Mastering Ion Transport at the Microscale in Solid Electrolytes for Solid-State Batteries
Lead Research Organisation:
Newcastle University
Department Name: Sch of Natural & Environmental Sciences
Abstract
The quest for improved energy storage is currently one of the most important scientific challenges. The UK is investing heavily in energy storage and renewable energy technologies and is committed to reducing its CO2 emissions by replacing the majority of its electricity generating capacity over the next few decades. Building better batteries is key to the use of electricity in a low-carbon future and for the exploitation of current and next-generation technologies. Current Li-ion batteries based on liquid electrolytes cannot meet the requirements of future applications. The creation of safer, cheaper, recyclable and higher energy density batteries is therefore essential for the electrification of transport and grid-scale storage of energy from renewable resources. This EPSRC New Investigator Award will develop transformative methods that will deliver solutions to these societally and industrially critical problems.
Solid-state Li-ion batteries are a rapidly emerging technology with the potential to revolutionise energy storage. This technology utilises solid electrolytes instead of the flammable liquid electrolytes found in current Li-ion batteries. The solid-state architecture has the potential to significantly increase both the safety and energy density of next-generation batteries. Their performance is, however, currently limited by a number of underlying challenges, including the presence of highly resistive interfaces and difficulties in controlling the microstructures of the solid electrolytes that these batteries are built around. These challenges greatly hinder Li-ion transport and are therefore highly detrimental to the operation of the battery.
To address these pertinent issues, the team will develop and apply state-of-the-art computational and experimental techniques to provide a fundamental understanding of ion transport at the microscale of solid electrolytes for solid-state batteries. Such an understanding will allow for the design of solid electrolyte microstructures that promote Li-ion transport instead of restricting it. The insights obtained for solid-state batteries in this project will also have direct implications for other battery and energy technologies where the microstructure and solid-solid interfaces again play crucial roles in determining their performance.
Solid-state Li-ion batteries are a rapidly emerging technology with the potential to revolutionise energy storage. This technology utilises solid electrolytes instead of the flammable liquid electrolytes found in current Li-ion batteries. The solid-state architecture has the potential to significantly increase both the safety and energy density of next-generation batteries. Their performance is, however, currently limited by a number of underlying challenges, including the presence of highly resistive interfaces and difficulties in controlling the microstructures of the solid electrolytes that these batteries are built around. These challenges greatly hinder Li-ion transport and are therefore highly detrimental to the operation of the battery.
To address these pertinent issues, the team will develop and apply state-of-the-art computational and experimental techniques to provide a fundamental understanding of ion transport at the microscale of solid electrolytes for solid-state batteries. Such an understanding will allow for the design of solid electrolyte microstructures that promote Li-ion transport instead of restricting it. The insights obtained for solid-state batteries in this project will also have direct implications for other battery and energy technologies where the microstructure and solid-solid interfaces again play crucial roles in determining their performance.
Organisations
- Newcastle University (Lead Research Organisation)
- Oak Ridge National Laboratory (Collaboration)
- Western University (Collaboration)
- Stanford University (Collaboration)
- Delft University of Technology (TU Delft) (Collaboration)
- Western University (Project Partner)
- Stanford University (Project Partner)
- Delft University of Technology (Project Partner)
- Imperial College London (Project Partner)
- Oak Ridge National Laboratory (Project Partner)
Publications
Dawson J
(2022)
A Nanoscale Design Approach for Enhancing the Li-Ion Conductivity of the Li 10 GeP 2 S 12 Solid Electrolyte
in ACS Materials Letters
Dawson J
(2021)
Anti-perovskites for solid-state batteries: recent developments, current challenges and future prospects
in Journal of Materials Chemistry A
Dutra ACC
(2023)
Computational Design of Antiperovskite Solid Electrolytes.
