IONIC-LIQUID IN CONFINED ENVIRONMENTS: EXPERIMENTS AND SIMULATION

Lead Research Organisation: Imperial College London
Department Name: Dept of Chemistry

Abstract

Electrical double layer capacitors (EDC) store energy using accumulation of ions of opposite charge in a nano-thick layer at high surface area electrodes. They can complement batteries in energy storage and harvesting, when high power density and fast delivery or uptake is needed. A notable improvement of EDCs has been achieved due to advances in nano-structured materials. Experimental results of the Gogotsi group that show that desolvation of electrolyte ions in pores smaller than the size of solvated ions. leads to higher capacitance, opened the door to improved devices using a variety of electrolytes. In the absence of faradic reactions across the interface, which degrade electrodes in batteries during charge/discharge cycles, EDCs can sustain millions of cycles, while batteries survive a few thousand at best. But EDCs suffer from a limited energy density. This is why EDC research is largely focused on increasing their energy performance and widening the temperature limits into the range where batteries experience thermal runaway (explosion). Energy density is proportional to capacitance and is roughly quadratic in voltage. Thus, the larger voltage window (determined by the electrolyte decomposition and Faraday processes at high potentials) and the larger capacitance are the targets in EDC research. Both are provided by room-temperature Ionic liquids (RTIL) --solvent-free liquid electrolytes; their voltage stability is thus only driven by the electrochemical stability of the ions. As was recently understood, RTILs made a revolution in solution chemistry, because RTILs and their mixtures are the 'designer solvents/electrolytes' of high fidelity, as they are non-volatile under a wide range of conditions. Many of them are environmentally friendly. These features present a world of advantages, but also a challenge: how to choose the best RTIL for a given application from hundreds available and thousands possible? In EDC-research, this is impossible without deep understanding of the properties of electrical double layer in ionic liquids on flat electrodes, for a start, and electrodes with nano-templated surfaces, as 'designer electrodes' must match the 'designer electrolytes'. Achieving this understanding through the interaction of theory, simulations and experiments is the task of this proposal. We will perform modelling and simulation of equilibrium properties, such as capacitance, and transport-dynamics to determine how ions diffuse to and from flat carbon and in and out of nano-porous (pore size <2 nm) and mesoporous (2 nm - 10 nm) carbon electrodes. The results will be compared with experimental data obtained on planar graphite, graphite with nano-trenches and nano-templated electrodes built of assemblies of carbon nanotubes. This will be done in a series of RTILs, with systematic variation of asymmetry in the size of cations and anions, and their anisotropy. Of particular interest will be understanding and implementation of the phenomenon recently discovered by Gogotsi: the maximum of capacitance as function of the average pore size, detected in the nano-porous regime. According to preliminary estimates of A. Kornyshev, the latter may be related with the screening of ion-ion interactions in the metallic nano-pores due to image forces. The latter will be incorporated in the simulation force-fields of ion-ion interactions. Of special interest will be the effects of polarity of EDCs caused by the interplay between different pore sizes on the two electrodes and different sizes of cations and anions. The project is conducted in collaboration between researchers from Drexel University in Philadelphia, US, (experiments) and Imperial College, London, UK (modelling). Its completion will bring a new level of understanding of the optimal nano-scale carbon structures and RTILs for optimization of energy storage, charging and power delivery.

Publications

10 25 50
 
Description This was an "International Cooperation in Chemistry" sister project of the NSF project of Professor Gogotsi at the Drexel University (USA) whose group was responsible for its experimental part; my group responsible for theoretical and simulation background. Generally, we substantially advanced understanding of the structure, electrical response, and charging dynamics of ionic liquids at flat electrodes and in ultrananoporous electrodes, and that understanding has resulted in a number of conclusions potentially of big importance for optimizing electrical properties of supercapacitors and their structures for the maximal energy storage and fast charging-discharging.

The findings of our work can be split into four categories, and are summarized under each title.

1. Theory of the structure and electrical response of ionic liquids near a flat electrode.

a) The study of the effect of asymmetry of charge distribution in one sort of ions by means a model Monte Carlo simulation has shown the effect of such features on the anatomy of the electrical double layer, changing with voltage variation. It has shown that neutral tails of cations act as latent voids for the voltage-induced rearrangement of the charge, and their mere presence leads to a double-hump camel shape of electrical capacitance of the interface even at high compacity of the liquid, in accordance with experimental observations.

b) We developed a theory of the overscreening effect in the electrical double layer in ionic liquids, by constructing a phenomenological Landau functional and minimizing it to obtain the charge and potential distributions in the double layer and its differential capacitance. The results have shown that overscreening is gradually destroyed by an applied voltage with a crossover to the regime of crowding (the so called 'lattice saturation') in which the capacitance decreases inversely proportionally to the square root of voltage. This was the first theory of this kind ever built. It has shown excellent agreement with our earlier Molecular Dynamic simulations of analogical systems.

2. Electrical response of ionic liquid in nanoconfinement.

Having taken into account that the interionic interactions inside a nanoscale pore of porous electrode are exponentially screened, we were first to build a theory of capacitance of ultra nanoporous electrodes and explain the Simon-Gogotsi anomalous growth of the capacitance per unit surface area with a decrease of the pore size. The structure of the theory is different for slit pores and for cylindrical single-file-like pores.

For a slit pore 2-dimensional model for which we have obtained a mean-field solution for the description of equilibrium properties such electrical capacitance and the amound of charge in the pores was developed, whereas for a cylindrical pore we were able to map the problem on exactly-solvable 1- dimensional models of statistical mechanics.

