When short plasma half-life drugs act only briefly, they require frequent or continuous administration. We report the engineering of a non-invasive oral drug delivery system for long-term, continuous administration of these drugs. Their non-invasive, long-term, continuous administration at daily doses exceeding 100 mg has, for many years, been considered an insurmountable challenge. We show that over 1200 mg/day of 4:1 levodopa-carbidopa (LD-CD) can be non-invasively and continuously extruded when formulated as a semisolid paste, loaded with 63%w/w of the solid drugs. The drug delivery system comprises a reusable orthodontic retainer with a co-molded pocket into which the patient inserts after each meal a new 1 mL propellant-driven, prefilled, disposable, drug delivery extruder. The paste is delivered to the lingual side of the teeth where it is mixed with saliva and swallowed. As reported elsewhere, a 15-day, 16 patient open label clinical trial of the drug delivery system continuously extruding LD-CD paste significantly reduces the variability of the plasma LD concentration and alleviates symptoms of advanced Parkinson’s disease (PD) as compared to LD-CD tablets.

Passivation of stainless steel by additives forming mass-transport blocking layers is widely practiced, where Cr element is added into bulk Fe-C forming the Cr2O3-rich protective layer. Here we extend the long-practiced passivation concept to Si anodes for lithium-ion batteries, incorporating the passivator of LiF/Li2CO3 into bulk Si. The passivation mechanism is studied by various ex situ characterizations, redox peak contour maps, thickness evolution tests, and finite element simulations. The results demonstrate that the passivation can enhance the (de)lithiation of Li-Si alloys, induce the formation of F-rich solid electrolyte interphase, stabilize the Si/LiF/Li2CO3 composite, and mitigate the volume change of Si anodes upon cycling. The 3D passivated Si anode can fully retain a high capacity of 3701 mAh g(-1) after 1500 cycles and tolerate high rates up to 50C. This work provides insight into how to construct durable Si anodes through effective passivation.