in The journal of physical chemistry. C, Nanomaterials and interfaces
Coutinho Dutra A
(2023)
Defect chemistry and ion transport in low-dimensional-networked Li-rich anti-perovskites as solid electrolytes for solid-state batteries
in Energy Advances
Poletayev AD
(2022)
Defect-driven anomalous transport in fast-ion conducting solid electrolytes.
in Nature materials
Quirk J
(2023)
Design Principles for Grain Boundaries in Solid-State Lithium-Ion Conductors
in Advanced Energy Materials
Forrester F
(2022)
Disentangling Cation and Anion Dynamics in Li 3 PS 4 Solid Electrolytes
in Chemistry of Materials
| Description | One of the major objectives of this award was to establish design principles for understanding and enhancing grain boundaries in solid electrolytes for solid-state batteries. This was achieved and our results published in the leading journal Advanced Energy Materials (2023, 13, 2301114). Specifically, first-principles simulations were carried out on representative grain boundaries in four important solid electrolytes (Li3OCl, Li2OHCl, Li3PS4 and Li3InCl6). The significantly different impacts that grain boundaries have on electronic structure and transport, ion conductivity and correlated ion dynamics were demonstrated. Our results showed that even when grain boundaries do not significantly impact ionic conductivity, they can still strongly perturb the electronic structure and contribute to potential lithium dendrite propagation. It was also illustrated how correlated motion can vary substantially at grain boundaries. Our findings revealed the dramatically different behaviour of solid electrolytes at the microscale compared to the bulk and its potential consequences and benefits for the design of solid-state batteries. These findings are expected to aid the synthesis and engineering of solid electrolytes at the microscale for preventing dendrite propagation and accelerating ion transport. This project also enabled high-profile collaborations between myself (Newcastle) and researchers at Stanford and Oxford on new methods and theory to understand ion transport in solid crystalline materials. These collaborations have so far led to publication in Nature Materials (2022, 21, 1066) and Nature (2024, 625, 691). In the former study, using large-scale simulations, we reproduced the frequency dependence of alternating-current ionic conductivity data in archetypal beta-alumina solid electrolytes. We showed how the distribution of charge-compensating defects, modulated by processing, drives static and dynamic disorder and leads to persistent subdiffusive ion transport at macroscopic timescales. We also deconvoluted the effects of repulsions between mobile ions, the attraction between the mobile ions and charge-compensating defects and geometric crowding on ionic conductivity. Such understanding helps to develop the 'atoms-to-device' optimisation of ion conductors. In the latter study, we used a combination of experimental and simulated terahertz pumps to impulsively trigger ionic hopping in solid electrolytes. This enabled us to direct probe anisotropy in ionic hopping at its fastest limit, distinguish correlated conduction mechanisms from a true random walk at the atomic scale and demonstrate the connection between transport and the thermodynamics of information. In collaboration with Professor Xueliang Sun at Western University, this award has enabled us to develop state-of-the-art halide-based Li-ion conductors. This collaboration has so far led to one published manuscript (Advanced Materials, 2023, 2302647) with three more submitted or in preparation. So far, we have established a proof of concept for the precise tailoring of lithium-ion transport in Li3InCl6, including intragranular (within grains) and intergranular (between grains) transport. The transport mechanism between the grains was determined by the elimination of voids between grains and the formation of unexpected conducting grain boundaries, boosting the lithium dendrite suppression ability of the electrolyte. The resulting all-solid-state lithium metal batteries coupled with a LiNi0.83Co0.12Mn0.05O2 cathode and a lithium anode demonstrated breakthroughs in electrochemical performance by achieving extremely long cycling life at a high current density. |
