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G. Girishkumar

Bio: G. Girishkumar is an academic researcher from IBM. The author has contributed to research in topics: Battery (electricity) & Coulometry. The author has an hindex of 4, co-authored 5 publications receiving 3739 citations.

Papers
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Journal ArticleDOI
TL;DR: In this article, the authors summarized the promise and challenges facing development of practical Li−air batteries and the current understanding of its chemistry, and showed that the fundamental battery chemistry during discharge is the electrochemical oxidation of lithium metal at the anode and reduction of oxygen from air at the cathode.
Abstract: The lithium−air system captured worldwide attention in 2009 as a possible battery for electric vehicle propulsion applications. If successfully developed, this battery could provide an energy source for electric vehicles rivaling that of gasoline in terms of usable energy density. However, there are numerous scientific and technical challenges that must be overcome if this alluring promise is to turn into reality. The fundamental battery chemistry during discharge is thought to be the electrochemical oxidation of lithium metal at the anode and reduction of oxygen from air at the cathode. With aprotic electrolytes, as used in Li-ion batteries, there is some evidence that the process can be reversed by applying an external potential, i.e., that such a battery can be electrically recharged. This paper summarizes the authors’ view of the promise and challenges facing development of practical Li−air batteries and the current understanding of its chemistry. However, it must be appreciated that this perspective ...

2,308 citations

Journal ArticleDOI
Bryan D. McCloskey1, Donald S. Bethune1, Robert M. Shelby1, G. Girishkumar1, Alan C. Luntz1 
TL;DR: Coulometry has to be coupled with quantitative gas consumption and evolution data to properly characterize the rechargeability of Li-air batteries, and chemical and electrochemical electrolyte stability in the presence of lithium peroxide and its intermediates is essential to produce a truly reversible Li-O2 electrochemistry.
Abstract: Among the many important challenges facing the development of Li–air batteries, understanding the electrolyte’s role in producing the appropriate reversible electrochemistry (i.e., 2Li+ + O2 + 2e– ↔ Li2O2) is critical. Quantitative differential electrochemical mass spectrometry (DEMS), coupled with isotopic labeling of oxygen gas, was used to study Li–O2 electrochemistry in various solvents, including carbonates (typical Li ion battery solvents) and dimethoxyethane (DME). In conjunction with the gas-phase DEMS analysis, electrodeposits formed during discharge on Li–O2 cell cathodes were characterized using ex situ analytical techniques, such as X-ray diffraction and Raman spectroscopy. Carbonate-based solvents were found to irreversibly decompose upon cell discharge. DME-based cells, however, produced mainly lithium peroxide on discharge. Upon cell charge, the lithium peroxide both decomposed to evolve oxygen and oxidized DME at high potentials. Our results lead to two conclusions; (1) coulometry has to b...

959 citations

Journal ArticleDOI
TL;DR: It is shown that there is a "sudden death" in charge transport when film thickness is ~5 to 10 nm, and the theoretical model shows that this occurs when the tunneling current through the film can no longer support the electrochemical current.
Abstract: Non-aqueous Li-air or Li-O(2) cells show considerable promise as a very high energy density battery couple. Such cells, however, show sudden death at capacities far below their theoretical capacity and this, among other problems, limits their practicality. In this paper, we show that this sudden death arises from limited charge transport through the growing Li(2)O(2) film to the Li(2)O(2)-electrolyte interface, and this limitation defines a critical film thickness, above which it is not possible to support electrochemistry at the Li(2)O(2)-electrolyte interface. We report both electrochemical experiments using a reversible internal redox couple and a first principles metal-insulator-metal charge transport model to probe the electrical conductivity through Li(2)O(2) films produced during Li-O(2) discharge. Both experiment and theory show a "sudden death" in charge transport when film thickness is ~5 to 10 nm. The theoretical model shows that this occurs when the tunneling current through the film can no longer support the electrochemical current. Thus, engineering charge transport through Li(2)O(2) is a serious challenge if Li-O(2) batteries are ever to reach their potential.

