2.1. Solvents 4307 2.1.1. Propylene Carbonate (PC) 4308 2.1.2. Ethers 4308 2.1.3. Ethylene Carbonate (EC) 4309 2.1.4. Linear Dialkyl Carbonates 4310 2.2. Lithium Salts 4310 2.2.1. Lithium Perchlorate (LiClO4) 4311 2.2.2. Lithium Hexafluoroarsenate (LiAsF6) 4312 2.2.3. Lithium Tetrafluoroborate (LiBF4) 4312 2.2.4. Lithium Trifluoromethanesulfonate (LiTf) 4312 2.2.5. Lithium Bis(trifluoromethanesulfonyl)imide (LiIm) and Its Derivatives 4313

/pdf/nonaqueous-liquid-electrolytes-for-lithium-based-uxm5ffbi18.pdf

Nonaqueous liquid electrolytes for lithium-based rechargeable batteries.

https://las493energy.files.wordpress.com/2014/11/2005_vetter_jpowsourc.pdf

Ageing mechanisms in lithium-ion batteries

Development of advanced energy-storage systems for portable devices, electric vehicles, and grid storage must fulfill several requirements: low-cost, long life, acceptable safety, high energy, high power, and environmental benignity. With these requirements, lithium-sulfur (Li-S) batteries promise great potential to be the next-generation high-energy system. However, the practicality of Li-S technology is hindered by technical obstacles, such as short shelf and cycle life and low sulfur content/loading, arising from the shuttling of polysulfide intermediates between the cathode and anode and the poor electronic conductivity of S and the discharge product Li2 S. Much progress has been made during the past five years to circumvent these problems by employing sulfur-carbon or sulfur-polymer composite cathodes, novel cell configurations, and lithium-metal anode stabilization. This Progress Report highlights recent developments with special attention toward innovation in sulfur-encapsulation techniques, development of novel materials, and cell-component design. The scientific understanding and engineering concerns are discussed at the end in every developmental stage. The critical research directions needed and the remaining challenges to be addressed are summarized in the Conclusion.

Lithium–Sulfur Batteries: Progress and Prospects

Lithium-ion batteries have had a tremendous impact on several sectors of our society; however, the intrinsic limitations of Li-ion chemistry limits their ability to meet the increasing demands of developing more advanced portable electronics, electric vehicles, and grid-scale energy storage systems. Therefore, battery chemistries beyond Li ions are being intensively investigated and need urgent breakthroughs toward commercial applications, wherein the use of metallic Li is one of the most intuitive choices. Despite several decades of oblivion due to safety concerns regarding the growth of Li dendrites, Li-metal anodes are now poised to be revived because of the advances in investigative tools and globally invested efforts. In this review, we first summarize the existing issues with regard to Li anodes and their underlying reasons and then highlight the recent progress made in the development of high-performance Li anodes. Finally, we propose the persisting challenges and opportunities toward the exploration of practical Li-metal anodes.

Towards practical lithium-metal anodes

https://onlinelibrary.wiley.com/doi/pdf/10.1002/aenm.201800933

Sulfide Solid Electrolytes for Lithium Battery Applications

The primary current‐collector materials being used in lithium‐ion cells are susceptible to environmental degradation: aluminum to pitting corrosion and copper to environmentally assisted cracking. Localized corrosion occurred on bare aluminum electrodes during simulated ambient‐temperature cycling in an excess of electrolyte. The highly oxidizing potential associated with the positive‐electrode charge condition was the primary factor. The corrosion mechanism differed from the pitting typically observed in aqueous electrolytes because each site was filled with a mixed metal/metal‐oxide product, forming surface mounds or nodules. Electrochemical impedance spectroscopy was shown to be an effective analytical tool for characterizing the corrosion behavior of aluminum under these conditions. Based on X‐ray photoelectron spectroscopy analyses, little difference existed in the composition of the surface film on aluminum and copper after immersion or cycling in electrolytes made with two different solvent formulations. Although Li and P were the predominant adsorbed surface species, the corrosion resistance of aluminum may simply be due to its native oxide. Finally, copper was shown to be susceptible to environmental cracking at or near the lithium potential when specific metallurgical conditions existed (work hardening and large grain size). © 1999 The Electrochemical Society. All rights reserved.