For pores strongly adsorbing ions it was a 1d two state Ising model and for any other pores - 1d three state Blume-Emergy-Griffith (BEG) model, both with nearest neighbor interactions, both having exact solutions. For the Ising model a stndard solution was available from textbooks, but for BEG model it had to be developed and we obtained it, having compared it with Monte Carlo simulations. These results are of textbook quality, which were not existing before in the science of nanostructured supercapacitors.

The results of all these models qualitatively explained the Simon-Gogotsi effect, but also predicted for the first time interesting dependences of capacitance on voltage. It has been shown, however, that some of those dependences are smeared out by pore size distribution, leading to a much milder voltage dependence. Nevertheless, we have shown that the differential capacitance of the pores diminishes to zero at large voltages, and this happens earlier in narrower pores than in wider pores, although the capacitance of small pores at small voltages is higher. Therefore, we have proposed a concept of an optimal size of the pore for the maximal energy storage at a given operation voltage, and have plotted it as a function of voltage.

All these findings were tested by computer simulations and compared with Gogotsi experiments; they were pioneering as we were first to report such results.

3. Next we went to terra-incognita: dynamics of charging-discharging of ultra narrow nanopores. Whereas charging of microscopic and mesoscopic pores have been studied in a large number of works by many authors (going back to the transmission line models of De Levi), we were first to analyze these processes in a nanopore. We have build a phenomenological theory of this process, which predicted different modes of pore charging for initially empty (ionophobic) and filled (ionophilic) pores. We find that charging of ionophobic pores proceeds in a front-like way, while charging of ionophilic pores is diffusive; in both cases, however, the accumulated charge grows at the beginning as a square root of time and at long time exponentially reaches saturation. These results have led to suggestions of a two-step complementary optimization of porous electrodes for supercapacitors. In a first step, the optimal pore width is chosen to maximize the stored energy density; in a second step, the optimal pore depth/length (that is, electrode's thickness) is chosen to satisfy the requirement on charging times. All these predictions of the theory has navigated the first molecular dynamic simulation study of the kinetics of charging of slit nanometer pores. The results of the phenomenological theory have been basically reproduced, but with a number of further findings, e.g. dramatic dependence of the diffusion coefficient of ions in the pore on electrode potential; the diffusion coefficient can change 2-3 order of magnitudes together with restructuring the layer of ions in the pore.

4. Based on our findings about the equilibrium charge storage and charging dynamics in ultra-narrow nanopores, we came to a new concept of the best performance of ionophobic pores and have published a 'pressing-a-spring manifesto' about it in the first issue of Nanoscale Horizon, a call to material scientists to create and test such pores. The research in this direction in the Gogotsi group is ongoing, but we expect that our new concept will be further explored by other groups such Clare Grey group in Cambridge.

5. All our theoretical constructions were based on ideally metallic properties of the electrodes. But the electrodes for supercapacitors are usually made of various types of carbon materials. We therefore needed to establish how the effect of electric field penetration into such materials can affect these results.

We have found that it renormalizes the effect of pore size on the screening of interionic interactions inside the pore, by just slightly increasing the exponential decay range by the Thomas-Fermi length, which is about 0.2 nm in such materials, thereby not dismissing any of the obtained results. This may be different between two sheets of graphene, where our preliminary results have shown the decay of interaction energy inversely proportional to the cube of radius. But it is still a short range interaction in 2d.

At flat electrodes, the field penetration into the electrode may have a more profound effect. This has been shown for graphite: at small voltage the capacitance of the interfacial capacitance is actually dominated by graphite, but not by the ionic liquids and it has U-shape as a function of voltage; only at large voltage the contribution to capacitance of the ionic liquid starts to dominate, and the capacitance will decrease with voltage. This perfectly corresponds to available experimental data.

6. We have developed a theory of electroactuators (relatives to capacitors: essentially capacitors with bendable electrodes) with single mobile charge carrier species. The principle of the work of such gadgets is as follows. A ionomer membrane is sandwiched between two nanoscale-thin bendable metallic electrodes, which contains anionic pendant groups that are attached to the rigid polymer backbone, and mobile bulky ionic liquid type cations. A voltage difference between the electrodes generates an electric field that drives mobile cations to migrate to the negative electrode, creating a cation accumulation layer there and a corresponding depletion layer at the positive electrode. Excess of bulky cations creates strain on the cation rich side and their absence on the opposite side causes membrane shrinking, and the plate bends. Just a few volts are needed to achieve substantial bending, making these systems prime candidates for smart robotics and prosthetics, as well as they can generate voltage if you bend them by force, say in a turbulent flow, which can be used for energy generation or sensing.

We developed the first transparent analytically tractable theory of electromechanical transduction for such electroactuators, in which the ion distribution and curvature are mutually coupled. We obtained expressions for the dependence of the curvature and charge accumulation on the applied voltage, as well as the electroactuation dynamics, and compared them with literature data. We found that the mechanical or sensor performance of such electroactuators is determined by just three cumulative parameters, permitting a scaling approach to their design.

7. In the follow up work, not initially planned in the project after the project was officially finished:

(a) We have investigated for the first time, using molecular dynamic simulations, the laws of the friction with ionic liquids filled nanoscale gaps allowing for just several layers of ions. We have studied the role of the charge on the solid plates, which opens new routes for an electrical control of nanoscale friction. We have found that polarizing the plates shifts the shear plane from the fist layer to the middle layers in the gap, which helps both to protect surfaces against wear and dramatically reduce friction. We have been able to characterise the in-plane structure of each layer and thereby give physical interpretation to our findings.