523 citations

Journal ArticleDOI
TL;DR: In this article, the authors present a physics-based model that incorporates the major thermodynamic, transport, and kinetic processes of the Li/oxygen battery, and obtain a good match between porous-electrode experiments and simulations by using an empirical fit to the resistance of the discharge products (which include carbonates and oxides when using carbonate solvents) as a function of thickness.
Abstract: The Li/oxygen battery may achieve a high practical specific energy as its theoretical specific energy is 11,400 Wh/kg Li assuming Li 2 O 2 is the product. To help understand the physics of the Li/oxygen battery we present the first physics-based model that incorporates the major thermodynamic, transport, and kinetic processes. We obtain a good match between porous-electrode experiments and simulations by using an empirical fit to the resistance of the discharge products (which include carbonates and oxides when using carbonate solvents) as a function of thickness that is obtained from flat-electrode experiments. The experiments and model indicate that the discharge products are electronically resistive, limiting their thickness to tens of nanometers and their volume fraction in one of our discharged porous electrodes to a few percent. Flat-electrode experiments, where pore clogging is impossible, show passivation similar to porous-electrode experiments and allow us to conclude that electrical passivation is the dominant capacity-limiting mechanism in our cells. Although in carbonate solvents Li 2 O 2 is not the dominant discharge product, we argue that the implications of this model, (i.e., electrical passivation by the discharge products limits the capacity) also apply if Li 2 O 2 is the discharge product, as it is an intrinsic electronic insulator.

282 citations


Cited by
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Journal ArticleDOI
18 Nov 2011-Science
TL;DR: The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.
Abstract: The increasing interest in energy storage for the grid can be attributed to multiple factors, including the capital costs of managing peak demands, the investments needed for grid reliability, and the integration of renewable energy sources. Although existing energy storage is dominated by pumped hydroelectric, there is the recognition that battery systems can offer a number of high-value opportunities, provided that lower costs can be obtained. The battery systems reviewed here include sodium-sulfur batteries that are commercially available for grid applications, redox-flow batteries that offer low cost, and lithium-ion batteries whose development for commercial electronics and electric vehicles is being applied to grid storage.

11,144 citations

Journal ArticleDOI
TL;DR: The energy that can be stored in Li-air and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed.
Abstract: Li-ion batteries have transformed portable electronics and will play a key role in the electrification of transport. However, the highest energy storage possible for Li-ion batteries is insufficient for the long-term needs of society, for example, extended-range electric vehicles. To go beyond the horizon of Li-ion batteries is a formidable challenge; there are few options. Here we consider two: Li-air (O(2)) and Li-S. The energy that can be stored in Li-air (based on aqueous or non-aqueous electrolytes) and Li-S cells is compared with Li-ion; the operation of the cells is discussed, as are the significant hurdles that will have to be overcome if such batteries are to succeed. Fundamental scientific advances in understanding the reactions occurring in the cells as well as new materials are key to overcoming these obstacles. The potential benefits of Li-air and Li-S justify the continued research effort that will be needed.

7,895 citations

Journal ArticleDOI
TL;DR: Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution as mentioned in this paper.
Abstract: Li-ion battery technology has become very important in recent years as these batteries show great promise as power sources that can lead us to the electric vehicle (EV) revolution. The development of new materials for Li-ion batteries is the focus of research in prominent groups in the field of materials science throughout the world. Li-ion batteries can be considered to be the most impressive success story of modern electrochemistry in the last two decades. They power most of today's portable devices, and seem to overcome the psychological barriers against the use of such high energy density devices on a larger scale for more demanding applications, such as EV. Since this field is advancing rapidly and attracting an increasing number of researchers, it is important to provide current and timely updates of this constantly changing technology. In this review, we describe the key aspects of Li-ion batteries: the basic science behind their operation, the most relevant components, anodes, cathodes, electrolyte solutions, as well as important future directions for R&D of advanced Li-ion batteries for demanding use, such as EV and load-leveling applications.

5,531 citations

Journal ArticleDOI
TL;DR: This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth, summarizing the theoretical and experimental achievements and endeavors to realize the practical applications of lithium metal batteries.
Abstract: The lithium metal battery is strongly considered to be one of the most promising candidates for high-energy-density energy storage devices in our modern and technology-based society. However, uncontrollable lithium dendrite growth induces poor cycling efficiency and severe safety concerns, dragging lithium metal batteries out of practical applications. This review presents a comprehensive overview of the lithium metal anode and its dendritic lithium growth. First, the working principles and technical challenges of a lithium metal anode are underscored. Specific attention is paid to the mechanistic understandings and quantitative models for solid electrolyte interphase (SEI) formation, lithium dendrite nucleation, and growth. On the basis of previous theoretical understanding and analysis, recently proposed strategies to suppress dendrite growth of lithium metal anode and some other metal anodes are reviewed. A section dedicated to the potential of full-cell lithium metal batteries for practical applicatio...

3,812 citations