Martin Z. Bazant

Massachusetts Institute of Technology | MIT · Department of Chemical Engineering

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries ¹ and electrocatalysts ² . Experimental characterizations of such materials by operando microscopy produce rich image datasets 3–6 , but data-driven methods to learn physics...

All-solid-state batteries are attracting increasing interest due to their higher promised energy densities without the use of flammable liquid electrolytes. Two main challenges for solid-state batteries are contact loss and interphase formation; these play a central role in the quality of the solid-electrolyte–electrode interfaces. Here, we present...

Lithium plating during fast charging of porous graphite electrodes in lithium-ion batteries accelerates degradation and raises safety concerns. Predicting lithium plating is challenging due to the close redox potentials of lithium reduction and intercalation, obscured by the nonlinear dynamics of electrochemically driven phase separation in hierarc...

A general theory of coupled ion-electron transfer (CIET) is presented, which unifies Marcus kinetics of electron transfer (ET) with Butler-Volmer kinetics of ion transfer (IT). In the limit of large...

Lithium plating during fast charging of porous graphite electrodes in lithium-ion batteries accelerates degradation and raises safety concerns. Predicting lithium plating is challenging due to the close redox potentials of lithium reduction and intercalation, obscured by the dynamic resistance originated from the interplay of multiphase behavior an...

High-dimensional linear regression is important in many scientific fields. This article considers discrete measured data of underlying smooth latent processes, as is often obtained from chemical or biological systems. Interpretation in high dimensions is challenging because the nullspace and its interplay with regularization shapes regression coeff...

As the design of single-component battery electrodes has matured, the battery industry has turned to hybrid electrodes with blends of two or more active materials to enhance battery performance. Leveraging the best properties of each material while mitigating their drawbacks, multi-component hybrid electrodes open a vast new design space that could...

Climate change demands the development of clean energy technologies, where rechargeable batteries and fuel cells promise a bright future by integrating with solar or wind energy. Li-ion batteries and fuel cells also play essential roles in electrifying transportation in replacement of internal combustion engines. Central to these electrochemical sy...

Lithium-ion insertion kinetics fundamentally hinges upon phase transformation behavior during (dis)charging and understanding the rate-dependent kinetics is crucial for the development of high-power batteries. At high c-rates, kinetic hysteresis is amplified and phase evolution becomes heterogeneous and unpredictable. Specifically, discharge become...

The mixed-ionic electronic conduction (MIEC) of gadolinium doped ceria (CGO) under reduced oxygen conditions makes it an excellent fuel electrode material for SOFC/SOEC applications. As part of a composite electrode (Ni/CGO), the nickel phase offers a fast electronic conduction pathway to the current collector and may act as an electrocatalyst at t...

Power sources of implantable cardioverter-defibrillators (ICD) require high energy density to ensure longevity and sufficient rate capability to provide high power pulses for treating abnormal heart rhythms. Such demands have led to the design of Li/CF x -SVO battery, which leverages the excellent energy density of carbon monofluoride (CF x ) and p...

Sub-nanometer carbon nanotube porins (n-CNTP) have been shown to achieve high water permeation with significant permselectivity precluding anion transport. Therefore, n-CNTPs are useful model systems to probe and optimize the nanoscale transport phenomena relevant for selective ionic separations. Surprisingly, these n-CNTPs demonstrate a unique con...

The phase separation dynamics in graphitic anodes significantly affects lithium plating propensity, which is the major degradation mechanism that impairs the safety and fast charge capabilities of automotive lithium-ion batteries. In this study, we present comprehensive investigation employing operando high-resolution optical microscopy combined wi...

Phase separation during the lithiation of redox-active materials is a critical factor affecting battery performance, including energy density, charging rates, and cycle life. Accurate physical descriptions of these materials are necessary for understanding underlying lithiation mechanisms, performance limitations, and optimizing energy storage devi...

Lithium plating on porous graphite electrodes during the fast charging of lithium-ion batteries ac- celerates degradation and raises safety concerns. The onset of lithium plating is obscured by the reaction and transport resistance within the porous graphite electrodes. We extend the classic porous electrode theory by incorporating a Cahn-Hilliard...

Understanding the charge transfer processes at solid oxide fuel cell (SOFC) electrodes is critical to designing more efficient and robust materials. Activation losses at SOFC electrodes have been widely attributed to the ambipolar migration of charges at the mixed ionic–electronic conductor–gas interface. Empirical Butler–Volmer kinetics based on t...