(b) By means of molecular dynamic simulations we have studied electrosorption of water from the bulk ionic liquid (contaminated by small amounts of water) into electrical double layer. We have found statistically preferential positions for water in the double layer and discovered that it will always be presented in the first layer and its population in the first layer increases both for positive and negative polarizations of the electrode, but asymmetrically stronger for positive electrode polarization. All conclusion were made so far only for carbon electrodes. They may appear to be different for metallic electrodes, due to different characters of interactions of cations and anions of ionic liquids and water with those electrodes.

(c) As a follow up development of our study of charging dynamics, we have explored the role of the earlier found effects in the cyclic voltammetry of charging of the same kind of pores, having predicted a number of effects the existence of which could be verified experimentally when the electrodes with monodisperse slit pores would be created.

(d) Having developed a simple theory, we have performed a speculative study of the role of the crowding effect on the rate of electrochemical reaction from ionic liquids controlled by electron transfer. We have found that instead of the classical Tafel law we may encounter with linear dependence of the logarithm of the electrode current on the square root of overpotential. This prediction is not easy to verify because unless special measures are taken, most of the electrode reactions in ionic liquids are diffusion limited. We furthermore intend to develop more sophisticated theory of such reactions (planned within our cooperation with MIT).
e) We have further developed the theory of electroactuation using porous electrodes, reveals scenarios which could enhance the strength of electroactuation by the orders of magnitude. We have created a theory of reverse actuation for electrical current generation from walking based on porous electrodes which can generate higher currents than earlier explored. f) We have explored electrosorption of water at electrodes, which is important for understanding where water absorbed from humid air into the liquids will be distributed with respect to the electrode in order to understand how to avoid undesirable consequences of its electrochemical reactivity.
Exploitation Route It is too early to advice on industrial exploitation of these findings, because the pioneering theories resulted from this project should still be developed on a number of fronts, and all (but not only some) of their predictions must be experimentally tested. However, one there is already a large set of such predictions, all formulated in the papers that we have published, concerning the properties of supercapacitors and electroactuators. They are related with the optimal size of pores, optimal operation voltage, the speed and mode of charging-discharging, benefits of ionophilization or ionophobization of the pores, and the role of pore size dispersion. Since supercapacitors are emerging competitors or complementary devices to batteries, all these aspects will be extremely important for the optimization of their energy storage and power delivery, to be achieved not by trial and error, but based on the fundamental theory. This is what the results of this project offer. The same refers to electroactuators, the convertors of electrical energy into motion and vice versa, that are considered to be promising for micro- and nanorobotics, sensors, and alternating-current generators. The potential acquired by this three year project, which continues running on minor available resources, is enormous. To maximally benefit from it will require further funding, most likely within a larger scale national or international project with the involvement of national laboratories and industrially related groups (the plans for it are in place).

1. The results on flat electrodes comprise the basics of the double layer theory in ionic liquids, the structure of which and response to charging underpins the kinetics electron transfer reactions at electrodes with ionic liquids, when the latter replace ordinary electrolytic solutions. Such reactions are crucial steps in electrosyntesis and extraction of metals. Next understanding the laws of ion layering near electrodes is instrumental for understanding friction. Exploitation of these results are seen in (i) developing the theory of electrochemical kinetics in relation to overscreening effects and lattice saturation, which may dramatically change the current voltage plots for slow electron transfer (redox) reactions at such electrodes; (ii) in systematic experimental testing of the predictions of our theortical results on quantized and electrotneable friction with ionic liquids, already started in the group of S. Perkin in Oxford University (once verified they can be used in developing new scenarios of super-lubricity that can be tuned on and off by applied voltage)

2. Results for the electrical response of ionic liquids in nanoconfinement lay the basis of understanding of functioning ultrananoporous supercapacitors.

- Whereas a number of these results have rationalized the existing experiments and some (such as investigation of optimal pore size and the role of pore size distribution) has triggered experiments that showed results in agreement with the theory, systematic experimental study of voltages dependence in nanoporous electrodes with a given geometry of the pore is still lacking. Such experiments with well defined monodispersed pores should be performed, and they expect to show the dramatic voltage dependence of capacitance, as predicted by the theory.

- Whereas, the ultra narrow nanopores have been described by the developed theory, as well as an opposite limit of semi-infinite flat electrodes, the intermediate size pores require different analysis. Three groups in US, inspired by our findings have studied them using different methods, exploring the size dependence, but voltage dependence has not been studied. This is to be the next task on the agenda, as such pores, although they do not deliver the highest capacitance, are also often present in nanoporous electrodes. The achieved results pave the way to such studies.

- The results for single file models can and should be extended to the case of different sizes of ions, their charge asymmetry and anisotropic shape; this should include also different propensity for cations and anions to occupy the uncharged pore. In the first most simple versions of the theory we have already done this (the results are submitted for publication but are not published yet).

- Both single-file and narrow slit-pore results has shown that the capacitance should depend dramatically on the propensity of ions to settle in the initially nonpolarized pores. This gives strong motivation to experimentalists to determine this propensity. Such experiments are in progress in Prof. Claire Grey group in Cambridge and Prof. Yuri Gogotsi at Drexel.

3. Our predictions of the dramatic difference in the statics and dynamics of charging of ionophilic and ionophobic pores demand both the determination of iophilicity /ionophobicity of pores (c.f.Clair Grey's experiments) and experimental verification of the modes of charging. This will be the immediate exploitation of the obtained results.