| Exploitation Route | Our research outcomes are already being used within the Faraday Institution SOLBAT project to improve the Li-ion conductivity of sulfide solid electrolytes at the microscale. Our established design principles for grain boundaries in solid electrolytes will be used within the academic and non-academic (including industry) communities to develop solid electrolytes with improved performance, which in the long term will benefit the energy and transport sectors through enhanced battery technologies. Given the importance of understanding ion transport at the microscale in other energy technologies, our findings will likely also benefit researchers in other fields, for example, photovoltaics and fuel cells. In fact, we have recently begun a collaboration with Professor Sam Stranks (Cambridge), to apply some of the methods we have developed here to developed improved hybrid perovskite materials with reduced ion migration and therefore better stability. During the project, the employed PDRA, Dr. James Quirk, has also worked in other complementary areas, such as electride discovery and structure prediction, which will benefit wider academic communities working in, for example, mechanochemistry and catalysis. The funds have also enabled me to contribute to a Nature paper on new techniques to measure ion transport in solid electrolytes. This work represents a new paradigm for understanding ion transport and will benefit researchers in many fields. |
| Sectors | Chemicals Energy Transport |
| Description | All-Solid State Lithium Anode Battery 2 |
| Amount | £5,320,543 (GBP) |
| Funding ID | FIRG026 |
| Organisation | The Faraday Institution |
| Sector | Charity/Non Profit |
| Country | United Kingdom |
| Start | 03/2021 |
| End | 03/2023 |
| Description | PhD studentship |
| Amount | £65,000 (GBP) |
| Organisation | Newcastle University |
| Sector | Academic/University |
| Country | United Kingdom |
| Start | 03/2021 |
| End | 04/2024 |
| Description | UKRI Frontiers Grant |
| Amount | £1,800,000 (GBP) |
| Funding ID | EP/Z000254/1 |
| Organisation | United Kingdom Research and Innovation |
| Sector | Public |
| Country | United Kingdom |
| Start | |
| Title | CCDC 2166151: Experimental Crystal Structure Determination |
| Description | Related Article: Nathan Davison, James A. Quirk, Corinne Wills, Casey Dixon, Paul G. Waddell, James A. Dawson, Erli Lu|2022|Inorg.Chem.|61|15204|doi:10.1021/acs.inorgchem.2c02457 |
| Type Of Material | Database/Collection of data |
| Year Produced | 2022 |
| Provided To Others? | Yes |
| URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2bq1vz&sid=DataCite |
| Title | CCDC 2166152: Experimental Crystal Structure Determination |
| Description | Related Article: Nathan Davison, James A. Quirk, Corinne Wills, Casey Dixon, Paul G. Waddell, James A. Dawson, Erli Lu|2022|Inorg.Chem.|61|15204|doi:10.1021/acs.inorgchem.2c02457 |
| Type Of Material | Database/Collection of data |
| Year Produced | 2022 |
| Provided To Others? | Yes |
| URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2bq1w0&sid=DataCite |
| Title | CCDC 2166153: Experimental Crystal Structure Determination |
| Description | Related Article: Nathan Davison, James A. Quirk, Corinne Wills, Casey Dixon, Paul G. Waddell, James A. Dawson, Erli Lu|2022|Inorg.Chem.|61|15204|doi:10.1021/acs.inorgchem.2c02457 |
| Type Of Material | Database/Collection of data |
| Year Produced | 2023 |
| Provided To Others? | Yes |
| URL | http://www.ccdc.cam.ac.uk/services/structure_request?id=doi:10.5517/ccdc.csd.cc2bq1x1&sid=DataCite |
| Description | Partnership with Oak Ridge National Laboratory (US) |
| Organisation | Oak Ridge National Laboratory |
| Country | United States |
| Sector | Public |
| PI Contribution | This is a computational-experimental partnership between my team and the team of Dr. Miaofang Chi at Oak Ridge National Laboratory. We have had a number of kick-off meetings with Dr. Chi and progress is now being made in understanding the role of grain boundaries at the atomic scale in solid electrolytes for solid-state batteries. Our contribution is the computational aspect of the project, which involves confirming preliminary structures sent from Dr. Chi and predicting new ones using computational methods such as density functional theory. |
| Collaborator Contribution | Dr Chi's contributions have been more limited by COVID than our own. Nevertheless, her team is now making important progress in carrying out the experimental characterisation of various solid electrolyte materials. |
| Impact | Publications are anticipated later in the project. |
| Start Year | 2021 |
| Description | Partnership with Stanford University (US) |
| Organisation | Stanford University |
| Country | United States |
| Sector | Academic/University |