Water and other polar liquids exhibit nanoscale structuring near charged interfaces. When a polar liquid is confined between two charged surfaces, the interfacial solvent layers begin to overlap, resulting in solvation forces. Here, we perform molecular dynamics simulations of polar liquids with different dielectric constants and molecular shapes a...

Machine learning (ML) is gaining popularity as a tool for materials scientists to accelerate computation, automate data analysis, and predict materials properties. The representation of input material features is critical to the accuracy, interpretability, and generalizability of data-driven models for scientific research. In this Perspective, we d...

As the design of single-component battery electrodes has matured, the battery industry has turned to hybrid electrodes with blends of two or more active materials to enhance battery performance. Leveraging the best properties of each material while mitigating their drawbacks, multi-component hybrid electrodes open a vast new design space that could...

In battery modeling, the electrode is discretized at the macroscopic scale with a single representative particle in each volume. This lacks the accurate physics to describe interparticle interactions in electrodes. To remedy this, we formulate a model that describes the evolution of degradation of a population of battery active material particles u...

Ion concentration polarization (CP, current‐induced concentration gradient adjacent to a charge‐selective interface) has been well studied for single‐phase mixed conductors (e.g., liquid electrolyte), but multiphase CP has been rarely addressed in literature. In our recent publication, we proposed that CP above certain threshold currents can flip t...

Conventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these properties can often be elucidated via the coordination environment of the cation. We develop a theory for the coordinat...

The global devastation of the COVID-19 pandemic has led to calls for a revolution in heating, ventilation, and air conditioning (HVAC) systems to improve indoor air quality (IAQ), due to the dominant role of airborne transmission in disease spread. While simple guidelines have recently been suggested to improve IAQ mainly by increasing ventilation...

Phase separation during the lithiation of redox-active materials is a critical factor affecting battery performance, including energy density, charging rates, and cycle life. Accurate physical descriptions of these materials are necessary for understanding underlying lithiation mechanisms, performance limitations, and optimizing energy storage devi...

Confined fluids and electrolyte solutions in nanopores exhibit rich and surprising physics and chemistry that impact the mass transport and energy efficiency in many important natural systems and industrial applications. Existing theories often fail to predict the exotic effects observed in the narrowest of such pores, called single-digit nanopores...

Electrochemical impedance spectroscopy (EIS) is a powerful tool in characterisation of processes in electrochemical systems, allowing us to elucidate the resistance and characteristic frequency of physical properties such as reaction and transport rates. The essence of EIS is the relationship between current and potential at a given frequency. Howe...

Recent advances in scientific machine learning have shed light on the modeling of pattern-forming systems. However, simulations of real patterns still incur significant computational costs, which could be alleviated by leveraging large image datasets. Physics-informed machine learning and operator learning are two new emerging and promising concept...

Single particle modeling, used in most battery simulations to describe intercalation and degradation, lacks the accurate physics to describe interactions between particles. To remedy this, we formulate a model that describes the evolution of degradation of a population of battery active material particles using ideas in population genetics of fitne...

Conventional lithium-ion batteries, and many next-generation technologies, rely on organic electrolytes with multiple solvents to achieve the desired physicochemical and interfacial properties. The complex interplay between these physicochemical and interfacial properties can often be elucidated via the coordination environment of the cation. We de...

Stabilised Li-rich and Li-poor surface domains formed during fast lithiation and delithiation, respectively, cause a large overpotential difference between discharging and charging.

Ion concentration polarization (CP, current-induced concentration gradient adjacent to a charge-selective interface) has been well studied for single-phase mixed conductors (e.g., liquid electrolyte), but multiphase CP has been rarely addressed in literature. In our recent publication, we proposed that CP above certain threshold currents can flip t...

Reaction rates at spatially heterogeneous, unstable interfaces are notoriously difficult to quantify, yet are essential in engineering many chemical systems, such as batteries [1] and electro-catalysts [2]. Experimental characterizations of such materials by operando microscopy produce rich image datasets [3, 4, 5, 6], but data driven methods to le...

We consider laminar, fully-developed, Poiseuille flows of liquid in the Cassie state through diabatic, parallel-plate microchannels symmetrically textured with isoflux ridges. Through the use of matched asymptotic expansions we analytically develop expressions for (apparent hydrodynamic) slip lengths and variously-defined Nusselt numbers. Our small...

Fast charging studies for lithium-ion batteries aim to minimize charging time while maximizing battery lifetime. Real-time optimal control problems are typically solved using empirical or simplified physical models with constraint-based model predictive control (MPC). In this article, we derive physics-based operating modes based on degradative gov...

