Martin Z. Bazant

Massachusetts Institute of Technology | MIT · Department of Chemical Engineering

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...

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...

It has been established that combinations of increased ventilation, improved filtration, and other HVAC techniques can reduce the likelihood of airborne disease transmission in buildings. However, with only qualitative guidance, it is difficult for building managers to make informed decisions. Furthermore, the possible actions almost always require...

Porous electrode theory (PET) is widely used to model battery cycling behavior by describing electrochemical kinetics and transport in solid particles and electrolyte, and modeling thermodynamics by fitting an open-circuit potential. The PET model consists of tightly coupled nonlinear partial differential-algebraic equations in which effective kine...

One of the obstacles hindering the scaling-up of the initial successes of machine learning in practical engineering applications is the dependence of the accuracy on the size and quality of the database that “drives” the algorithms. Incorporating the already-known physical laws into the training process can significantly reduce the request for data...

The COVID-19 pandemic has renewed interest in assessing how the operation of HVAC systems influences the risk of airborne disease transmission in buildings. Various processes, such as ventilation and filtration, have been shown to reduce the probability of disease spread by removing or deactivating exhaled aerosols that potentially contain infectio...

This article presents PETLION, which is an open-source, high-performance computing implementation of the porous electrode theory (PET) model in Julia. A typical runtime for a dynamic simulation of full charge or discharge is 3 ms on a laptop while allocating about 1 MB of total memory, and the software is seen to be two orders of magnitude faster t...

The COVID-19 pandemic has renewed interest in assessing how the operation of HVAC systems influences the risk of airborne disease transmission in buildings. Various processes, such as ventilation and filtration, have been shown to reduce the probability of disease spread by removing or deactivating exhaled aerosols that potentially contain infectio...

E-mobility, especially electric cars, has been scaling up rapidly because of technological advances in lithium-ion batteries (LIBs). However, LIBs degrade significantly with service life cycles. With the current increase in the adoption of electric vehicles (EVs), a large volume of retired LIB packs, which can no longer provide satisfactory perform...

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

Layered oxides widely used as lithium-ion battery electrodes are designed to be cycled under conditions that avoid phase transitions. Although the desired single-phase composition ranges are well established near equilibrium, operando diffraction studies on many-particle porous electrodes have suggested phase separation during delithiation. Notably...

It has been established that combinations of increased ventilation, improved filtration, and other HVAC techniques can reduce the likelihood of airborne disease transmission in buildings. However, with only qualitative guidance, it is difficult for building managers to make informed decisions. Furthermore, the possible actions almost always require...

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-supp...

Salt-in-ionic liquid electrolytes have attracted significant attention as potential electrolytes for next generation batteries largely due to their safety enhancements over typical organic electrolytes. However, recent experimental and computational studies have shown that under certain conditions alkali cations can migrate in electric fields as if...

In this work, the performance of electrodeionization (EDI) in seawater desalination was investigated. EDI stack design and operating parameters (applied voltage, recovery, and multi-stage process) were examined during a batch-mode desalination process. The results show that EDI can achieve 99.5% salt removal in a stack with 4 mm spacer thickness (a...

Lithium ion battery is the mainstream technology that is powering most of mobile applications (consumer electronics, power tools etc.) and in the future, our transportation by electrifying the vehicles. Current lithium ion battery can only support 1C charging (~50 mins for 80% charge), which is much longer than refilling gasoline car ( < 5 min). Ex...

Electrochemically mediated selective adsorption is an emerging electrosorption technique that utilizes Faradaically enhanced redox active electrodes, which can adsorb ions not only electrostatically, but also electrochemically. The superb selectivity (>100) of this technique enables selective removal of toxic or high-value target ions under low ene...

Water-in-salt electrolytes (WiSEs) are a class of super-concentrated electrolytes that have shown much promise in replacing organic electrolytes in lithium-ion batteries. At the extremely high salt concentrations of WiSEs, ionic association is more complicated than the simple ion pair description. In fact, large branched clusters can be present in...

Redox flow batteries are an emerging technology for stationary, grid-scale energy storage. Membraneless batteries in particular are explored as a means to reduce battery cost and complexity. Here, a mathematical model is presented for a membraneless electrochemical cell employing a single laminar flow between electrodes, consisting of a continuous,...

Electrochemical ion insertion involves coupled ion–electron transfer reactions, transport of guest species and redox of the host. The hosts are typically anisotropic solids with 2D conduction planes but can also be materials with 1D or isotropic transport pathways. These insertion compounds have traditionally been studied in the context of energy s...

Significance Airborne transmission arises through the inhalation of aerosol droplets exhaled by an infected person and is now thought to be the primary transmission route of COVID-19. By assuming that the respiratory droplets are mixed uniformly through an indoor space, we derive a simple safety guideline for mitigating airborne transmission that w...

A new guideline for mitigating indoor airborne transmission of COVID-19 prescribes a limit on the time spent in a shared space with an infected individual (Bazant and Bush, 2021). Here, we rephrase this safety guideline in terms of occupancy time and mean exhaled carbon dioxide concentration in an indoor space, thereby enabling the use of CO 2 moni...

Electrochemical and mechanical properties of lithium‐ion battery materials are heavily dependent on their 3D microstructure characteristics. A quantitative understanding of the role played by stochastic microstructures is critical for the prediction of material properties and for guiding synthesis processes. Furthermore, tailoring microstructure mo...

Shock electrodialysis is a recently developed electrochemical water treatment method which shows promise for water deionization and ionic separations. Although simple models and scaling laws have been proposed, a predictive theory has not yet emerged to fit experimental data and enable system design. Here, we extend and analyze existing "leaky memb...

We propose a set of simple formulae for interpreting “mercury cyclic porosimetry” measurements where multiple intrusion–extrusion cycles are carried out. By employing two parameters α∈[0,1] and κ∈[0,1], our theory quantitatively breaks down any hysteresis observed in cyclic porosimetry data into contributions due to connectivity effects and contact...

Here we present a theory of ion aggregation and gelation of room temperature ionic liquids (RTILs). Based on it, we investigate the effect of ion aggregation on correlated ion transport-ionic conductivity and transference numbers-obtaining closed-form expressions for these quantities. The theory depends on the maximum number of associations a catio...

Water-in-salt electrolytes (WiSEs) are a class of super-concentrated electrolytes that have shown much promise in replacing organic electrolytes in lithium-ion batteries. At the extremely high salt concentrations of WiSEs, ionic association is more complicated than the simple ion pair description. In fact, large branched clusters can be present in...

Forecasting the health of a battery is a modeling effort that is critical to driving improvements in and adoption of electric vehicles. Purely physics-based models and purely data-driven models have advantages and limitations of their own. Considering the nature of battery data and end-user applications, we outline several architectures for integra...

The forward problems of pattern formation have been greatly empowered by extensive theoretical studies and simulations, however, the inverse problem is less well understood. It remains unclear how accurately one can use images of pattern formation to learn the functional forms of the nonlinear and nonlocal constitutive relations in the governing eq...