The solid-state batteries that are on the market today are thin-film batteries, which, on account of their limited capacity, can only be used for micro-storage, for example to provide power for sensors. But as a result of innovations in materials and architecture, solid-state batteries may soon be used also for large storage systems, for example for electric cars or the smart grid. The development of solidstate electrolytes with high Li-ion conductivity is an important link in achieving that aim. At imec, an international research institute that performs research in different fields of nano-electronics, a nano-composite electrolyte has been developed which can bring solid-state batteries one step closer to the market.
The current ‘wet’ Li-ion battery
The introduction of the rechargeable Li-ion battery in 1991 brought about a genuine revolution in the battery landscape. As a result of its high energy density, more energy could be stored in a small volume, which meant that the electronic devices, such as a laptop or cell phone, could be made smaller. As such, the emergence of this battery enabled the rapid rise of smart, portable electronics.
Without the Li-ion battery, our smart devices could never have been designed with such small and elegant form factor. Today, it is also chosen as a solution for systems that require more energy, such as electric vehicles or as temporary local energy storage or home storage for the smart electricity grid.
For these applications, other parameters are important, such as the storage capacity (expressed in Ah) and the lifetime. For electric vehicles, the power (maximum current flow) is also important: the car must be capable of accelerating quickly, and we also want to recharge the vehicle in a short time. Current day electric cars drive entirely on Li-ion batteries.
To generate current, both electrons and lithium ions move from the negative to the positive electrodes. During charging, they move in the opposite direction. The amount of electrode material mainly determines the storage capacity. The electrolyte provides the ionic conductance between the electrodes and defines the power of the battery.
The liquid electrolytes which are used today have a number of limitations. For instance, the use of the liquid electrolyte requires the use of special housing, as well as a membrane between the porous anode and cathode. This arrangement puts restrictions on the dimensions and design of this ‘wet’ battery. The liquid electrolytes are typically also flammable and corrosive, which creates safety and health risks.
The solid-state Li-ion battery
Several options are being explored for the battery of the future that overcomes these limitations without compromising on performance — or doing even better. Imec’s choice here is the concept of the (inorganic) solid-state battery.
With a solid electrolyte, the electrodes can be placed closer together, making the battery more compact and thus delivering greater energy density. Unfortunately, the solidstate electrolytes available at the moment have too low an ion conductivity. As a result, the lithium ions are only able to span a short distance so that these batteries only exist in the form of planar thin-film batteries. These batteries can only be used for micro-storage on account of their limited capacity. There are already a number of these batteries on the market today.
Jef Poortmans, scientific director for Photovoltaics at imec and R&D strategy coordinator for EnergyVille told Metering & Smart Energy International: “The solid-state battery is the next big thing on the battery roadmaps. For the moment, it is the most probable next step to improve the present batteries in terms of power density, energy density and energy reliability. Although alternative systems like Li-air, Li-S are also being investigated, many questions about these technologies remain and stretch beyond the time needed to fulfill the storage needs for electrical mobility and stationary energy storage – which will have to be tackled in the next decade.
“3D thin-film batteries would be ideal for building the autonomous sensor networks required for correct grid state estimation and control, whereas the material developments for the nano-composite electrolyte and powder-composite electrode materials will be implemented in large storage systems as well as distributed storage systems. This goes hand in hand with the deployment of large PV power plants as well as distributed building-integrated PV.”
The 3D thin-film battery for micro-storage
The solid-state design lends itself to completely new battery architectures, such as the compact 3D thin-film battery.
In this type of battery, the thin-film stack is coated over a micro-structured substrate instead of on a planar substrate. This method enables very thin films to be used for the electrode and the electrolyte, while achieving energy densities comparable with current-day battery technology. However, the actual capacity will still be limited due to the intrinsically small dimensions of these batteries.
For this reason, it is important that this battery can be recharged quickly or topped up in the background so that the battery is never completely discharged and the microsystem falls never without power. This is made possible by using thin films of at most a few hundred nanometers thick. As a result, the ions only need to travel a short distance and the battery can be recharged in a matter of minutes. These small form batteries are intended for microsystems such as implants, sensors and ‘smart cards’.
The nano-composite electrolyte
The electrolyte plays a key role in the development of batteries with larger storage capacities. As electrolytes gain higher ion conductivities, new battery architectures will become possible, with ever-thicker electrodes and hence higher storage capacity (more electrode material). A larger ion conductivity of the electrolyte means that the lithium ions will be able to span a longer distance. With today’s solid-state electrolytes (such as LiPON, lithium-phosphate-salt doped with nitrogen) we can currently achieve intrinsic conductivities of only 10-7-10-6 S/cm, which means that the electrolyte layer is limited to about one micrometer in thickness. To make batteries suitable for electric cars or home storage, we need to span several hundreds of micrometers which requires ion conductivities of 10-3-10-2 S/cm.
imec invests quite some effort in the development of the solid electrolyte, engineering materials at the nanoscale in order to achieve high ion conductivity.