Conventional battery simulation tools offer current, voltage, and power operating modes. This article presents general operating modes (GOMs), which move beyond these standard modes and allow battery models of any scale to simulate novel operating modes such as constant temperature, constant lithium plating overpotential, and constant concentration...

Disorder-driven degradation phenomena, such as structural phase transformations and surface reconstructions, can significantly reduce the lifetime of Li-ion batteries, especially those with nickel-rich layered-oxide cathodes. We develop a general free energy model for layered-oxide ion-intercalation materials as a function of the degree of disorder...

Lithium plating is one major degradation mechanism of the anode in lithium-ion batteries. The redox potential of graphite, the most widely used anode material, is 0.1 V vs. Li ⁺ /Li, thus making parasitic Li plating inevitable during operation without precise control. Capturing the onset of lithium plating on graphite on the fly usually relies on b...

Understanding the microscopic mechanism of Li-ion insertion in intercalation solids is crucial for the design of energy storage devices with optimal power and energy densities. Li intercalation kinetics has been traditionally treated by the phenomenological Butler-Volmer kinetics, but remains poorly measured and understood. For example, reported li...

A physics-based, reduced order framework is developed to calculate the charge capacity loss contributions from spatially homogeneous and heterogeneous degradation mechanisms, chemomechanical cycling and initial capacity recovery. The formulation goes well beyond prevalent coulomb-counting models and is tuned solely based on experimentally measurabl...

Electrochemical methods are known to have attractive features and capabilities when used for ion separations and water purification. In this study, we developed a new process called shock ion extraction (shock IX) for selective and chemical-free removal of toxic heavy metals from water. Shock IX is a hybrid process that combines shock electrodialys...

Ion-surface interactions can alter the properties of nanopores and dictate nanofluidic transport in engineered and biological systems central to the water-energy nexus. The ion adsorption process, known as "charge regulation", is ion-specific and is dependent on the extent of confinement when the electric double layers (EDLs) between two charged su...

Water-based anti-corrosion coatings, which are environmentally-friendly replacements for organic solvent-based coatings, do not perform well enough for use in the most challenging corrosion environments. The high water absorption capacity of water-based latex films may reduce barrier performance by contributing to corrosive reactant/product transpo...

Understanding the bulk and interfacial properties of super-concentrated electrolytes, such as ionic liquids (ILs), has attracted significant attention lately for their promising applications in supercapacitors and batteries. Recently, McEldrew et al. developed a theory for reversible ion associations in bulk ILs, which accounted for the formation o...

Agricultural development, extensive industrialization, and rapid growth of the global population have inadvertently been accompanied by environmental pollution. Water pollution is exacerbated by the decreasing ability of traditional treatment methods to comply with tightening environmental standards. This review provides a comprehensive description...

Disorder-driven degradation phenomena, such as structural phase transformations and surface reconstructions, can significantly reduce the lifetime of Li-ion batteries, especially those with nickel-rich layered-oxide cathodes. We develop a general free energy model for layered-oxide ion-intercalation materials as a function of the degree of disorder...

Nonvolatile resistive-switching (RS) memories promise to revolutionize hardware architectures with in-memory computing. Recently, ion-interclation materials have attracted increasing attention as potential RS materials for their ion-modulated electronic conductivity. In this Letter, we propose RS by multiphase polarization (MP) of ion-intercalated...

This talk will describe the physics of driven nucleation and growth in battery materials. The resulting nonequilibrium pattern formation may be either reaction-limited or transport limited. Examples of the former include driven phase separation in Li-ion batteries, electrodeposition in Li-air batteries, and Li plating in Li-ion batteries, controlle...

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including deca...

Nanopores lined with hydrophobic groups function as switches for water and all dissolved species, such that transport is allowed only when applying a sufficiently high transmembrane pressure difference or voltage. Here we show a hydrophobic nanopore system whose wetting and ability to transport water and ions is rectified and can be controlled with...

Replacing fossil fuels with energy sources and carriers that are sustainable, environmentally benign, and affordable is amongst the most pressing challenges for future socio-economic development. To that goal, hydrogen is presumed to be the most promising energy carrier. Electrocatalytic water splitting, if driven by green electricity, would provid...

Nonvolatile resistive-switching (RS) memories promise to revolutionize hardware architectures with in-memory computing. Recently, ion-interclation materials have attracted increasing attention as potential RS materials for their ion-modulated electronic conductivity. In this Letter, we propose RS by multiphase polarization (MP) of ion-intercalated...