| PI Contribution | This is an experimental-computational project between my group and the groups of Profs. Aaron Lindenberg and Will Chueh at Stanford to develop THz-driven diffusion models of solid electrolytes for batteries. This has already been a very productive partnership with one manuscript under review and another almost ready for submission. Our role is to carry out classical molecular dynamics simulations to help predict and understand the experimental outputs. |
| Collaborator Contribution | The teams of Profs. Chueh and Lindenberg are responsible for the synthesis and characterisation of the materials. |
| Impact | This has already been a very productive partnership with one manuscript under review and another almost ready for submission. |
| Start Year | 2021 |
| Description | Partnership with TU Delft (Netherlands) |
| Organisation | Delft University of Technology (TU Delft) |
| Country | Netherlands |
| Sector | Academic/University |
| PI Contribution | This is a partnership between our group and the group of Prof. Marnix Wagemaker. We are carrying out computational simulations of halide solid electrolytes and how their properties are influenced by their interfaces. |
| Collaborator Contribution | Prof. Wagemaker and his team are carrying out the synthesis and characterisation aspects of the project. |
| Impact | This partnership is still new but is expected to lead publications in future. A member of Prof. Wagemaker's group is currently undertaking a 'virtual' secondment with us (see secondments section for further details). |
| Start Year | 2021 |
| Description | Partnership with Western University (Canada) |
| Organisation | Western University |
| Country | Canada |
| Sector | Academic/University |
| PI Contribution | This is an ongoing computational-experimental partnership between my team and the team of Prof. Xueliang Sun at Western University. Our role is the computational aspects, which have been made possible by this EPSRC grant. We are investigating the role of microstructure in state-of-the-art halide solid electrolytes for solid-state batteries using atomistic simulations, including density functional theory and molecular dynamics. This has already been a very fruitful partnership with two manuscripts currently being prepared for publication this or next year. |
| Collaborator Contribution | Prof. Sun's team has carried out a wide variety of synthesis and characterisation activities to support the partnership. These include, but are not limited to, synthesis of halide solid electrolytes using new synthetic routes based on mechanochemistry and hydrothermal approaches, electrochemical performance testing, standard and synchrotron X-ray diffraction, scanning electron microscopy and X-ray tomography. |
| Impact | As noted above, we are currently in the process of preparing two manuscripts for publishing in leading materials science journals. This partnership has only been going for less than one year but is expected to go beyond the duration of this grant and provide significant impact. |
| Start Year | 2021 |
| Description | School visits (Newcastle) |
| Form Of Engagement Activity | Participation in an activity, workshop or similar |
| Part Of Official Scheme? | No |
| Geographic Reach | Regional |
| Primary Audience | Schools |
| Results and Impact | A PhD student in our group, Ana, who is directly funded as a result of this award, is a particularly passionate advocate of public engagement. She has worked with others at Newcastle University to deliver presentations and workshops for local school students on several occasions. At least one these events was focused on how batteries work and the research she is carrying out in the group. Future plans for more activities are currently ongoing. |
| Year(s) Of Engagement Activity | 2021 |
| Description | Working groups |
| Form Of Engagement Activity | A formal working group, expert panel or dialogue |
| Part Of Official Scheme? | No |
| Geographic Reach | Regional |
| Primary Audience | Industry/Business |
| Results and Impact | I am part of several working groups, including the Newcastle University Battery Working Group, the North East Battery Alliance and the Low-carbon Battery Materials Interest Group. As part of these groups, we have organised a number of workshops with local and national companies interested net-zero activities. Many events are also planned for the forthcoming year. Future interactions with the recently opened Faraday Institution North East Office and Britishvolt are also being planned. |
| Year(s) Of Engagement Activity | 2021,2022 |