Analysis probes reactions in porous battery electrodes for the first time
The electrochemical reactions inside the porous electrodes of batteries and fuel cells have been described by theorists, but never measured directly. Now, a team at MIT has figured out a way to measure the fundamental charge transfer rate — finding some significant surprises.
The study found that the Butler-Volmer (BV) equation, usually used to describe reaction rates in electrodes, is inaccurate, especially at higher voltage levels. Instead, a different approach, called Marcus-Hush-Chidsey charge-transfer theory, provides more realistic results — revealing that the limiting step of these reactions is not what had been thought.
The new findings could help engineers design better electrodes to improve batteries' rates of charging and discharging, and provide a better understanding of other electrochemical processes, such as how to control corrosion. The work is described this week in the journal Nature Communications by MIT postdoc Peng Bai and professor of chemical engineering and mathematics Martin Bazant.
Previous work was based on the assumption that the performance of electrodes made of lithium iron phosphate — widely used in lithium-ion batteries — was limited primarily by how fast lithium ions would diffuse into the solid electrode from the liquid electrolyte. But the new analysis shows that the critical interface is actually between two solid materials: the electrode itself, and a carbon coating used to improve its performance.
Limited by electron transfer
Bai and Bazant's analysis shows that both transport steps in solid and liquid — ion migration in the electrolyte, and diffusion of "quasiparticles" called polarons — are very fast, and therefore do not limit battery performance. "We show it's actually electrons, not the ions, transferring at the solid-solid interface," Bai says, that determine the rate.
Bazant says researchers had not suspected, despite extensive research on lithium iron phosphate, that the material's electrochemical reactions might be limited by electron transfer between two solids. "That's a completely new picture for this material; it's not something that has even been mentioned before," he says.
While coating the electrode surface with a thin layer of carbon or graphene had been shown to improve performance, there was no microscopic and quantitative understanding of why this made a difference, Bazant says. The new findings will help explain a number of apparently conflicting results in the scientific literature, he says.
Unexpectedly low reaction rates
For example, the classical equations used to predict the performance of such materials have indicated that the logarithm of the reaction rate should vary linearly as voltage is increased — but experiments have shown a nonlinear response, with the uptake of lithium flattening out at high voltage. The discrepancies have been significant, Bazant says: "We find the reaction rate is much lower than what is predicted."
The new analysis means that to make further improvements in this technology, the focus should be on "how you engineer the surface" at the solid-solid interface, Bai says.
Bazant adds that the new understanding could have implications far beyond electrode design, since the fundamental processes the team uncovered apply to electrochemical processes including electrodeposition, corrosion, and fuel cells. "It's also important for basic science," he says, since the process is both ubiquitous and poorly understood.
The BV equation is purely empirical, and "doesn't tell you anything about what's going on microscopically," Bazant says. By contrast, the Marcus-Hush-Chidsey equations — for which Rudolph Marcus of the California Institute of Technology was awarded the 1992 Nobel Prize in chemistry — are based on a precise understanding of atomic-level activity. So the new analysis, Bazant maintains, could lead not only to new practical solutions, but also to a deeper understanding of the underlying mechanisms.
Written by David Chandler, MIT News Office
Andrew Carleen | EurekAlert!
Cost-efficiently modernising heating networks
11.02.2016 | FIZ Karlsruhe – Leibniz-Institut für Informationsinfrastruktur GmbH
Demonstration of smart energy storage technologies and -management systems on the island of Borkum
11.02.2016 | Steinbeis-Europa-Zentrum
Today, plants and microorganisms are heavily used for the production of medicinal products. The production of biopharmaceuticals in plants, also referred to as “Molecular Pharming”, represents a continuously growing field of plant biotechnology. Preferred host organisms include yeast and crop plants, such as maize and potato – plants with high demands. With the help of a special algal strain, the research team of Prof. Ralph Bock at the Max Planck Institute of Molecular Plant Physiology in Potsdam strives to develop a more efficient and resource-saving system for the production of medicines and vaccines. They tested its practicality by synthesizing a component of a potential AIDS vaccine.
The use of plants and microorganisms to produce pharmaceuticals is nothing new. In 1982, bacteria were genetically modified to produce human insulin, a drug...
Atomic clock experts from the Physikalisch-Technische Bundesanstalt (PTB) are the first research group in the world to have built an optical single-ion clock which attains an accuracy which had only been predicted theoretically so far. Their optical ytterbium clock achieved a relative systematic measurement uncertainty of 3 E-18. The results have been published in the current issue of the scientific journal "Physical Review Letters".
Atomic clock experts from the Physikalisch-Technische Bundesanstalt (PTB) are the first research group in the world to have built an optical single-ion clock...
The University of Würzburg has two new space projects in the pipeline which are concerned with the observation of planets and autonomous fault correction aboard satellites. The German Federal Ministry of Economic Affairs and Energy funds the projects with around 1.6 million euros.
Detecting tornadoes that sweep across Mars. Discovering meteors that fall to Earth. Investigating strange lightning that flashes from Earth's atmosphere into...
Physicists from Saarland University and the ESPCI in Paris have shown how liquids on solid surfaces can be made to slide over the surface a bit like a bobsleigh on ice. The key is to apply a coating at the boundary between the liquid and the surface that induces the liquid to slip. This results in an increase in the average flow velocity of the liquid and its throughput. This was demonstrated by studying the behaviour of droplets on surfaces with different coatings as they evolved into the equilibrium state. The results could prove useful in optimizing industrial processes, such as the extrusion of plastics.
The study has been published in the respected academic journal PNAS (Proceedings of the National Academy of Sciences of the United States of America).
Exceeding critical temperature limits in the Southern Ocean may cause the collapse of ice sheets and a sharp rise in sea levels
A future warming of the Southern Ocean caused by rising greenhouse gas concentrations in the atmosphere may severely disrupt the stability of the West...
12.02.2016 | Event News
09.02.2016 | Event News
02.02.2016 | Event News
12.02.2016 | Physics and Astronomy
12.02.2016 | Life Sciences
12.02.2016 | Medical Engineering