metal surfaces will be conducted in order to provide more information on passive layer formations and to supply input parameters for the development of impedance spectra models. In WP4, information gathered in other work packages will be compiled to prepare a model of the cell operation, which will be used to simulate impedance spectra. The simulations will be used for qualitative and quantitative analysis of spectra in order to identify physical processes behind each impedance contribution, how they change during cycling, as well as the bottle-neck of the mechanism of operation.

List of tasks

(WP1)

T1.1 Evaluation of Mg metal anode impedance properties at OCV in various electrolytes

T1.2 The effect of variation of cell parameters on the OCV impedance spectra

T1.3 Operando electrode cutting for study of passive layer growth

 (WP2)

T2.1 Development and measurement of dynamic EIS on symmetrical two-electrode magnesium metal anode cells

T2.2 The effect of variation of cell parameters on the dynamic impedance spectra

T2.3 Evaluation of current density influence and cycle life on the dynamic impedance spectra

T2.4 Three-electrode magnesium metal cell impedance measurement

 (WP3)

T3.1 Microscopy analysis of metal anode surface morphology

T3.2 Chemical characterization of passive layer composition and properties

 (WP4)

T4.1 Quantitative and qualitative analysis of measured impedance spectra

T4.2 Reaction and transport mechanism proposal

T4.3 Impedance spectra simulations

T4.4 Model validation for calcium metal anode
 

4. Bibliography produced during the project
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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

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Past ARRS projects

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

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Redox active organic materials

Research activities within the project are target oriented with aim to synthesize redox electroactive organic material which can be applied in the different battery systems. As a final aim we plan to obtain several prototype batteries in the size of coin cells which will show stable cycling over 1000 cycles with capacity fading less than 20% of the initial capacity. Work on the project will be divided into four work packages. They are subsequently divided into individual tasks, which are interconnected to each other and follow each other in the logical order. Three research organizations will participate in the project as equal partners. Work between organizations is equally distributed and complement in between and does not duplicate.

Financial Support: The project is financed from Slovenian research agency (ARRS) under the code J2-8167 (C). The duration is of the project is 1.5.2017 - 30.4.2020.

Project research group

National Institute of Chemistry (KI):

Izr. prof. dr. Robert Dominko (SICRIS): A project leader is an experienced and internationally recognized researcher on the field of modern battery systems. He is also a coordinator of EU project with acronym HELIS (H2020 project).

dr. Klemen Pirnat (SICRIS) & dr. Alen Vižintin (SICRIS): They will contribute to synthesis, functionalization and polymerization redox active organic monomers

doc. prof. dr. Ivan Jerman (SICRIS): with experiences on the field of characterization of materials by using FTIR spectroscopy.

Faculty for Chemistry and Chemical Technology (FKKT):

doc. prof. dr. Boštjan Genorio (SICRIS): He will work on functionalization of carbon materials and since he is also trained organic chemist he will work on the organic synthesis as well.

Institut Josef Stefan (IJS):

doc. prof. dr. Matjaž Kavčič (SICRIS): His responsibility will be to write applications for beam time and to actively work during beam time shifts and to analyze results.

Izr. prof. dr. Matjaž Žitnik (SICRIS): His task will be to link the recorded XAS, XRS and FTIR spectra to the molecular orbital picture and generate useful estimates for preparation of experimental proposals.
 

Project management & realization

 

 

M6

M12

M18

M24

M30

M36

WP1

Synthesis

Task1.1: Organic synthesis

 

 

 

 

 

 

Task1.2: Functionalization

 

 

 

 

 

 

WP2

Composites

Task2.1: Polymerization

 

 

 

 

 

 

Task2.2: Hybrid composites

 

 

 

 

 

 

WP3

Characterization

Task3.1: Electrochemical characterization

 

 

 

 

 

 

Task3.2: Operation mechanism

 

 

 

 

 

 

WP4

Optimization

Task4.1: Improvement of the energy density

 

 

 

 

 

 

Task4.1: Prototype as a coin cell batteries

 

 

 

 

 

 

 

Workpackage 1 (members KI and FKKT): in this workpackage we will synthesize redox electroactive organic materials and perform structural and chemical characterization. Prepared materials will be appropriately functionalized to enable their polymerization and synthesis of hybrid materials.

