Ionic Liquid Electrolytes for Metal-Anode Batteries
Lead Research Organisation:
University of Oxford
Department Name: Materials
Abstract
The need for increasingly high-energy batteries is becoming realised in such applications as electric vehicles, intermittent renewable energy sources and consumer electronics. Over the past few decades, lithium-ion batteries (LIB) have taken a huge share of the battery market, but with a theoretical specific energy limitation of 250 - 300 W h kg-1, it's clear a higher energy battery is required.
With a theoretical 10-fold increase in specific energy to LIBs, the lithium metal battery (LMB) has long been considered as the ultimate goal: Li metal used as the anode has a high specific capacity (3861 mA h g-1) and a very negative potential (-3.04 V vs. SHE).
Unlike LIBs, which usually utilize graphite as the anode, LMBs require the plating and stripping of the Li anode surface during charge and discharge. The passivation layer, or the so-called solid electrolyte interface (SEI), on the surface of the Li metal, is therefore in a constant state of repair. The morphology and composition of the SEI can lead to such problems as Li dendrite formation, which is a huge safety concern, as the protrusion could bridge the "inter-electrode space" and thereby short-circuit the cell. If one uses a volatile electrolyte this could lead to thermal runaway and disastrous cell failure.
With the SEI consisting of organic and inorganic species from the electrolyte decomposition products, which electrolyte one uses is a significant factor in the success of the cell. To curb the Li dendrite concerns, an electrolyte that leads to an elastic SEI with low resistance for uniform Li deposition is needed.
Organic electrolytes (e.g. carbonates), which are typically used in LIBs, are responsible for a variety of concerns due to their high volatility, poor thermal stability, high flammability and environmental hazards. A viable alternative electrolyte gaining increasingly more attention, are room temperature ionic liquids (RTILs). There are many advantages to using RTILs as electrolytes for LMBs, including their high thermal stability, high electrochemical stability (large electrochemical window) and low vapour pressure. RTILs also cater the ability to adjust physiochemical properties with the anion and cation, which can thus lead to a stable SEI. Considered disadvantages to using RTILs as electrolytes are their relatively high viscosity, and therefore low conductivity, plus the low Li+ transference number.
This project's aim is to investigate the nature of the SEI of LMBs, using novel RTILs. Additionally, SEIs of other secondary metal batteries will be studied, including sodium and magnesium batteries. The importance of studying the SEI is that it can better inform the design of new RTILs, and ultimately use ionic liquids in commercial batteries.6 Further aims include investigating strategies to increase the transference number (e.g. nanoparticle decorated ILs)7, and increase the conductivity using RTILs (e.g. organic-IL mixtures).
RTILs used will be based on ones that have shown promise, including tetraalkylammonium cations and bis(fluoromethanesulfonyl)imide (FSI) anions.8 The synthesis of the RTILs will follow a 2-stage process: the preparation of the precursor salt and the subsequent metathesis reaction.
Techniques to characterize the SEI will be employed, namely X-Ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR), Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscopy (SEM) and X-Ray Reflectivity. To measure electrochemical properties, cyclic voltammetry (CV) and galvanostatic cycling techniques will be used. Additionally, to calculate transference numbers, self-diffusion coefficients can be measured using pulsed field gradient echo- nuclear magnetic resonance spectroscopy (PGSE-NMR).
This project falls within the EPSRC physical sciences research area.
With a theoretical 10-fold increase in specific energy to LIBs, the lithium metal battery (LMB) has long been considered as the ultimate goal: Li metal used as the anode has a high specific capacity (3861 mA h g-1) and a very negative potential (-3.04 V vs. SHE).
Unlike LIBs, which usually utilize graphite as the anode, LMBs require the plating and stripping of the Li anode surface during charge and discharge. The passivation layer, or the so-called solid electrolyte interface (SEI), on the surface of the Li metal, is therefore in a constant state of repair. The morphology and composition of the SEI can lead to such problems as Li dendrite formation, which is a huge safety concern, as the protrusion could bridge the "inter-electrode space" and thereby short-circuit the cell. If one uses a volatile electrolyte this could lead to thermal runaway and disastrous cell failure.