4. Our theory of the static and dynamic bending modes of ionic-liquid- based electroactuators driven by applied voltage is a pure challenge for experimental groups. There is a broad set of predictions in our two published papers, related in the first place to the size and chemical nature of mobile ions that all ask to be experimentally tested and if verified can be recommended for optimizing the performance of electractutors. Reduction of their multiple characteristics to three dimensionless parameters, can navigate the design of electroactuators.

The theory, however, has been developed for flat electrodes. Nevertheless, it gives a platform and a reference frame for extending it to nanostructures electrodes.

5. The first results on the non-ideally metallic response may be put into basis of developing of a more sophisticated theory, approximate analytical or based on electron density functional theory.

6. Having considered the electroactuators to be able to swell, we next have explored some effects of swelling insupercapacitors (the 'unwanted' electroactuation). The latter do experience internal stresses and strain that are experimentally measurable. This phenomenon is important to understand as it has a damaging effect on supercapacitors. Our results were in good agreement with the first results of Volker Presser group at the University of Saarbruecken, and will be continued test in his group.

Many of our results and predictions we made on the basis of simple, generic models; this was done deliberately to reveal the basic physics behind the found effects. They were pioneering and followed by a number of more sophisticated computer simulations, based on more realistic force field of interactions between ions and electrodes. And many of our finding has already been reproduced (c.f. works of M. Sallane and B. Rothenberg in Paris, Watamanu and Bedrov in Utah, etc.), we continue to lead in exploring the unknown territories in this area with many followers (which is documented by the high and immediate impact of the most of our publications.
Our latest predictions concerning the distribution of water at electrodes as a function of electrode potential in ifluenced groups in Japan (Supporo University), USA (MIT) and Russia (Institute of Liquids and Solutions, RAS, Ivanovo) to explore these effects in further details. With the latter two groups we have started collaboration and are working on new joint publications.
Sectors Energy

 
Description The prediction about ionophobic channels enhancing simultaneously energy storage and power of supercapacitors are currently being tested in several experimental labs. If approved, they will offer new scenarios in design of supercapacitors. The results on new structures for electroactuators and reverse actuators are going to b eimplemented in collaboration with a company adffiliated with the Department of Mechanical Engineering of Virgina Tech; agreement under preparation.
First Year Of Impact 2017
Sector Energy
 
Description Collaboration with Clemson University continued to Virginia Tech, with the move of the PI there, in theory and computer simulation of charging dynamics of nanoporous supercapacitors 
Organisation Clemson University
Country United States 
Sector Academic/University 
PI Contribution The collaboration is focused on perfomance on novel specially designed computer simulations for charging dynamics of slit nanopores of ultrananoporous supercapacitors navigated by model theory. The theory driving the formulation of the basic conditions for simulation, sysetm properties and charactersitics to simulate was our main contribution, together with analysis of results, feedback that pushed performance of new simulations, preparation of publications Collaboration comprises information exchange, joint research, supervision of research students, preparation of joint publications, presenting joint results at conferences.
Collaborator Contribution In both cases these were groups of Prof. Rui Qiao, who was first at Clemson University and then moved to Virginia Tech. He and his students and collaborators have contributed unique knowledge and codes for molecular dynamics simuulations at fixed electrode potentials.
Impact Three publications in high profile journals (Nature Materials, ACS Nano, J.Phys.Chem.Letters) have been published on charging dynamics of nanoporous electrodes, and electrosorption of water from water-contaminated ionic liquids.
Start Year 2012
 
Description Collaboration with Clemson University continued to Virginia Tech, with the move of the PI there, in theory and computer simulation of charging dynamics of nanoporous supercapacitors 
Organisation Imperial College London
Department Department of Mechanical Engineering
Country United Kingdom 
Sector Academic/University 
PI Contribution The collaboration is focused on perfomance on novel specially designed computer simulations for charging dynamics of slit nanopores of ultrananoporous supercapacitors navigated by model theory. The theory driving the formulation of the basic conditions for simulation, sysetm properties and charactersitics to simulate was our main contribution, together with analysis of results, feedback that pushed performance of new simulations, preparation of publications Collaboration comprises information exchange, joint research, supervision of research students, preparation of joint publications, presenting joint results at conferences.
Collaborator Contribution In both cases these were groups of Prof. Rui Qiao, who was first at Clemson University and then moved to Virginia Tech. He and his students and collaborators have contributed unique knowledge and codes for molecular dynamics simuulations at fixed electrode potentials.
Impact Three publications in high profile journals (Nature Materials, ACS Nano, J.Phys.Chem.Letters) have been published on charging dynamics of nanoporous electrodes, and electrosorption of water from water-contaminated ionic liquids.
Start Year 2012
 
Description Collaboration with MIT on ionic liquids at interfaces and confinement 
Organisation Massachusetts Institute of Technology
Country United States 
Sector Academic/University 
PI Contribution Collaboration has started with the development of a theory of the electrical double layer in ionic liquids, including the ovescreening effect. It has resulted in a paper in Physical Review Letters cited 220 times by 05 /03/2016, according to WOS, as quoted in one of the Publication outcomes. Currently now we have plans for two new related projects, one started already, the precise topics of which we will not disclose at this stage. The collaboration comprises information exchange, joint research, skype conferences, involving supervision of project students, preparing joint publications, presenting joint results at conferences. The contributions of the research team of Professor Kornyshev is ideas for new scenarios in energy storage and harvesting, first pioneering theories for further joint developement
Collaborator Contribution Professor Bazant and his collaborators contribute important knowledge and methods of the theory of electrokinetic phenomena excelled in MIT
Impact Our first joint publication Physical Review Letters has been cited 220 times (by 05 /03/2016) according to WOS. Collaboration is interdisciplinary (condensed matter physics, chemical physics, electrochemistry, smart materials). M.Bazant and A.Kornyshev have submitted an application for seed grant for cooperation between MIT and Imperial College.
Start Year 2010
 