Realization of the goal 66 % (Feb 2018). All planed syntheses of redox active monomers were conducted and were successful. Two types of functional materials were prepared: dihalogenated monomers for further polymerization with Ni(COD)2 and vinyl monomers for further polymerization in dispersed media. Generally yields were high and materials were purified by extraction, crystallization or column chromatography. As prepared monomers were characterized by NMR, IR and other techniques needed to fully confirm the chemical structure and purity. Also new redox material with almost doubled theoretical capacity was proposed based on 1,2,3,4-tetrahydroxybenzene redox center. Also this compound was successfully synthesized despite long four step synthesis. This WP1 is not finished yet as there are also some new materials to be synthesized in the future.

Workpackage 2 (members KI and FKKT): in this workpackage we will synthesize composites based on redox active molecules either by direct polymerization of monomer units prepared in the WP1 or by polymerization in the presence of carbon nanostructured materials (graphene, graphene nanoribbons or carbon nanotubes).

Realization of the goal 25 % (Feb 2018). All prepared monomers from WP1 were successfully polymerized with one exception of poly(napthoquinone) K237 where last oxidation step didn’t work. As already mentioned two polymerization reactions were used: polymerization with Ni(COD)2 and polymerization in dispersed media. Polymers using first polymerization have high theoretical capacities due to low MW of redox unit (no additional redox inactive functional groups). The second polymerization method benefited from very small polymer nanoparticles in the range 40-100 nm. This is very important improvement in the field of redox polymers for use in Li and other battery systems. To our knowledge there are no publications connected to preparation of redox active polymer nanoparticles and their use in Li and other battery systems. Polymerization of PFQ polymer was also performed in the presence of reduced graphene oxide (rGO) to get composite material PFQ/rGO with improved electrochemical properties. In the field of polymerization and composite preparation is still a lot of room for modifications and improvements (33 % realization).  Future plans are preparation of crosslinked polymers (capacity stabilization) and composites with carbon additives (carbon black, carbon nanotubes, graphene, etc.).

Workpackage 3 (members KI and IJS): in this workpackage we will perform a preliminary characterization of polymers prepared within WP2. Additionally, we will study mechanism of charge transfer by using FTIR spectroscopy. Synchrotron measurements are planned to be done within this workpackage as well.

Realization of the goal 20 % (Feb 2018). All synthesized redox active polymer materials were tested in Li-battery systems. Polymer PFQ was further improved by addition of graphene resulting in a PFQ/rGO composite, which has a capacity 200 mAh/g and very stable cycling tested in 500 cycles. This is attributed to polymer insolubility in organic electrolyte. Poly(benzoquinonyl) K174 and polymers synthesized with polymerization in dispersed media on the other hand shows much lower initial capacities and fast capacity fading during cycling which is can be explained by solubility in organic electrolyte in Li battery. In WP3 these are only initial results and future plan is to stabilize the capacity by preparation of crosslinked polymer nanoparticles, which are not soluble in electrolytes.

Testing in other battery systems (Mg, Ca, Zn): First redox active polymers need to be prepared which in Li battery systems exhibit high capacity and stable cycling. The reason is that Li battery system is the most reliable system and Li electrolytes are already optimized for both: metallic lithium anode and organic cathode materials. Other battery systems (Mg, Ca, Zn) are new research fields and there are additional problems as electrolytes not optimized yet. Currently the research is going on to develop better electrolytes which are compatible with metallic anodes and organic cathodes at the same time but is still in it’s infant stage.

Workpackage 4 (member KI): based on measurements performed in the WP3 we are going to tune synthesis in the WP1 and polymerization process in WP2 in order to obtain active materials which show good electrochemical characteristics. Selected samples will be built into the coin cell prototype batteries and tested for the longer period of time.

Realization of the goal 0 % (Feb 2018). According to the timetable no work on WP4 was performed yet.


Equipment:

EQUIPMENTPotentiostat/galvanostat board with EIS(/Z) option
Year of purchase2017
FinancingProject ARRS
Access to equipmentThe equipment is located at D10 at the Institute of Chemistry. It is used in the laboratory, but since it is a portable equipment, it is also used for the operando measurements.
Purpose of equipment and additional informationIt is used for the purpose of testing laboratory batteries. The maximum current is 500mA at the voltage of 10V testing.
Price for use of equipment (EUR/h)5.00
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