Ehud Keinan's invitation to write for Rosarium Philosophorum has given me an opportunity to alert colleagues to drivers of government-funded, media-driven, non-innovative research. It is a managed, development-like activity, performed by large groups. Unlike development, which produces ready-for-engineering pre-prototypes, it produces multi-authored publications. It does not uncover truths of Nature, nor does it report novel product, process, or service-concepts. My purpose here is to make colleagues who are performing such research, as well as governmental colleagues who fund it, reflect upon it, and consider funding instead development of essential, but non-patentable, products, processes, and services, that ventures and established industries do not pursue because of their low profit potential. Innovation, irrespective of practicality, is the most important outcome of research. Innovators think differently than others – otherwise they would not innovate. Innovation is a divergence from the prevalent, and as such it only thrives in communities, social strata, societies, and nations where divergent thought is not only accepted, but cherished. It is confined to communities and societies that accept divergent truths. It is absent from societies, social strata and nations that do not. In Israel, a country with one of the world's most innovative societies, innovation is confined to the open-minded societal segment; and in the United States, innovation is confined to communities in geographic pockets, where divergence-of-thought is accepted. There is no innovation in the larger area where it is not. Innovative research does not depend on wealth. There are only few thought-changing per-capita publications by scientists who are citizens of high per-capita GDP countries in which divergence-of-thought is societally unacceptable and there are only few issued United States patents per-capita by inventors from these countries. Innovators of countries, who were prevented by the traditional social norms of their extended families and communities from thinking differently flock to diversity accepting pockets of the United States, where they thrive. Their innovations enrich their adopted communities, where difference including difference in thought, gender, color, and ethnicity is accepted. Some innovations change the way we think. Nothing is a greater achievement than the uncovering of a truth that, after its uncovering, becomes obvious. Currently, academic researchers uncover most truths of Nature, but in the past, researchers at major corporate research laboratories, such as Bell Labs, uncovered most. Innovators in business, science, and technology are individuals or small teams of peers, rather than large, managed, research groups. In large managed research groups, it is the managing investigator who defines the boundaries of thought, and the thinking of the subordinate members of the group are confined to within these. While I was Head of the Electronic Materials Research Department of Bell Labs, I was, like all other Members of the Technical Staff, including our Vice President of Research Nobel prize winner Arno Penzias, assisted by only one Associate or Postdoctoral Member of the Technical Staff. Bell Labs Research had about 500 researchers, constituting only about 4 % of its Members of Technical Staff. They covered vast segments of knowledge, including communication, psychology, physiology, linguistics, economics, mathematics, logistics, computer science, statistics, atmospheric science, astronomy, physics, chemistry and materials science to mention some. There were only 2 or 3 researchers in any sub-field. When a new truth emerged, creating significant opportunities, peer-researchers voluntarily joined in, often from different departments and disciplines, forming small, potently innovative, teams comprising only 2 or 3, members. There are few Bell Labs research publications with many co-authors. Researchers published only one paper, or a few papers, each year. Thought-changing scientific publications rarely have more than two authors. Nobel prizes are not awarded to large groups. Innovative companies like Google, Dell, Amazon, or Apple were not conceived by many people. Their large, managed, development teams were only subsequently built to provide society with the fruits of the innovation. Innovation can have massive monetary value. When it does, fiscal valuation measures its success. By this measure, ventures are now most successful, followed by corporate research centers, followed by universities, tailed by managed national laboratories. Because the essence of innovation is divergent thought, it cannot be managed. Management's role is not to manage research, but to foster an innovative environment, to encourage divergent thinking, to recognize innovation, and to reward innovators. Innovative environments exist currently mostly in ventures, less so at corporate research centers and in academia, and least so at national laboratories, where managers attempt to manage research. Management of Bell Labs, that meticulously managed Development and Engineering, did not manage Research. Bell Lab's Research Department Heads, Directors, Executive Directors, and Vice Presidents were expected to pursue personal research that did not overlap research of Members of the Technical Staff reporting to them. When I was appointed to head Bell Labs’ Electronic Materials Research Department my mentor and Executive Director William P. (Bill) Slichter told me that in my personal research I should continue to do anything that I see as having the potential of uncovering a truth, or of being of value to society; but my personal research must not overlap that of the members of my department. This distinguished research at Bell Labs from research at almost all other organizations. It was one of the reasons why many of the truths underlying today's age of information, communication and entertainment were uncovered by the researchers of Bell Labs; and why the research at Bell Labs resulted in 9 Nobel Prizes, 4 Turing Awards, 3 Japan Prizes, 12 US National Medals of Science and 12 US National Medals of Technology and Innovation. Research, Development, and Engineering are distinct activities, requiring different mindsets, management, and resources. If the difference is not recognized, the project is almost certain to fail. Development requires management of a team, often peopled by experts of different disciplines; it is coordinated, planned, and has milestones. Failure to achieve any critical development milestone results in termination of the project. At points where multiple developmental paths exist choosing of any but the best option results in an inferior pre-prototype. When a project manager falls in love with any critical element, be it a method, a tool or a material, the project often fails. Admiral Hyman Rickover,1 the engineer and lifelong public servant who, facing massive political adversity, managed one of the most demanding governmental development and engineering programs of the United States and led to the launching of the United States nuclear navy remarked: It is a human inclination to hope things will work out, despite evidence or doubt to the contrary. A successful manager must resist this temptation. This is particularly hard if one has invested much time and energy on a project and thus has come to feel possessive about it. Although it is not easy to admit what a person once thought correct now appears to be wrong, one must discipline himself to face the facts objectively and make the necessary changes – regardless of the consequences to himself. The man in charge must personally set the example in this respect. He must be able, in effect, to “kill his own child” if necessary and must require his subordinates to do likewise. I have had to go to Congress and, because of technical problems, recommended terminating a project that had been funded largely on my say-so. It is not a pleasant task, but one must be brutally objective in his work.” Unlike most science and technology organizations, past or present, academic, industrial, or governmental, Bell Labs recognized by different criteria excellence in Research, in Development, and in Engineering. Bell Labs’ unmanaged researchers searched for new truths, except in emergencies when they were tasked to assist in problem solving. Development was managed and answered whether a newly uncovered truth might serve society, designing, constructing, and testing prototypes, processes, algorithms, and software tools. Engineering established that Development's prototyped products, processes and tools could cost-effectively meet standards of performance, reliability, and dependability. For several years Louis E. Brus and I recruited for Bell Labs’ chemists at Columbia University. When I interviewed them, I already knew from their records and professors that they were competent, so I posed them the following question: Assume that for your research you were provided with an empty room full of money – what would you do? When the candidates answer was that they would work on Bell System needs, or follow their thesis advisor's research, I would not recommend inviting them for interviews in Research. I would, however, recommend them for interviews in Development, or in Engineering whenever an opening requiring their talents appeared. Today, academic, and government-associated developers aiming to create people-serving products and services underperform when their primary objective is to prove that their idea, method, or tool is “right”. Almost always there are multiple ways and means to create a novel product, process, or service; if the developer assumes that his or hers is the “right” one, the project is likely to be doomed to failure. Even in a mildly complex development project with only 5 critical points, where the manager must choose between 3 or 4 paths, the likelihood of an optimal outcome drops precipitously if the manager favors his or her own, dropping at the first branching-point to between 0.33 and 0.25; at the second, to between 0.332 and 0.252 ; and at the 5th to between 0.335 and 0.255, i. e. to between 0.004 and 0.001. Much of the government-funded, media-driven, non-innovative research is performed by large teams, mostly of the same discipline. It is sustained by large budgets, provided by well-meaning political leaders and legislators. The Grand Masters of such research are the best proposal-writers and the best report-writers in human history. Their proposals create the illusion of addressing a human need. But, by the time the allocated funds are spent, the need is unmet. The outcome of the expended resources is a multitude of publications. The more there are, the more they are cited, the more they are cited, the more they are used to justify further allocation of funds. The Masters are well-regarded and are well-rewarded by the officers of their organizations who depend them for part of their livelihood. They are also well regarded by their subordinates, who also depend on them for part or all their livelihood. They even serve as examples to peers, who justify their own government-funded, media-driven, non-innovative research by citing those of the Masters. When the prime objective of research was still the uncovering of a truth of Nature and its other important objective was still the conception of a people-serving product, process, or service, few introductory sections of publications mentioned a human need, even though needs always existed. An introduction to an article on pesticide-research, on ammonia-research, or on fertilizer-research, did not mention that hunger prevailed in the world. At this time, introductions to government-funded, media-driven, non-innovative research publications almost always refer to a great human affliction: global warming, polluted environment, exhaustion of our planet's resources, to mention a few. The reader is confronted with publications on fictitious means that meet the great needs, the fictitious means fitted to the expertise of the principal investigator. A back-of-the-envelope, 5-minute, calculation would usually reveal prohibitive costs, dimensions, or throughputs. Even though the largest government-funded, media-driven, non-innovative research projects are funded by Engineering-size budgets, the fund-allocating political leaders and legislators rarely consult engineers who have engineered a society-serving product, process, or service. In the United States, organizations receiving a large share of the government-funded, media-driven, non-innovative research funds maintain a professional lobbying staff in Washington and ride political waves. Legislators and political leaders, to whom science and technology officers