At imec, we use, for example, nanoporous silica, a material that we have a great deal of experience with in the chip industry. When combined with a lithium salt into a composite, faster ion conduction can be achieved as the lithium ions move through this material along the surface of the silica.
Their conductivity is further enhanced by what we call ‘pore confinement’ — the ‘locking’ of the lithium ions in the pore structure. As a result of this ‘pore confinement,’ the properties of the bulk material are altered. Using this method, we have been successful in developing a nano-composite electrolyte with a conductivity of a several mS/cm at room temperature. So this is more than enough to produce a high-capacity battery based on powder electrodes.
The powder-composite battery for large storage systems
With this electrolyte, imec researchers have reached the transition point and have started with the development of a solidstate powder-composite battery. In this battery, the electrode structures are much thicker (>70 micrometers) and as a result the battery capacity is much larger. The new electrolyte with an ion conductivity of over mS/cm means that the lithium ions are able to span the distances in and between the electrodes.
With this cell we are aiming at capacities in the order of Ah. As these batteries can be more compact than the existing ‘wet’ Li-ion batteries, they will provide greater energy density. This means they can be used in batteries for portable electronics (such as laptops or cameras), but also for electric cars of the future, and in home storage systems for the electricity grid. Moreover, these solid-state batteries will offer a safer alternative to the ‘wet’ Li-ion battery. This will be a major asset for applications such as the electric car.
To make this battery, imec researchers follow as much as possible the same coating technology as that used in the fabrication of ‘wet’ batteries.
For the electrode coatings, micron sized active electrode particles are used. To increase the electronic conductivity through these porous electrodes, carbon is added. A binder polymer holds the active particles and the carbon in the electrodes together on a metal foil. After drying and compressing the electrode coating, the anode and cathode are brought together, with a porous membrane between them as separator. The assembled battery stack is then soaked with the liquid electrolyte so that it is present both inside the porous electrodes and inside the porous separator between the cathode and the anode layers.
imec’s solid-state powder-composite battery is fabricated in a similar way. But now the nano-composite electrolyte is applied as a wet coating and then dried to obtain a solid-state electrolyte. We have built first demonstrators of this battery, using LFP (LiFePO4) as the cathode and LTO or lithium metal as the anode. The electrodes were coated at JSR using their specific aqueous binder material. So far we are achieving 50% of the capacity for a similar cell with a liquid electrolyte. In a next step, the capacity and rate performance will be improved.
The development of the powder-composite battery is part of EnergyVille’s activities, a Flemish centre of expertise that unites KU Leuven, VITO, Hasselt University and imec for research into sustainable energy and intelligent energy systems.
Hasselt University and imec’s affiliated lab IMOMEC are also involved in this work. imec collaborates with them in its research into powder coatings and electrode nano-particles. The next stage will be to upscale the technology. This will be done mainly in the new battery lab (with a dry room) that will be built in Genk, Belgium, as part of EnergyVille. MI
ABOUT THE AUTHORS
Philippe Vereecken, principal scientist and programme manager ‘Electrochemical Storage’ at imec.
Prof. Dr. Philippe Vereecken obtained his PhD in physical chemistry in 1998 from Ghent University. After seven years’ experience in the US, first as a postdoctoral researcher at The Johns Hopkins University and then as research staff member at IBM Research, he joined imec in 2005, working in the Nanomaterials group. In 2010, he was appointed associate professor at the Centre for Surface Chemistry and Catalysis in the Faculty of Bioscience Engineering at KU Leuven. In the same year, Prof. Vereecken started up the energy storage activities at imec. His work is currently focused on the development of solid-state Li-ion batteries.
Jef Poortmans, scientific director ‘Photovoltaics’ at imec and R&D strategy coordinator for EnergyVille.
Dr. Jozef Poortmans received his degree in electronic engineering from the Katholieke Universiteit of Leuven, Belgium, in 1985. He has been the scientific director of imec’s PV and Energy Activities since 2013. In the same year he was appointed an imec Fellow. In September 2016 he was appointed director of R&D strategy at EnergyVille, an institutional partnership between imec, VITO, KU Leuven and University Hasselt focused on the themes of smart cities and smart grids.
Image Credit: 123rf.