An official website of the United States government
Increasing electrode thickness is one route to improve the energy density of lithium-ion battery cells. However, restricted Li+ transport in the electrolyte phase through the porous microstructure of thick electrodes limits the ability to achieve high current densities and rates of charge/discharge with these high energy cells. In this work, processing routes to mitigate transport restrictions were pursued. The electrodes used were comprised of only active material sintered together into a porous pellet. For one of the electrodes, comparisons were done between using ice-templating to provide directional porosity and using sacrificial particles during processing to match the geometric density without pore alignment. The ice-templated electrodes retained much greater discharge capacity at higher rates of cycling, which was attributed to improved transport properties provided by the processing. The electrodes were further characterized using an electrochemical model of the cells evaluated and neutron imaging of a cell containing the ice-templated pellet. The results indicate that significant improvements can be made to electrochemical cell properties via templating the electrode microstructure for situations where the rate limiting step includes ion transport limitations in the cell.
more »
« less
Thick Sintered Electrode Lithium-Ion Battery Discharge Simulations: Incorporating Lithiation-Dependent Electronic Conductivity and Lithiation Gradient Due to Charge Cycle
In efforts to increase the energy density of lithium-ion batteries, researchers have attempted to both increase the thickness of battery electrodes and increase the relative fractions of active material. One system that has both of these attributes are sintered thick electrodes comprised of only active material. Such electrodes have high areal capacities, however, detailed understanding is needed of their transport properties, both electronic and ionic, to better quantify their limitations to cycling at higher current densities. In this report, efforts to improve models of the electrochemical cycling of sintered electrodes are described, in particular incorporation of matrix electronic conductivity which is dependent on the extent of lithiation of the active material and accounting for initial gradients in lithiation of active material in the electrode that develop as a consequence of transport limitations during charging cycles. Adding in these additional considerations to a model of sintered electrode discharge resulted in improved matching of experimental cell measurements.
more »
« less
- PAR ID:
- 10361740
- Publisher / Repository:
- The Electrochemical Society
- Date Published:
- Journal Name:
- Journal of The Electrochemical Society
- Volume:
- 167
- Issue:
- 14
- ISSN:
- 0013-4651
- Page Range / eLocation ID:
- Article No. 140542
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Nanoscale Depth and Lithiation Dependence of V2O5 Band Structure by Cathodoluminescence SpectroscopyVanadium pentoxide (V2O5) is a very well-known cathode material that has attracted considerable interest for its potential use in solid-state lithium-ion batteries. We pioneer the use of depth-resolved cathodoluminescence spectroscopy (DRCLS) to monitor the changes in the electronic structure of lithiated V2O5 from the free surface to the thin film bulk several hundred nm below as a function of lithiation. DRCLS measurements of V2O5 interband transitions are in excellent agreement with density functional theory (DFT) calculations. The direct measure of V2O5's electronic band structure as a function of lithiation level provided by DRCLS can help inform solid-state battery designs to further withstand degradation and increase efficiency. In particular, these unique electrode measurements may reveal physical mechanisms of lithiation that change V2O5 irreversibly, as well as methods to mitigate them in solid-state batteries.more » « less
-
Higher energy density batteries continue to be pursued by researchers. One general route to increase energy density is to increase electrode thickness, which reduces the relative fraction of the cell allocated to inactive components. One route to fabricate thick electrodes is to use mildly thermally treated, or sintered, electrodes comprising only electroactive materials. In this report, the concept of sintered electrodes comprising two different electroactive components will be reported. Conventional composite electrodes with multiple electroactive materials have previously been investigated with the goal of combining desirable attributes of the different components. Sintered electrodes have additional complexity relative to composite electrodes in that interfaces can be formed during processing, and consideration of the location of the different component materials must be taken into account due to the need for electronic conduction through the electrode matrix to proceed through the electroactive materials themselves. Both additional considerations and outcomes will be discussed in this report where multicomponent sintered electrodes of LiCoO 2 and LiMn 2 O 4 were fabricated and characterized.more » « less
-
Pre-lithiation is the most effective method to overcome the initial capacity loss of high-capacity electrodes and has the potential to be used in beyond-conventional lithium-ion batteries. In this article we focus on two types of pre-lithiation: the first type can be applied to batteries in which the cathode has been fully lithiated but the anode has a large initial capacity loss, such as batteries made with lithium metal oxide cathode and silicon-carbon anode. The second type can be applied to batteries in which both electrodes are initially lithium-free and suffer a loss of lithium during the initial cycles, such as batteries made with sulfurized-polyacrylonitrile cathode and silicon-carbon anode. We describe the pre-lithiation procedures and electrode potential profiles during pre-lithiation corresponding to different pre-lithiation sources for both types of pre-lithiation. We also derive formulas for the theoretical specific energy and energy density that are based entirely on measurable parameters such as specific capacities, porosities, mass densities of two electrodes and extra lithium source, Coulombic efficiencies of electrodes, and the voltage of the cell. These formulas can be applied to different pre-lithiation sources to predict the specific energy of conventional and beyond-conventional lithium-ion batteries as a function of the type of pre-lithiation.more » « less
-
null (Ed.)Lithium-ion batteries have received significant research interest due to their advantages in energy and power density, which are important to enabling many devices. One route to further increase energy density is to fabricate thicker electrodes in the battery cell; however, careful consideration must be taken when designing electrodes as to how increasing the thickness impacts the multiscale and multiphase molecular transport processes, which can limit the overall battery operating power. Design of these electrodes necessitates probing the molecular processes when the battery cell undergoes electrochemical charge/discharge. One tool for in situ insights into the cell is neutron imaging, because neutron imaging can provide information of where electrochemical processes occur within the electrodes. In this manuscript, neutron imaging is applied to track the lithiation/delithiation processes within electrodes at different current densities for a full cell with a thick sintered Li 4 Ti 5 O 12 anode and LiCoO 2 cathode. The neutron imaging reveals that the molecular distribution of Li + during discharge within the electrode is sensitive to the current density, or equivalently discharge rate. An electrochemical model provides additional insights into the limiting processes occurring within the electrodes. In particular, the impact of tortuosity and molecular transport in the liquid phase within the interstitial regions in the electrodes are considered, and the influence of tortuosity was shown to be highly sensitive to the current density. Qualitatively, the experimental results suggest that the electrodes behave consistent with the packed hard sphere approximation of Bruggeman tortuosity scaling, which indicates that the electrodes are largely mechanically intact but also that a design that incorporates tunable tortuosity could improve the performance of these types of electrodes.more » « less