Description Collaboration with Penn State University on theory and design of electroactuators with ionic liquids 
Organisation Penn State University
Country United States 
Sector Academic/University 
PI Contribution The collaboration comprised information exchange, joint research, skype conferences, involving supervision of project students, preparing joint publications, presenting joint results at conferences. Most of the technical work in terms of the formulation of the problems and their solutions was performed by my group.
Collaborator Contribution Professor R.Colby of PennState is one of the internationally leading experts in the physics of complex polymer systems and dynamics of polymers. He contributed his knowledge of the polymer composite systems related to the electroactuation systems that we have been studying, participated in the choice of the most adequate and economic models, the analysis of results and of the experimental data. Furthermore Colby's general physical intuition was very useful in this work.
Impact This collaboration has resulted in two original papers containing the theory of electroactuators with single charge mobile ionomer mebranes listed in the publication section. it has cause invited talks at conferences (as quoted in the negagement section. The predictions of theory had already been compared with the existing experiments, but further specially designed experiments have been envisaged to be performed in the group of Professor Q.Zhang at PennState. They were put on hold due to the lack of funds on the subject of electroactuation in that group. We are planning to continue in that direction within the framework of a new round of cooperation with the group of Professor Bazant at MIT, as described in the other subsection of Collaborations. Collaboration was interdisciplinary, at the interface of physics of polymers, electrochemistry, and the science of smart materials.
Start Year 2011
 
Description Collaboration with the Center for Nanomaterials of Drexel University 
Organisation Drexel University
Country United States 
Sector Academic/University 
PI Contribution Our task in collaboration was developing the theory of charge storage in ultranarrow supercapacitors, both equilibrium properties and dynamics.
Collaborator Contribution The role of Director of Center for Nanomaterials at the Drexel University was in providing us with experimental data being obtained in his group, advice on adequacy of the models we have been formulation, and problem targeting.
Impact We have published in 2012 paper in high impact journal ENERGY & ENVIRONMENTAL SCIENCE, as quoted in the publication section, a joit paper with Gogotsi group with important results on the charge storage in ultrananoporous electrodes, which by 05.03.16 has been cited, according to the WoS 112 times. The results of our joint work have been included in many talks (listed in Engagement section) The collaboration was interdisciplinary at the interface of physics, physical chemistry and electrochemistry, and material science.
Start Year 2011
 
Description Collaboration with the Laboratory of Theoretical Condensed Matter Physics, CNRS, France, on dynamics of ion transport and transport of biopolymers in nanoporous electrodes and through nanoporous membranes in single file nanopores 
Organisation Sorbonne University (Paris IV)
Country France 
Sector Academic/University 
PI Contribution Collaboration has been started on the specific project of charging dynamics of quasi-single-file nanopore and the first joint paper with Dr. G.Oshanin, Director of Research at CNRS has been published (the paper in IOP Nanotechnology quited in publications outcome) . Inspired by some findings and the experimental work running in our Department, we have started a new, only indirectly related project, associated with the trasport of DNA plasmids through nanoporous mebranes (part of the work performed in Max Planck Institute in Stuttgart, Germany). Collaboration comprises information exchange, joint research, supervision of research students, preparation of joint publications, presenting joint results at conferences. Our contributions to the joint work was in the problem formulation, discussion of the methods of solution, joint work on solutions of the problems, preparation of publications, dissemination of results.
Collaborator Contribution Joint discussions of problem formulation, discussion of the methods of solution, joint work on solutions of the problems, preparation of publications, dissemination of results.
Impact The quoted first publication in IOP Nanotechnology quated in the publication section and inclusion of results into the multiple talks at conferences quoted in the engagement section. Interdisciplinary: electrochemistry, physical kinetics, statistical physics
Start Year 2010
 
Description 1st Invited talk at Symposium " Ionic Liquids and Coulomb Fluids at Interfaces" at Interfaces, Windsor Park, 25-27 June, 2012 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on the subject of Ionic liquids at electrified interfaces and nanoconfinement have been delivered by Prof. A.Kornyshev followed by a related talk of a senior PDRA on the project S.Kondrat.

Professor Kornyshev gave an an overview of the project achievements with a focus on the laws of charging single file pores.
Year(s) Of Engagement Activity 2012
 
Description 2nd Invited talk on Ionic Liquids and Coulomb Fluids at Interfaces, Cumberland Lodge, UK, 25-27 June, 2012. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on "Ionic Liquids in nano-confinement for energy storage".

This was continuation of the previous talk presented at the same symposium by A.Kornyshev. Kondrat's talk focused on the latest findings of the project on charging dynamics.
Year(s) Of Engagement Activity 2012
 
Description 68 Annual Meeting of the International Society of Electrochemistry (27 August - 1 September 2017, Providence, Rhode Island, USA), Invited Keynote lecture of Prof. A. Kornyshev at Symposium 7: Supercapacitors from Materials and Processes to Applications 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact The lecture focused on the steps from supercapacitors to the sister systems like electroactuators, inverse actuators, and electrotuneable nanotribology, and caused interest of electrochemical community to these novel electromechanical metamaterials.
Year(s) Of Engagement Activity 2017
URL http://annual68.ise-online.org/symposia.php#s7
 
Description Award Lecture of Prof. A.Kornyshev on - New Horizons in Ionics: Electrochemical 'Metamaterials - at the IV International Conference on the Ionic Liquid Materials, Santiago de Compostela, Spain (24-27 October 2017) 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact This was a 50 min Lecture on occasion of receiving the 1st Lynden Bell Award for a distinguished career in the field of chemical physics of ionic systems. It has caused a lot of interest to novel electrochemical metamaterials from the ionic liquid community.
Year(s) Of Engagement Activity 2017
URL https://www.ilmat.net/ruth-lynden-bell-award
 
Description Invited 36 min lecture at the Annual Spring Meeting of the American Physical Society, (15-19 March, 2010, Portland, Oregon, USA) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Keynote presentation at Session Y8.00001



"Nonlinear polarization of ionic liquids: theory, simulations, experiments".