ultimately report, have political agendas. These reflect the wishes of their constituents whose sources of information are the media. Reporters are not engineers, nor are they experts in the underlying technologies. Their reporting is rarely based on interviews with engineers; instead, it is often based on interviews with opinionated advocates of social movements, or with beneficiaries of large, government-funded, non-innovative research grants. I shall use, as an example, humanity's great challenge of climate change. Climate change is linked by the media, and is consequently politically linked, with environmental pollution, even though the two are fundamentally different. Global warming is driven primarily by the increase in atmospheric CO2 concentration. CO2, which we exhale, is not a pollutant. While economists know this, few scientists appreciate that the increase in atmospheric CO2 concentration continues to scale linearly, as it has always scaled, with the increase in global wealth. Global wealth is the product of the world's population and its per-capita GDP. Because many people of our planet are disinclined to have smaller families, and nearly all strive for affluence, the linear dependence of the increase in atmospheric CO2 concentration on the increasing global wealth persists now, and is likely to persist during the lives of our children. The linear dependence has persisted with only a modest change in the slope in spite of the exquisite successes of the past 50 years in lowering the costs of wind and solar power; in efficient gas turbines that unlike coal-burning power stations are turned off when electrical power is not in demand; in increases in energy efficiencies of vehicles; in energy efficient LED lighting; in thermal insulation of buildings; and in biofuels and plant-derived chemicals. Climate engineering research aims to assess the feasibility and the beneficial and the adverse effects of intervention in the Earth's climate system to counter climate change. It includes research on removal of CO2 from the atmosphere by enhancing the photosynthetic activity in Southern Oceans by trace-amounts of nutrients, and research on cooling the Earth by reflecting solar energy back to space. Climate engineering research is presently suppressed, because the public has not been told by the media that humanity has either to stop its pursuits of affluence and procreation, or it must intensify its climate engineering research. Only one or the other can avert almost certain catastrophic climate change. Instead of alerting the public of the need for innovative climate engineering research unless sacrifices in family size and affluence are made, the media has accepted, and continues to advocate, the dogma of the environmental movement that climate engineering is sinful. This has led to a greater number of publications on engineering-wise questionable microbial biofuel cells than on climate engineering research. Only outstanding funding officers make decisions based on their own judgement; most rely on advisory committees whose members often consider their own research highly. Never have I been a member of an advisory committee that promoted search for a truth of Nature, nor have I been a member of an advisory committee that promoted people-serving product, process, or service conception. Only the finest of funding officers have stood against wrong committee-recommendations and none whom I knew was ever rewarded for taking such a risk. Patent applications are filed, and clinical trials are initiated, before, when, or after research leads to a new concept for a product, process, or service. Table 1 column 2 shows the number of SciFinder Scholar abstracted publications of letters, journal articles, and reviews for the search terms listed in column 1; column 3 shows the number of SciFinder Scholar abstracted patents and clinical trials for the same terms; and column 4 shows the ratio of patents and clinical trials to publications for these terms. SciFinder Search Term Journal Articles, Letters and Reviews Patents and Clinical Trials Patents/Publications Ratio Nanotechnology 2,254,000 496,000 0.22 Fuel cells 127,000 116,000 0.91 Electrocatalysis 121,000 17,000 0.14 Lithium batteries 103,000 130,000 1.26 Integrated circuits 56,800 145,300 2.55 Photoelectrochemical 36,000 4,000 0.11 Electrochemical biosensors 25,000 4,000 0.16 Microelectronics 21,000 10,400 0.50 Microbial fuel cells 10,500 2,000 0.19 The number of journal articles, letters, and reviews containing the term “nanotechnology” is staggering: It exceeds the combined number of publications containing the other 8 listed terms. Yet the ratio of nanotechnology patents and clinical trials to publications is modest, 11.6 times smaller than it is for integrated circuits, 5.7 times smaller than it is for lithium batteries, and 4.1 times smaller than for fuel cells. This suggests disproportionate investment of governmental funds in nanotechnology. The ratio of patents and clinical trials to letter, journal articles, and reviews declines in the following order: integrated circuits≫lithium batteries>fuel cells≫microelectronics≫nanotechnology>microbial fuel cells>electrochemical biosensors>electrocatalysis>photoelectrochemical. There are only twice as many SciFinder Scholar abstracted papers on widely used microelectronics than on microbial fuel cells, having as yet no utility. Of the group of fuel cells, electrocatalysis, and lithium batteries, the ratio is high for fuel cells and for lithium batteries, but not for electrocatalysis. Overall, it does not appear that resources are optimally allocated for creating electrochemical products or processes. I consider both new truth-seeking academic research, as well as innovative product, process, or service-creating venture research to be important for society. Academic researchers often produce answer and then look for relevant questions, and in doing so often propose fictitious products, processes, or services. In contrast, venture researchers who create products, processes, or services rarely claim to have uncovered new truths of Nature. While my colleagues in the start-up stage of ventures focus on meeting a need and accordingly adjust their methods and means, most of my academic colleagues focus on their methods and means and try to adjust a need to these. This reduces the fiscal return on academic research relative to the return on research by early stage ventures. A start-up will drop a project as soon as it becomes evident that it was mis-aimed, has been obviated, or is impractical. In contrast, the academic researcher tends to persist, and only the discontinuation of his or her funding stops the project. It is rare for an academic researcher to tell the manager of his or her governmental funding agency that the use of allocated funds should be re-directed. In contrast, a CEO of a startup promptly advises the investors if a target is no longer valid. Overall, research funds are less efficiently used for academic research than by startups. This is so also because academic research is burdened by larger overhead administrative and facilities costs. Over the 20 years life of a patent, a university, spending 10 billion USD for research over these 20 years, may derive about 0.5 billion USD from its generated intellectual property. The aggregate annual rate of return on investment in small start-ups is about 15 %, for a return of more than USD 20 billion over the 20 years. A recipient of development funds should be held accountable for their use. Development, being a managed activity requiring and provided with more funds than research, should deliver a pre-prototype of a product, a process, or a service, not just perform work aimed at delivering one of these. The project manager must either deliver the pre-prototype, or expeditiously shut down the project if failure to deliver becomes likely. When a manager repeatedly fails to deliver the promised or implied pre-prototype, or fails to shut down the activity in a timely manner, he or she should not be considered for future funds. The decision to allocate governmental Development funds should be made by a cognizant technical officer with sufficient engineering knowledge for oversight. This public servant should be responsible for the decision and have the authority to terminate the funding if it becomes clear that the objective will not be achieved. Once I saw a governmental funding document signed by 17 officials. The 17 signatures signified that no one had assumed responsibility for the expenditure, that no one had authority over the project, and no one was technically responsible for its execution. The governmental allocator of the development funds should transfer full authority over managing the project to the development project manager, whom the allocator should hold responsible for efficacious management. The governmental fund allocator should be provided with timely reports, monthly for the costliest development programs, and quarterly for the others. I can do no better here than to again cite Hyman Rickover:1 “A major flaw in our system of government, and even in industry, is the latitude allowed to do less than is necessary. Too often officials are willing to accept and adapt to situations they know to be wrong. The tendency is to downplay problems instead of actively trying to correct them. Recognizing this, many subordinates give up, contain their views within themselves, and wait for others to take action. When this happens, the manager is deprived of the experience and ideas of subordinates who generally are more knowledgeable than he in their particular areas. A manager must instill in his people an attitude of personal responsibility for seeing a job properly accomplished. Unfortunately, this seems to be declining, particularly in large organizations where responsibility is broadly distributed. To complaints of a job poorly done, one often hears the excuse, “I am not responsible.” I believe that is literally correct. The man who takes such a stand in fact is not responsible; he is irresponsible. While he may not be legally liable, or the work may not have been specifically assigned to him, no one involved in a job can divest himself of responsibility for its successful completion. The man in charge must concern himself with details. If he does not consider them important, neither will his subordinates. Yet “the devil is in the details.” It is hard and monotonous to pay attention to seemingly minor matters. In my work, I probably spend about ninety-nine percent of my time on what others may call petty details. Most managers would rather focus on lofty policy matters. But when the details are ignored, the project fails. No infusion of policy or lofty ideals can then correct the situation. One must create the ability in his staff to generate clear, forceful arguments for opposing viewpoints as well as for their own. Open discussions and disagreements must be encouraged, so that all sides of an issue will be fully explored.” If today I were to allocate governmental research funds, I would limit these to individual researchers, supporting only one assistant, or a single postdoctoral fellow. I would reward original thinking and penalize large budget, multi-publication, research. I would consider favorably a novel idea. Most importantly, I would not use research funds for development. I would, at the same time, fund large development teams, developing essential products, processes, and services, that are neither patentable nor likely to produce large profits. An example of such an activity is that of the Oxford RECOVERY Collaborative Group. Its 26-member team recently demonstrated the utility of the long-established, non-patentable, and inexpensive drug dexamethasone in reducing the mortality of ventilated COVID-19 patients.2 Our norm is to ostracize a researcher reporting experimental results that were not observed or reporting results of others as his or her own. Our society also condemns criminals who embezzle public funds or sell worthless securities. It is a moral question if a managers who obtain taxpayer funds for an activity that they know cannot result in the proposed product, process, or service, e. g., because of its intrinsic cost, its dimension, or its throughput, should also be ostracized. Organizations legally protect themselves by a clause in taxpayer-funded research proposals saying that they will diligently work toward the product, process, or service. I propose, however, that they also certify, through a single paragraph, that the product, process, or service is not absurd in cost, size, or throughput, and that it has the potential of out-performing at lower cost, or without raising the cost, any existing equivalent.