https://iopscience.iop.org/article/10.1149/1.1391627/pdf

Corrosion of Lithium‐Ion Battery Current Collectors

Nuclear waste canister corrosion studies pertinent to geologic isolation

Ion-beam irradiation and ion implantation were used to evaluate the influence of point defects and alloying elements on the sulfidation rate of copper films in atmospheric environments containing H 2 S. Low-energy ions from an oxygen plasma were used to grow thin metal oxide passivation layers on Cu films that were subsequently irradiated and exposed to sulfidizing environments (50–600 ppb H 2 S in air with 0.5–85% relative humidity). The type of oxide proved to be important in that a CuO layer essentially prevented sulfidation whereas a Cu 2 O layer permitted sulfidation. For the native copper oxide (Cu 2 O), density-functional theory modeling of Cu divacancy binding energies suggested that alloying with In or Al would cause vacancy trapping and possibly slow the rate of sulfidation. This finding was then experimentally verified for an In-implanted Cu film. A series of marker experiments using unalloyed Cu showed that sulfidation proceeds by solid-state transport of Cu from the substrate through the Cu 2 S product layer.

/pdf/determination-of-solid-state-sulfidation-mechanisms-in-ion-30fvza8m6l.pdf

Determination of solid-state sulfidation mechanisms in ion-implanted copper

A physics-based understanding of material aging mechanisms helps to increase reliability when predicting the lifetime of mechanical and electrical components. This report examines in detail the mechanisms of atmospheric copper sulfidation and evaluates new methods of parallel experimentation for high-throughput corrosion analysis. Often our knowledge of aging mechanisms is limited because coupled chemical reactions and physical processes are involved that depend on complex interactions with the environment and component functionality. Atmospheric corrosion is one of the most complex aging phenomena and it has profound consequences for the nation's economy and safety. Therefore, copper sulfidation was used as a test-case to examine the utility of parallel experimentation. Through the use of parallel and conventional experimentation, we measured: (1) the sulfidation rate as a function of humidity, light, temperature and O{sub 2} concentration; (2) the primary moving species in solid state transport; (3) the diffusivity of Cu vacancies through Cu{sub 2}S; (4) the sulfidation activation energies as a function of relative humidity (RH); (5) the sulfidation induction times at low humidities; and (6) the effect of light on the sulfidation rate. Also, the importance of various sulfidation mechanisms was determined as a function of RH and sulfide thickness. Different models for sulfidation-reactormore » geometries and the sulfidation reaction process are presented.« less

/pdf/mechanisms-of-atmospheric-copper-sulfidation-and-evaluation-2ihpowxswt.pdf

Mechanisms of Atmospheric Copper Sulfidation and Evaluation of Parallel Experimentation Techniques

An analytical capability is being developed that can be used to predict the effect of corrosion on the performance of electrical circuits and systems. The availability of this ''toolset'' will dramatically improve our ability to influence device and circuit design, address and remediate field occurrences, and determine real limits for circuit service life. In pursuit of this objective, we have defined and adopted an iterative, statistical-based, top-down approach that will permit very formidable and real obstacles related to both the development and use of the toolset to be resolved as effectively as possible. An important component of this approach is the direct incorporation of expert opinion. Some of the complicating factors to be addressed involve the code/model complexity, the existence of large number of possible degradation processes, and an incompatibility between the length scales associated with device dimensions and the corrosion processes. Two of the key aspects of the desired predictive toolset are (1) a direct linkage of an electrical-system performance model with mechanistic-based, deterministic corrosion models, and (2) the explicit incorporation of a computational framework to quantify the effects of non-deterministic parameters (uncertainty). The selected approach and key elements of the toolset are first described in this paper. These descriptions are followed by some examples of how this toolset development process is being implemented.

/pdf/a-modeling-approach-for-predicting-the-effect-of-corrosion-4mf265tquv.pdf

J. W. Braithwaite

Papers

Corrosion of Lithium‐Ion Battery Current Collectors

Nuclear waste canister corrosion studies pertinent to geologic isolation

Determination of solid-state sulfidation mechanisms in ion-implanted copper

Mechanisms of Atmospheric Copper Sulfidation and Evaluation of Parallel Experimentation Techniques

A Modeling Approach for Predicting the Effect of Corrosion on Electrical-Circuit Reliability