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MIT researchers find a simple formula could guide the design of faster-charging, longer-lasting batteries

The model explains lithium intercalation rates in lithium-ion batteries

2025-10-02
(Press-News.org) CAMBIRDGE, MA -- At the heart of all lithium-ion batteries is a simple reaction: Lithium ions dissolved in an electrolyte solution “intercalate” or insert themselves into a solid electrode during battery discharge. When they de-intercalate and return to the electrolyte, the battery charges.

This process happens thousands of times throughout the life of a battery. The amount of power that the battery can generate, and how quickly it can charge, depend on how fast this reaction happens. However, little is known about the exact mechanism of this reaction, or the factors that control its rate.

In a new study, MIT researchers have measured lithium intercalation rates in a variety of different battery materials and used that data to develop a new model of how the reaction is controlled. Their model suggests that lithium intercalation is governed by a process known as coupled ion-electron transfer, in which an electron is transferred to the electrode along with a lithium ion.

Insights gleaned from this model could guide the design of more powerful and faster charging lithium-ion batteries, the researchers say.

“What we hope is enabled by this work is to get the reactions to be faster and more controlled, which can speed up charging and discharging,” says Martin Bazant, the Chevron Professor of Chemical Engineering and a professor of mathematics at MIT.

The new model may also help scientists understand why tweaking electrodes and electrolytes in certain ways leads to increased energy, power, and battery life — a process that has mainly been done by trial and error.

“This is one of these papers where now we began to unify the observations of reaction rates that we see with different materials and interfaces, in one theory of coupled electron and ion transfer for intercalation, building up previous work on reaction rates,” says Yang Shao-Horn, the J.R. East Professor of Engineering at MIT and a professor of mechanical engineering, materials science and engineering, and chemistry.

Shao-Horn and Bazant are the senior authors of the paper, which appears today in Science. The paper’s lead authors are Yirui Zhang PhD ’22, who is now an assistant professor at Rice University; Dimitrios Fraggedakis PhD ’21, who is now an assistant professor at Princeton University; Tao Gao, a former MIT postdoc who is now an assistant professor at the University of Utah; and MIT graduate student Shakul Pathak.

Modeling lithium flow

For many decades, scientists have hypothesized that the rate of lithium intercalation at a lithium-ion battery electrode is determined by how quickly lithium ions can diffuse from the electrolyte into the electrode. This reaction, they believed, was governed by a model known as the Butler-Volmer equation, originally developed almost a century ago to describe the rate of charge transfer during an electrochemical reaction.

However, when researchers have tried to measure lithium intercalation rates, the measurements they obtained were not always consistent with the rates predicted by the Butler-Volmer equation. Furthermore, obtaining consistent measurements across labs has been difficult, with different research teams reporting measurements for the same reaction that varied by a factor of up to 1 billion. 

In the new study, the MIT team measured lithium intercalation rates using an electrochemical technique that involves applying repeated, short bursts of voltage to an electrode. They generated these measurements for more than 50 combinations of electrolytes and electrodes, including lithium nickel manganese cobalt oxide, which is commonly used in electric vehicle batteries, and lithium cobalt oxide, which is found in the batteries that power most cell phones, laptops, and other portable electronics.

For these materials, the measured rates are much lower than has previously been reported, and they do not correspond to what would be predicted by the traditional Butler-Volmer model. 

The researchers used the data to come up with an alternative theory of how lithium intercalation occurs at the surface of an electrode. This theory is based on the assumption that in order for a lithium ion to enter an electrode, an electron from the electrolyte solution must be transferred to the electrode at the same time.

“The electrochemical step is not lithium insertion, which you might think is the main thing, but it’s actually electron transfer to reduce the solid material that is hosting the lithium,” Bazant says. “Lithium is intercalated at the same time that the electron is transferred, and they facilitate one another.”

This coupled-electron ion transfer (CIET) lowers the energy barrier that must be overcome for the intercalation reaction to occur, making it more likely to happen. The mathematical framework of CIET allowed the researchers to make reaction rate predictions, which were validated by their experiments and substantially different from those made by the Butler-Volmer model. 

Faster charging

In this study, the researchers also showed that they could tune intercalation rates by changing the composition of the electrolyte. For example, swapping in different anions can lower the amount of energy needed to transfer the lithium and electron, making the process more efficient.

“Tuning the intercalation kinetics by changing electrolytes offers great opportunities to enhance the reaction rates, alter electrode designs, and therefore enhance the battery power and energy,” Shao-Horn says.

Shao-Horn’s lab and their collaborators have been using automated experiments to make and test thousands of different electrolytes, which are used to develop machine-learning models to predict electrolytes with enhanced functions.

The findings could also help researchers to design batteries that would charge faster, by speeding up the lithium intercalation reaction. Another goal is reducing the side reactions that can cause battery degradation when electrons are picked off the electrode and dissolve into the electrolyte. 

“If you want to do that rationally, not just by trial and error, you need some kind of theoretical framework to know what are the important material parameters that you can play with,” Bazant says. “That’s what this paper tries to provide.”

###

The research was funded by Shell International Exploration and Production and the Toyota Research Institute through the D3BATT Center for Data-Driven Design of Rechargeable Batteries.

 

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[Press-News.org] MIT researchers find a simple formula could guide the design of faster-charging, longer-lasting batteries
The model explains lithium intercalation rates in lithium-ion batteries