Doping is a well-known strategy to enhance the electrochemical energy storage performance of layered cathode materials. Many studies on various dopants have been reported; however, a general relationship between the dopants and their effect on the stability of the positive electrode upon prolonged cell cycling has yet to be established. Here, we explore the impact of the oxidation states of various dopants (i.e., Mg2+, Al3+, Ti4+, Ta5+, and Mo6+) on the electrochemical, morphological, and structural properties of a Ni-rich cathode material (i.e., Li[Ni0.91Co0.09]O2). Galvanostatic cycling measurements in pouch-type full Li-ion cells show that cathodes featuring dopants with high oxidation states significantly outperform their undoped counterparts and the dopants with low oxidation states. In particular, Li-ion pouch cells with Ta5+- and Mo6+-doped Li[Ni0.91Co0.09]O2 cathodes retain about 81.5% of their initial specific capacity after 3,000 cycles at 200 mAh g-1. Furthermore, physicochemical measurements and analyses suggest substantial differences in the grain geometries and crystal lattice structures of the various cathode materials, which contribute to their widely Myung et al. ACS Energy Lett. 2017, 2, 196-223. Kim et al. Energy Environ. Sci. 2018, 11, 1271-1279. Kim et al. energy. 2020, 5, 860-869. Kim et al. ACS Energy Lett. 2017, 2, 1848-1854.