Constitutive laws underlie most physical processes in nature. However, learning such equations in heterogeneous solids (for example, due to phase separation) is challenging. One such relationship is between composition and eigenstrain, which governs the chemo-mechanical expansion in solids. Here we developed a generalizable, physically constrained...

Understanding the bulk and interfacial properties of super-concentrated electrolytes, such as ionic liquids (ILs), has attracted significant attention lately for their promising applications in supercapacitors and batteries. Recently, McEldrew \textit{et al.} developed a theory for reversible ion associations in bulk ILs, which accounted for the fo...

The structure of polar liquids and electrolytic solutions, such as water and aqueous electrolytes, at interfaces underlies numerous phenomena in physics, chemistry, biology, and engineering. In this work, we develop a continuum theory that captures the essential features of dielectric screening by polar liquids at charged interfaces, including osci...

Dip coating consists of withdrawing a substrate from a bath to coat it with a thin liquid layer. This process is well understood for homogeneous fluids, but heterogeneities, such as particles dispersed in liquid, lead to more complex situations. Indeed, particles introduce a new length scale, their size, in addition to the thickness of the coating...

In this paper, we explore the electrokinetics in the complex two-dimensional geometries via conformal mapping and experimental comparison. A general theoretical frame of conformal mapping is provided for the application in electrokinetics, and three geometries are taken as an example to derive concentration polarization, potential, and electric fie...

Ionic liquids (ILs) are charged fluids composed of anions and cations of different size and shape. The ordering of charge and density in ILs confined between charged interfaces underlies numerous applications of IL electrolytes. Here, we analyze the screening behavior and the resulting structural forces of a representative IL confined between two c...

Lithium-ion batteries are one of the most commonly used energy storage device for electric vehicles. As battery chemistries continue to advance, an important question concerns how to efficiently determine charging protocols that best balance the desire for fast charging while limiting battery degradation mechanisms which shorten battery lifetime. C...

The development of highly efficient separation membranes utilizing emerging materials with controllable pore size and minimized thickness could greatly enhance the broad applications of membrane-based technologies. Having this perspective, many studies on the incorporation of nanosheets in membrane fabrication have been conducted, and strong intere...

The COVID-19 pandemic has focused renewed attention on the ways in which building HVAC systems may be operated to mitigate the risk of airborne disease transmission. The most common suggestion is to increase outdoor-air ventilation rates so as to dilute the concentrations of infectious aerosol particles indoors. Although this strategy does reduce t...

The electrostatic screening of charge in one-dimensional confinement leads to long-range breakdown in electroneutrality within a nanopore. Through a series of continuum simulations, we demonstrate the principles of electroneutrality breakdown for electrolytes in one-dimensional confinement. We show how interacting pores in a membrane can counteract...

Ultrathin membranes with nanoporous conduits show promise for ionic separations and desalination applications, but the mechanisms underlying the nonlinear ionic transport observed in these systems are not well understood. Here, we demonstrate how induced charge at membrane interfaces can lead to nonlinear ionic transport and voltage-dependent condu...

Freezing in charged porous media can induce significant pressure and cause damage to tissues and functional materials. We formulate a thermodynamically consistent theory to model freezing phenomena inside charged heterogeneous porous space. Two regimes are distinguished: free ions in open pore space lead to negligible effects of freezing point depr...

A variety of polymeric surfaces, such as anti-corrosion coatings and polymer-modified asphalts, are prone to blistering when exposed to moisture and air. As water and oxygen diffuse through the material, dissolved species are produced, which generate osmotic pressure that deforms and debonds the coating. These mechanisms are experimentally well-sup...

Simultaneous multilayer coating techniques are widely known, but their industrial application remains limited to narrow market sectors. One barrier to adoption may be the mismatch between industries that are familiar with such processes but have no need, and industries that have need but are not familiar. Moreover, there are application-specific te...

Dip-coating consists in withdrawing a substrate from a bath to coat it with a thin liquid layer. This process is well-understood for homogeneous fluids, but heterogeneities such as particles dispersed in the liquid lead to more complex situations. Indeed, particles introduce a new length scale, their size, in addition to the thickness of the coatin...

Advancing lithium-ion battery technology requires the optimization of cycling protocols. A new data-driven methodology is demonstrated for rapid, accurate prediction of the cycle life obtained by new cycling protocols using a single test lasting only 3 cycles, enabling rapid exploration of cycling protocol design spaces with orders of magnitude red...