With the SEI consisting of organic and inorganic species from the electrolyte decomposition products, which electrolyte one uses is a significant factor in the success of the cell. To curb the Li dendrite concerns, an electrolyte that leads to an elastic SEI with low resistance for uniform Li deposition is needed.
Organic electrolytes (e.g. carbonates), which are typically used in LIBs, are responsible for a variety of concerns due to their high volatility, poor thermal stability, high flammability and environmental hazards. A viable alternative electrolyte gaining increasingly more attention, are room temperature ionic liquids (RTILs). There are many advantages to using RTILs as electrolytes for LMBs, including their high thermal stability, high electrochemical stability (large electrochemical window) and low vapour pressure. RTILs also cater the ability to adjust physiochemical properties with the anion and cation, which can thus lead to a stable SEI. Considered disadvantages to using RTILs as electrolytes are their relatively high viscosity, and therefore low conductivity, plus the low Li+ transference number.
This project's aim is to investigate the nature of the SEI of LMBs, using novel RTILs. Additionally, SEIs of other secondary metal batteries will be studied, including sodium and magnesium batteries. The importance of studying the SEI is that it can better inform the design of new RTILs, and ultimately use ionic liquids in commercial batteries.6 Further aims include investigating strategies to increase the transference number (e.g. nanoparticle decorated ILs)7, and increase the conductivity using RTILs (e.g. organic-IL mixtures).
RTILs used will be based on ones that have shown promise, including tetraalkylammonium cations and bis(fluoromethanesulfonyl)imide (FSI) anions.8 The synthesis of the RTILs will follow a 2-stage process: the preparation of the precursor salt and the subsequent metathesis reaction.
Techniques to characterize the SEI will be employed, namely X-Ray Photoelectron Spectroscopy (XPS), Fourier Transform Infrared Spectroscopy (FTIR), Electrochemical Impedance Spectroscopy (EIS), Scanning Electron Microscopy (SEM) and X-Ray Reflectivity. To measure electrochemical properties, cyclic voltammetry (CV) and galvanostatic cycling techniques will be used. Additionally, to calculate transference numbers, self-diffusion coefficients can be measured using pulsed field gradient echo- nuclear magnetic resonance spectroscopy (PGSE-NMR).
This project falls within the EPSRC physical sciences research area.
Organisations
People |
ORCID iD |
| Mauro Pasta (Primary Supervisor) | |
| Jack Fawdon (Student) |
Studentship Projects
| Project Reference | Relationship | Related To | Start | End | Student Name |
|---|---|---|---|---|---|
| EP/N509711/1 | 30/09/2016 | 29/09/2021 | |||
| 1938301 | Studentship | EP/N509711/1 | 30/09/2017 | 07/09/2021 | Jack Fawdon |
| Description | My work has primarily focused on developing an accurate and reliable way of measuring the transference number of liquid electrolytes for lithium metal anode batteries. The transference number is a property of the electrolyte that looks at how well one ion moves with respect to all other ions in solution. This is important because if the active ion, in this case Li+, has a transference number of less than 1 then a concentration gradient develops across the interelectrode space. This could be extended to a concentration drop at the surface of the lithium, when plating, which has been suggested as a reason to why dendritic structures grow readily on while charging. There have been a variety of methods been developed for measuring the transference number over the years: some having assumptions with regards to ideality & convection, and others being difficult when emulating real applications. The methods I have developed acknowledge the ideality assumptions made in other methods - one involves the use of electrochemical impedance spectroscopy (EIS) and nuclear magnetic resonance spectroscopy (NMR), and the other Raman spectroscopy. The method involving Raman is particularly powerful because one can see the concentration gradient form with time, linking it to transference number and other electrolyte properties that we can measure. |
| Exploitation Route | Both measuring the transference number accurately and monitoring the concentration gradients of electrolytes with time is highly valuable for the science community, especially those working in the battery/electrochemistry field. With many researchers working on the suppression of dendrite growth on lithium metal anodes, this method is a step forward at understanding why using some electrolytes dendrites will form and cause the failure of the battery. These methods can be extended and used for all liquid electrolytes, and perhaps even used for some solid electrolytes. |
| Sectors | Chemicals Energy Environment |