ADVERTISEMENT RETURN TO ISSUEPREVCommentNEXTDetlev Müller's Discovery of Glucose Oxidase in 1925Adam Heller*Adam HellerUniversity of Texas, Austin, Texas 78712, United States*Email: [email protected]More by Adam Hellerhttp://orcid.org/0000-0003-0181-1246 and Jens UlstrupJens UlstrupTechnical University of Denmark, DK-2800 Kongens Lyngby, DenmarkMore by Jens Ulstruphttp://orcid.org/0000-0002-2601-7906Cite this: Anal. Chem. 2021, 93, 18, 7148–7149Publication Date (Web):April 27, 2021Publication History Published online27 April 2021Published inissue 11 May 2021https://pubs.acs.org/doi/10.1021/acs.analchem.1c01191https://doi.org/10.1021/acs.analchem.1c01191article-commentaryACS PublicationsCopyright © 2021 American Chemical Society. This publication is available under these Terms of Use. Request reuse permissions This publication is free to access through this site. Learn MoreArticle Views1656Altmetric-Citations4LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InRedditEmail PDF (9 MB) Get e-AlertscloseSUBJECTS:Carbohydrates,Fungi,Granular materials,Peptides and proteins,Sensors Get e-Alerts

The highly reactive nature and rough surface of Li foil can lead to the uncontrollable formation of Li dendrites when employed as an anode in a lithium metal battery. Thus, it could be of great practical utility to create uniform, electrochemically stable, and "lithiophilic" surfaces to realize homogeneous deposition of Li. Herein, a LiZn alloy layer is deposited on the surface of Li foil by e-beam evaporation. The idea is to introduce a uniform alloy surface to increase the active area and make use of the Zn sites to induce homogeneous nucleation of Li. The results show that the alloy film protected the Li metal anode, allowing for a longer cycling life with a lower deposition overpotential over a pure-Li metal anode in symmetric Li cells. Furthermore, full cells pairing the modified lithium anode with a LiFePO4 cathode showed an incremental increase in Coulombic efficiency compared with pure-Li. The concept of using only an alloy modifying layer by an in-situ e-beam deposition synthesis method offers a potential method for enabling lithium metal anodes for next-generation lithium batteries.