This lecture on the subject of the proposal, commissioned for one of the symposia of a major annual congress in physics - APS meeting, has resulted with a successful collaboration with the symposium organizer Prof. R.Colby. The reported findings have been later broadly used and quoted by one of the leading simulation groups performing simulations of ionic liquids at electrified interfaces (University of Utah), present at the symposium.
Year(s) Of Engagement Activity 2010
URL http://meetings.aps.org/Meeting/MAR10/APS_Invited
 
Description Invited lecture at the training school on Ionic liquids in Santiago de Compostela, 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Interfacial and Transport Properties of Ionic Liquids
REGALIs Training School 2014: Frontiers in Ionic Liquids
November 11th to November 13th , 2014, Physics Faculty, University of Santiago de Compostela, Spain
Invited lecture on STRUCTURE AND DYNAMICS OF IONIC LIQUIDS IN NANOCONFINEMENT: FROM FUNDAMENTALS TO APPLICATIONS
delivered by Prof. A. Kornyshev
Year(s) Of Engagement Activity 2014
 
Description Invited lecture of Prof. A.Kornyshev ""Supercapacitors and electroactuators with ionic liquids: the essential physics at the nanoscale"" at 11 -13 October, 1917 (Bonn, Germany) at the Forum "Fundamental Concepts and Principles of Chemical Energy Conversion", 7th Award Winners Forum of Alexander von Humboldt Foundation 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact New contact and interaction between participants, all renowned scientists, former an dpresen5t Awardees of the Alexander von Humbold Foundation; intensive interactions with the policy maker and the Humboldt Foundations
Year(s) Of Engagement Activity 2017
URL https://www.humboldt-foundation.de/pls/web/docs/text_id_53077145/F-1660726057/Programm_BHPF__2017.pd...
 
Description Invited seminar at the Joint Condensed Matter Physics Colloqium of University of Stuttgart/Max Planck Institute of Intelligent Systems, Stuttgart, Germany, 26 November 2011. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk at a Seminar of internationally acknowledged centre of excellence on "Physics of nano-porous supercapacitors", delivered by senior PDRA of the project Dr.S.Kondrat

Useful feedback for the theoretical modelling of the charging dynamics was obtained during discussions of the talk with the colleagues at Max-Planck Institute.
Year(s) Of Engagement Activity 2011
 
Description Invited seminar in Cambridge University, UK, 15 November, 2012. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact "Nanoporous supercapacitors: from applications to understanding and from understanding to applications".
Year(s) Of Engagement Activity 2012
 
Description Invited talk at CECAM Workshop "Ab Initio Electrochemistry" (12-14 July, 2010, Lausanne, Switzerland) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on "Nonlinear polarization of ionic liquids: theory, simulations, experiments" to an international workshop experts in computer simulations of electrochemical interafaces.

Dissemination of our work; research networking.
Year(s) Of Engagement Activity 2010
URL http://www.esf.org/index.php?eID=tx_nawsecuredl&u=0&g=0&t=1457264061&hash=f5a5ea7ca8e862af8a68f7b268...
 
Description Invited talk at CECAM Workshop, Toulouse, France, May 2012, "New Challenges in electrostatics of soft and disordered matter". 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk of Prof. A.Kornyshev on "Fundamentals and applications of electrical double layer in ionic liquids: from supercapacitors to artificial muscles".

Introduction of the principles of the double layer theory of ionic liquids at flat and in nanoporous electrodes,developed in the project, to the group of theorists working on different aspects of electrostatic phenomena in soft matter. Participation in the meeting and discussions with its participants has resulted in novel ideas that laid into basis of a new theory of charging single-file pores.
Year(s) Of Engagement Activity 2012
URL http://www.cecam.org/workshop-2-689.html
 
Description Invited talk at Christmas Discussions, Lviv, Ukraine, 3-4 January 2012. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Talk on "Physics of nano-porous super-capacitors with ionic liquids", delivered by Dr. S.Kondrat.
Year(s) Of Engagement Activity 2013
 
Description Invited talk at Inaugural ICTC Network Meeting, June 27-28, 2013 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach National
Primary Audience Professional Practitioners
Results and Impact Inaugural networking event was organized by UCL and Diamond Light Source to promote National and regional cooperation in energy storage. The talk was presented on

"Understanding energy storage and charging dynamics of nanostructured supercapacitors: theory, simulations, experiments". This presentation and participation in the discussions resulted in an idea of a new National initiative on Supercapacitors that will be worked out by the University of Sheffield, UCL (Prof. P.Hall), UCL (Dr. P.Shearing) and Imperial College (Prof.A.Kornyshev). This will start with inaugural Workshop in January 2014 with representatives of universities, research centres, and industrial companies, with a goal to build a new UK consortium for the promotion of multifaceted research and creation of new generation of high energy density and high power density supercapacitors.