In layered oxide cathodes for lithium-ion batteries, nickel provides high capacity but compromises stability. Although much progress has been made in upsetting this trade-off, the stability of Ni-rich cathodes is not yet adequate to satisfy the expectations of commercial batteries. Here, a layered Li[Ni0.89Co0.10Sb0.01]O2 cathode material, which overcomes the instabilities associated with highly Ni-rich cathodes to deliver excellent capacity retention, is reported. This cathode shows a significantly enhanced resistance to performance deterioration and microcrack propagation compared to the more conventional Li[Ni0.885Co0.10Al0.015]O2 material. Furthermore, it delivers more capacity than its counterpart despite the same nickel content. The robustness of the material arises from the ordering of the grains into a dense flower-petal arrangement, which collectively preserves the coherency of the particle. Through extensive cross-sectional imaging and chemical mapping, a correlation between microcracks and electrolyte infiltration into the particle is demonstrated. Figure 1

This Perspective discusses the prospective strategies for overcoming the stability and capacity trade-off associated with increased Ni content in layered Ni-rich Li[NixCoyMnz]O2 (NCM) and Li[NixCoyAlz]O2 (NCA) cathodes. The Ni-rich NCM and NCA cathodes have largely replaced the LiCoO2 cathodes in commercial batteries because of their lower cost, higher energy density, good rate capability, and reliability that has been extensively field-tested. Nevertheless, they suffer from microcrack generation along grain boundaries and Ni3+/4+ reactivity that rapidly deteriorate electrochemical performance. Doping and coating have been efficient strategies in delaying the onset of the damage, but they fail to overcome the degradation. There are, however, alternative strategies that directly counter the inherent degradation through micro- and nanostructural modifications of the Ni-rich NCM and NCA cathodes.

Although Li-ion batteries have emerged as the battery of choice for electric vehicles and large-scale smart grids, significant research efforts are devoted to identifying materials that offer higher energy density, longer cycle life, lower cost, and/or improved safety compared to those of conventional Li-ion batteries based on intercalation electrodes. By moving beyond intercalation chemistry, gravimetric capacities that are 2-5 times higher than that of conventional intercalation materials (e.g., LiCoO2 and graphite) can be achieved. The transition to higher-capacity electrode materials in commercial applications is complicated by several factors. This Review highlights the developments of electrode materials and characterization tools for rechargeable lithium-ion batteries, with a focus on the structural and electrochemical degradation mechanisms that plague these systems.

Imaging of lithium electrodepositions revealed that in the absence of a compressed porous separator, achievedviaa plastic washer, dendrite-free lithium was deposited from glyme solutions of 1 M LiNO3.

Nickel adds to the capacity of layered oxide cathodes of lithium-ion batteries but comprises their stability. We report a petal-grained Li[Ni0.89Co0.10Sb0.01]O2 cathode that is, nevertheless, stable. The stability originates from the ordering of the nanosized grains in a dense, flower-petal-like array, where the elongated and nearly parallel grains radiate from the center to the surface. The ordering of the grains prevents microcrack generation from abrupt lattice changes of the stressful H2-H3 phase transition. The tight packing of the nanograins is conserved upon cycling, preventing destructive seepage of the electrolytic solution into the particles. The half-cell, cycling between 2.7-4.3 V versus Li/Li+ at a 0.5 C rate retains 95.0% of its initial capacity of 220 mAh g-1 after 100 cycles. The full-cell, cycling with a graphite anode and between 3.0-4.2 V at a 1 C rate, retains 83.9% of its initial capacity after 1000 cycles.

The low cost, abundance, and high capacity of sodium and sulfur make them attractive battery materials. However, formation and migration of polysulfides in sulfur batteries causes rapid capacity fade, limiting battery cycle life. Most strategies to mitigate polysulfide shuttling address migration rather than formation and require complicated or expensive synthetic steps. Here, we introduce an amorphous, sulfur-rich molybdenum sulfide as a sulfur equivalent cathode that is simple and easy to make and shows excellent cycling performance with a specific capacity of 537 mAh g–1 at 50 mA g–1, retaining over 200 mAh g–1 at a rate of 1 A g–1.

We report a nanoparticulate lead oxide-carbon composite based rechargeable lithium battery anode. The composite is formed by pyrolyzing lead citrate, produced in the recycling of the lead paste of old lead acid batteries. The lead oxide nanoparticles of the composite are encased in, and supported by, flexible and conductive carbon. The encasing carbon buffers the expansion/shrinkage caused by lithiation/de-lithiation of lead, aiding in the maintenance of structural integrity and capacity retention throughout extensive cycling. 90% of the initial reversible gravimetric capacity of 385 mAh g(-1) and volumetric capacity of 622 mAh cm(-3) is retained after 400 cycles at a specific current density of 225 mA g(-1) (C/2). 94% of the initial reversible gravimetric capacity of 429 mAh g(-1) and volumetric capacity of 673 mAh cm(-3) is retained after 400 cycles at a specific current of 113 mA g(-1) (C/4). Employing techniques such as X-ray diffraction, thermal gravimetric analysis, cross-sectional scanning electron microscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy, we investigate how the structural composition of the PbO-C promotes its high capacity retention throughout prolonged galvanostatic cycling. (C) 2020 The Electrochemical Society ("ECS"). Published on behalf of ECS by IOP Publishing Limited.

Knowing that Alzheimer's disease (AD) nucleates in the entorhinal cortex (EC), samples of 12 EC specimens were probed for crystals by a protocol detecting fewer than 1/5000th of those present. Of the 61 crystals found, 31 were expected and 30 were novel. Twenty-one crystals of iron oxides and 10 atherosclerosis-associated calcium pyrophosphate dihydrate crystals were expected and found. The 30 unexpected crystals were NLRP3-inflammasome activating calcium oxalate dihydrate (12) and titanium dioxide (18). Their unusual distribution raises the possibility that some were of AD origination sites.

Forty years after the failed introduction of rechargeable lithium-metal batteries and 30 years after the successful commercialization of the lower capacity, graphite-anode-based lithium-ion battery by Sony, demand for higher energy density batteries is leading to reinvestigation of the problem of dendrite growth that makes the metallic lithium anodes unsafe and prevented commercialization to begin with. One strategy to mitigate dendrite growth is to deposit thin, tailored, corrosion-passivating coatings on the metallic lithium, instead of allowing the metal to spontaneously react with the organic electrolyte solution to form its passivating solid electrolyte interface (SEI). The challenge is to find and to deposit a coating that is electronically insulating yet allows uniform permeation of Li+ at a high cycling rate, such that Li-metal is electrodeposited uniformly on the nanoscale below the tailored coating. Recently, a number of studies have examined multicomponent films, taking advantage of the properties of two different materials, which can be tuned separately or chosen for their complementary properties. Use of these multicomponent coatings will likely enable future researchers to create rationally designed SEIs capable of effectively suppressing the growth of Li dendrites. This review discusses recent developments in micro- and nanoscale tailored coatings to meet that need.

Silicon (Si) films are promising anode materials in thin-film lithium batteries due to their high capacity of 3578 mAh g(-1), but the huge volume expansion of lithiated Li15Si4 and the unstable solid electrolyte interphase (SEI) preclude their practical application. Here lithium fluoride (LiF) coated Si nanocolumns are fabricated by glancing angle evaporation to address the obstacle. The LiF coating can elevate the lithium ion diffusion coefficient (LDC) of Si electrodes upon the alloying reaction and reduce the LDC upon the SEI formation. The composition evolution of the outer SEI layer in the LiF/Si electrodes is studied by ex situ X-ray photoelectron spectroscopy. The modified surface and mitigated volume expansion enable the LiF/Si nanocolumns to exhibit superior rate capability and higher cycling stability compared with the pristine Si nanocolumns. This work demonstrates the positive effect of LiF coating for reducing the polarization and forming a robust SEI film on Si anodes.

To address the growing demand for both energy density and cycling stability, a layered nanorod gradient (NRG) Li[Ni0.81Co0.06Mn.0.13]O2 cathode was synthesized with a high Ni-content bulk and a radially columnar nano-rod comprised surface and benchmarked against the widely used constant concentration (CC) Li[Ni0.82Co0.14Al0.04]O2. The NRG cathode delivered a discharge capacity of 225 mAh g-1, equivalent to ~ 830 Wh kg-1 at the cathode level, with 91% capacity retention in half-cells after 100 cycles (210 mAh g-1 and 79 % for CC cathode) and 88% capacity retention in full-cells after 1000 cycles (56 % for CC cathode). Through a combination of in-situ and time-resolved X-ray diffraction (XRD), cross-section scanning electron microscopy imaging (SEM), and high-resolution transmission electron microscopy (HR-TEM), we confirm that the exceptional electrochemical performance of the NRG material, both in energy density and cycling performance, is attributed to its radially columnar concentration graded nano-rods at the surface. These nano-rods function as a buffer to diminish abrupt stress from the high Ni-content bulk during the H2 → H3 phase transition by suppressing crack propagation to preserve particle coherency, enabling reversibility of the cathode particle. This is important because electrolyte infiltration into the reactive Ni-rich bulk and subsequent formation of the electrically insulating rocksalt nano-structure (NiO) along the cracks are prevented, thereby minimizing impedance increase during long-term cycling. Furthermore, the nano-rods also enhance the thermal stability by delaying the layered to rocksalt phase transition on the surface through an increased concentration of Mn on the exterior.