The fruits of the meeting were explained above. If the consortium on Supercapacitance in Britain will take off as planned it, the potential achieved as a results of the project will get a broad platform for future development.
Year(s) Of Engagement Activity 2013
 
Description Invited talk at International Conference on Functional and Nanontructured Materials, Szczecin, Poland, 6-9 September, 2011. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on "Physics of nano-porous supercapacitors with ionic-liquids"' to Prof. A.Kornyshev, re-commissioned to Senior PDRA on the project Dr. S.Kondrat and delivered by him.

This talk presented results of the project to an audience of scientists specializing in development of novel nanostructured materials.
Year(s) Of Engagement Activity 2011
URL http://fnma11.gda.pl/
 
Description Invited talk at International Workshop "Wetting and capillarity in complex systems", Dresden, 18-22 February 2013 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on "Ultra Low voltage electrowetting and beyond".

The talk has overviewd the laws of electrowetting with electrolytic systems
Year(s) Of Engagement Activity 2013
URL http://www.mpipks-dresden.mpg.de/~wccs13/
 
Description Invited talk at an International workshop Complex Fluids at Structured Surfaces 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk of Professor A. Kornyshev at an International workshop Complex Fluids at Structured Surfaces-Theory meets experiments on the subject: Ionic liquids at electrified interfaces and nanoconfinement, and the physics of supercapacitors at the nanoscale. The talk presented the results obtained during the duration of the projects and a set of followup studies that emerged and have been developed after it had been finished.
The audience of the conference was not the one which is directly working in this area but was dominated by theoretical physicists generally working in interfacial phenomena with complex fluids. Ionic liquids as a new type of complex fluids for them, and the talk has broadened the horizons of this field.
Year(s) Of Engagement Activity 2015
URL https://sites.google.com/site/workshopberlin2015/home
 
Description Invited talk at at a Workshop on Current Problems in Physics, Zielona G _ora, Poland, 24-26 October, 2011. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Talk on "Nano-porous supercapacitors: from understanding to applications", delivered by senior PDRA on the project, Dr Kondrat. He promoted physical ideas of the project to a different physics audience and received some useful feedback.
Year(s) Of Engagement Activity 2011
 
Description Invited talk at the 61st Annual Meeting of the International Society of Electrochemistry (September 26th - October 1st, 2010, Nice, France) 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact An invited talk at a symposium on electrochemistry of ionic liquids on

"The Anatomy of the Double Layer Structure and Capacitance in Ionic Liquids".

This presentation has established our priority in seminal works towards understanding of the structure of electrical double layer in ionic liquids to a broad audience of electrochemist. The conference was also used for a project meeting between the Imperial group, Drexel group of Prof.Gogotsi, and Prof.Fedorov.
Year(s) Of Engagement Activity 2010
URL http://www.ise-online.org/annmeet/folder/10-program.pdf
 
Description Invited talk at the Royal Society Discussion "Functional bulk nanostructures for energy generation and storage, 16 Nov 2011 - 17 Nov 2011 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited talk on "Electrical phenomena in ionic liquids and supercapacitors: what happens at the nanoscale?", initially offered to the PI of the NSF counterpart of this project, Professor Y.Gogotsi, but then re-comissioned to and delivered by Professor A.Kornyshev.

Talk addressed predominantly to British scientists and few foreign guests, the audience dominated by physicists working or entering the area of electrochemical energy storage.

The existing URL on this effect is inadequate, as it does not show all talks and neither it has a programme of the conference. After the talk, a detailed discussion of results took place together with the Editor of Nature Materials. Later a n important paper on soem results of the projects was published in that Nature journal.
Year(s) Of Engagement Activity 2011
 
Description Invited talk of Prof. A. Kornyshev at the Solvay Workshop on: Ionic liquids: from fundamentals to applications (Brussels, 20 - 23 February 2017) 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Study participants or study members
Results and Impact Presenting the talk helped to propagate information about the achievements obtained during and after this EPSRC granted project and establish new contacts.
Year(s) Of Engagement Activity 2017
URL http://www.solvayinstitutes.be/event/workshop/ionic_liquids_2017/ionic_liquids_2017.html
 
Description Key note lecture at 62nd Annual Meeting of the International Society of Electrochemistry, Nigata, Japan, 11- 15 September, 2011 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact 40 min Invited Keynote lecture at Symposium 2: Unusual Electrochemical Phenomena in Ionic Liquids and Related Systems of Professor A. Kornyshev "Double layer in ionic liquids: from fundamentals to applications" .

The lecture gave a broad overview of the whole area with the focus on the achievements of this project.
Year(s) Of Engagement Activity 2011
URL http://personal.its.ac.id/files/pub/5340-Arseto%20Y%20Bagastyo-TL-ISE%2062nd.pdf
 
Description Key note lecture at Electrochem 2011, 05-06 September 2011 , Bath, UK 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited Keynote lecture on "Double layer in ionic liquids: from fundamentals to applications", delivered by Professor A. Kornyshev

The lecture overviewed the whole area with the focus on the achievements of the projects. It helped to disseminate our findings on the national level in the first place, as well as to the foreign participants.
Year(s) Of Engagement Activity 2011
URL https://www.regonline.co.uk/custImages/240000/247966/Electrochem%202011%20Flyer.pdf.pdf
 
Description Keynote Lecture at ISEE Cap 2013 Third international Symposium on Enhanced Electrochemical Capacitors, 03-07.13 Taormina, Italy. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited lecture on ""Understanding the laws of charge storage in supercapacitors with ionic liquids", which overviewed the whole field with a focus on the latest findings of the project.