Layered nickel-rich cathode particles for lithium-ion batteries can fail and severely limit the cycling performance via cracking from anisotropic strain which allows electrolyte penetration and the formation of electrically insulating material and a decreased capacity. Self-assembled layered nanorod gradient (NRG) Li[Ni0.81Co0.06Mn0.13]O-2 cathode particles cycle more stably with improved performance compared to its constant concentration counterpart. NRG cathode material was synthesized with a Ni-rich bulk (for higher lithium storage) and a radially columnar nanorod comprised surface and benchmarked against the widely used constant concentration (CC) LI[Ni0.82Co0.14Al0.04]O-2 cathode and in both half- and full-cells. Through a combination of in situ and time-resolved X-ray diffraction (XRD), cross-section scanning electron microscopy imaging (SEM), and high-resolution transmission electron microscopy (HR-TEM), we confirm that the enhanced durability of the NRG material is attributed to its radially columnar concentration graded nanorods at the surface. These nanorods function as a buffer to diminish abrupt stress from the high Ni-content bulk during the H-2 -> H-3 phase transition by suppressing crack propagation to preserve particle coherency, enabling reversibility of the cathode particle. Notably, we show that electrolyte infiltration into the reactive Ni-rich bulk and subsequent formation of the electrically insulating rock-salt nanostructure (NiO) along the cracks are prevented, thereby minimizing impedance increase during long-term cycling. Furthermore, the increased Mn concentration at the outer surface of the nanorods also enhances the thermal stability by delaying the layered to rock-salt phase transition on the surface.

Increasingly modern society relies on the use of electrical energy for a large portion of their everyday tasks. Many of these tasks require the use of portable energy sources. Currently, lithium ion batteries (LIBsdominate the portable energy storage market.1 Almost exclusively, these LIBs utilize a graphite anode, due to graphite’s long lifetime and high capacity retention.2 This project aims to develop a cheap, high capacity alternative to graphite via a SnO2-C based anode material. Tin oxide is an effective candidate for an anode due to its low price and tin’s high abundance. Tin oxide anodes have been studied previously, motivated by its high theoretical capacity (1494 mAh/g).2 However, tin oxide is not currently used in commercial cells because of the large volumetric expansion during lithiation (up to 300%) leading to fracturing of the particle.3 In turn, the fracturing can cause the particle to electrically disconnect from the current collector and lose effectiveness. We believe these issues can be counteracted through the employment of a carbon backbone. The presence of semi-crystalline carbon could act as a flexible component to resist the expansion of the tin atoms, preventing the degradation and fracturing of the particle caused by expansion.4 Previous studies have utilized SnO2-C composites to form anodic materials with high capacities and high columbic efficiencies, but tend to display sub-par cycling lifetimes.4,5 However, these studies did not examine how the effects of doping and extent of crystallinity can influence the overall electrochemical performance. The analysis of these factors could lead to the production of a higher capacity and more economically viable alternative to graphitic anodes. The goal of this research is to develop SnO2-C anodes and investigate the storage and transport of Li within the electrodes to improve the efficiency and cost of LIBs. Due to their higher tap densities and industrial viability, micron-sized anode materials were generated for this study. Ditin citrate was chosen as a tin containing pyrolysis precursor because of its novelty and inexpensive synthesis.6 Precursors such as sucrose and citric acid were added to pyrolysis mixture to form a semi-graphitized framework around the tin-oxide particles. XRD, Raman, XPS, and SEM/EDX data suggest the uniform coating of a semi-graphitized coating around the SnO2 particles. Preliminary data suggest this process has led to the formation of a high specific capacity (750 mA/g) anode material with satisfactory cycling performance. The future pursuits of this study is to optimize the cycling performance and determine the effects of using dopants such as nitrogen and sulfur. 1. Tenan, M. S.; LaFiandra, M. E.; Ortega, S. V. The Effect of Soldier Marching, Rucksack Load, and Heart Rate on Marksmanship. Hum. Factors 2017, 59 (2), 259–267. https://doi.org/10.1177/0018720816671604 2. Thampan, T.; Shah, D.; Cook, C.; Novoa, J.; Shah, S. Development and Evaluation of Portable and Wearable Fuel Cells for Soldier Use. J. Power Sources 2014, 259, 276–281. https://doi.org/10.1016/j.jpowsour.2014.02.099 3. Zhu, X.; Zhu, Y.; Murali, S.; Stoller, M. D.; Ruoff, R. S. Reduced Graphene Oxide/Tin Oxide Composite as an Enhanced Anode Material for Lithium Ion Batteries Prepared by Homogenous Coprecipitation. J. Power Sources 2011, 196 (15), 6473–6477. https://www.sciencedirect.com/science/article/pii/S0378775311008020 4. Winter, M.; Besenhard, J. O. Electrochemical Lithiation of Tin and Tin-Based Intermetallics and Composites. Electrochim. Acta 1999, 45 (1), 31–50. https://www.sciencedirect.com/science/article/pii/S0013468699001917 5. Paek, S.-M.; Yoo, E.; Honma, I. Enhanced Cyclic Performance and Lithium Storage Capacity of SnO2/Graphene Nanoporous Electrodes with Three-Dimensionally Delaminated Flexible Structure. Nano Lett. 2009, 9 (1), 72–75. https://pubs.acs.org/doi/10.1021/nl802484w 6. Derrien, G.; Hassoun, J.; Panero, S.; Scrosati, B. Nanostructured Sn–C Composite as an Advanced Anode Material in High-Performance Lithium-Ion Batteries. Adv. Mater. 2007,19 (17), 2336–2340. https://onlinelibrary.wiley.com/doi/abs/10.1002/adma.200700748 Figure 1