This lecture was addressed predominantly to applied researchers and engineers developing new supercapacitors or investigating measures for their optimization. It was the most efficient event for dissemination of the applied aspects of the findings of the project.
Year(s) Of Engagement Activity 2012
URL http://www.itae.cnr.it/iseecap2013/
 
Description Keynote Lecture of Prof. Kornyshev "Energy harvesting and storage with ionic liquids: the essential physics at the nanoscale" at ETE 2017 Workshop on emerging technology for energy (18-20, December 2017, Porto, Portugal), 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact That helped establishing new links with the research leaders presented at the workshop incluiding the hosts at the University of Porto in the area of sustainable energy and energy storage
Year(s) Of Engagement Activity 2017
URL http://ete17.dcc.fc.up.pt/
 
Description Keynote lecture at the Spring Meeting of the International Society of Electrochemistry, Washington,DC, Georgetown University DC, 23-25 May, 2012 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Invited Keynote Lecture of Professor A.Kornyshev on "Physics of supercapacitors and electroactuators at the nanoscale".

Introduction of the wide audiences of electrochemists and engineers to the latest achievement of the project with special focus on nanoporous supercapacitors and electroactuators.
Year(s) Of Engagement Activity 2012
URL http://spring11.ise-online.org/
 
Description Panel talk at Faraday Discussion 164 - Electroanalysis at Nanoscale, 1-3 July, Durham and participation in discussion 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Prof. A. Kornyshev's Presentation of "The simplest model of charge storage in single file metallic nanopores"and panel question time.

One special paper of the project was presented at the meeting which contains a text-book quality results: analytical model of charge storage in a narrow quasi-one dimensional ultra narrow metallic nanopore, mapped on an exactly solvable 1d-Ising model with nearest neighbour interactions. The paper presented an example how complex problems can be described in simple terms, bringing light on the mechanisms of charge storage.
Year(s) Of Engagement Activity 2013
URL http://pubs.rsc.org/en/journals/print?issueid=fd013164&issnprint=1359-6640&sercode=fd&journalname=fa...
 
Description Plenary lecture on International Symposium on Energy Challenges and Mechanics 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Plenary lecture of Professor A.Kornyshev at 4th International Symposium on Energy Challenges and Mechanics - Working on Small Scale (11-13 August, Aberdeen, UK), on the subject:
The essential physics of supercapacitors and electroactuators at the nanoscale: electricity vs mechanics

The talk gave a broad overview of the achievements of the projects and further new results results that have been abatained after it was finished. It has been attended by all participants of the meeting, and has stimulated new contacts and collaborations. In the first place this are: the started collaborations with Professor Guang Feng (HUST, Wuhan, China) on the investigation of the role of water in electrochemistry of ionic liquids and with CEO of SME Dr. David Rogers on the use of Columnar ZnO structures (in the now running EPSRC Project "Electrotuneable Molecular Alarm").
Year(s) Of Engagement Activity 2015
URL http://nscj.co.uk/ecm4/speakers.html
 
Description Presentation of results at the final project workshop with invitation of all project participants and guests, Imperial College London, Workshop on Ionic Liquids in Confined geometries, 15 April, 2013. 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach International
Primary Audience Professional Practitioners
Results and Impact Talk on the theory and simulations of "Nanoporous supercapacitors: Energy storage and charging dynamics", delivered by Dr. Kondrat, preceded by Introductory opening talk of Prof. A.Kornyshev.

This was a final project workshop which outlined the results achieved and avenues for future development and cooperations. There were 20 participants at the workshop, including Prof. Y.Gogotsi and his group members involved in the project, Prof. R. Qiao who joined the project during its last year, representatives from Cambridge, Oxford, and Hamburg. The workshop resulted in a series of follow-up projects which are under development involving different participants including Dr.Kondrat
Year(s) Of Engagement Activity 2013
 
Description Prof. A. Kornyshev - Organization and Chairing of Faraday Discussion on Chemical Physics of Electroactive Materials 
Form Of Engagement Activity Participation in an activity, workshop or similar
Part Of Official Scheme? No
Geographic Reach International
Primary Audience Study participants or study members
Results and Impact There is currently a great interest in finding new ways of in situ control of structure and dynamical properties of materials at the micro and nano scales. One of the most attractive routes is to use variation of applied voltage, an approach shared by a wide spectrum of disciplines including nano- and micro-fluidics, optofluidics, nanotribology, microrobotics,and tunable optical metamaterials. With portable applications and energy saving demands in mind, the most promising scenarios are related to ultra-low voltage control. The latter is generally achievable under electrochemical conditions which require involvement of electrolytic components and electrical double layer effects at the nanoscale. This Faraday Discussion conference bought together internationally leading researchers in this new interdisciplinary field, who described and exchanged ideas on the physical and chemical principles underlying these phenomena.
Year(s) Of Engagement Activity 2017
URL http://www.rsc.org/events/detail/20368/chemical-physics-of-electroactive-materials-faraday-discussio...
 
Description Seminar at the Department of Materials and Drexel Nanotechnology Institute, Drexel University (6 April 2010), Philadelphia, PA, USA 
Form Of Engagement Activity A talk or presentation
Part Of Official Scheme? Yes
Geographic Reach Regional
Primary Audience Professional Practitioners
Results and Impact Invited lecture on "Double layer in ionic liquids; paradigm change?" for scientists, PhD and project stuidents of Drexel Nanotechnology Institute (Director: Professor Y.Gogotsi).

The lecture was targeted on various associates of the Drexel Nanotech Instuture and PhD and project students. Centered on the group of Prof.Gogotsi, the main US partner on the grant.
Year(s) Of Engagement Activity 2010