"Winning the Champions League and at least a title with the national side," the Manchester City midfielder wrote on Instagram when asked by a fan about his dreams for the future.
Gundogan, 27, joins Toni Kroos, 28, and Sami Khedira, 31, in declaring a desire to keep playing for the national team and make amends for Germany's disastrous early World Cup exit last month.
The Premier League stars posed for pictures with the Turkish leader in May, ahead of his successful re-election campaign, and Gundogan presented Erdogan with a Manchester City signed "to my president".
The meeting raised questions about the pair's loyalty to Germany and sparked fierce debate on the eve of the World Cup about integration in Germany.


text:
Following recent ESA announcements, what will be the future of Loot boxes?
Oscar Rojas
Just a few days ago, the Entertainment Software Association (ESA) announced that Microsoft, Nintendo, and Sony, the main online gaming platforms, will implement new policies that will allow players to know the odds of loot boxes in their games.
Michael Warnecke, Senior Advisor to ESA commented: "I am pleased to announce that this morning Microsoft, Nintendo and Sony have indicated to ESA their commitment to new platform policies regarding the use of pay-as-you-go Loot boxes in games developed for their platforms".
© Microsoft, Nintendo, Sony | Esports.net
This new policy will be implemented from 2020 and other companies such as Activision, Blizzard, Bandai, Namco, Bethesda, Electronic Arts, and Ubisoft, among others, have also agreed to implement a similar disclosure policy by the end of next year.
About this new control element, Sony Interactive Entertainment executives stated "We support the industry's efforts to disclose the likelihood of obtaining random virtual items, known as booty boxes. And we are committed to providing consumers with this information for all the games we produce and publish".
What is the problem with Loot boxes?
Loot boxes are digital products that offer a combination of random game rewards at a fixed price.
This way, the attraction of buying them is getting "rare" outfits or weapons for your character, ones you'll never get in the store and for which many players are willing to pay good money.
Nevertheless, there are divided opinions about these reward mechanisms.
About this, Marcus Carter, professor of digital cultures at the University of Sydney, explains that "Reviews conclude that loot boxes do not meet the existing game definition (…) that does not mean that players are not playing, but that looting boxes are outside the [legal] definitions that exist in most cases".
While in most countries there is not much concern about the issue, the United States Senator Josh Hawley attempts to prohibit minors from accessing transaction games at all, and other countries such as Belgium, have completely prohibited looting boxes implementation.
To sum up, the issue is that reward boxes are attractive due to the possibility of obtaining super rare items, although the loot box odds for a rare item can be as low as 0.01%, and there is great concern about how to protect children from a system so similar to gambling.
© Blizzard Entertainment
Is this the doom of random rewards?
The industry is unlikely to give up easily.
While it is true that some brands, such as the Rocket League, have abandoned this system, the truth is that it still reports millionaire profits for the sector, especially in popular games such as "NBA 2K" and "Fortnite".
On the other hand, some companies had to compromise in this field, such as the example of Valve who deactivated the booty boxes on the Counterstrike Global Offensive and Dota 2 platforms under command of the Dutch government during 2018.
This happened after there were complaints about downloadable content being more expensive than the actual game, which for many was inadmissible.
Others defend Looting Boxes implementation, claiming that gambling does not offer any reward, while these reward mechanisms always give the player something, even if it is not exactly a strange article in the vast majority of cases.
Even so, it seems that ESA has everything in its favor to regulate the loot box odds, as Epic Games (creators of Fortnite) has also shown collaboration regarding random pay rewards.
In fact, in January 2019 they made the flames of "Fortnite: Save the World" show the random contents they brought before paying for them.
Finally, the future does not look very bright for companies in the sector in their effort to keep surprise boxes at the forefront.
In the United States and Europe, there is serious talk about the subject –everyone wants to protect their children-, but economic interests have prevented loot boxes from being banned altogether.
We will have to wait until the end of 2020 to see whether this ESA regulation has the desired effect, in the meanwhile, you can still try to get some super rare content from loot boxes in most games.
Read all our Esports news and stay informed about everything that happens in the competitive gaming world.
Loot box Scandal Redoubt – will loot boxes be banned?
Spending money on microtransactions is a touchy subject. Fans opinions are split. While most gamers can agree that pay toMore
Our interview with League of Legends Cosplayer Mowky
In the world of cosplay, few are as accomplished as Mowky. Whether it's creating your own costumes, participating in competitions,More
NA LCS: Breaking down all the trade drama and roster rumors for every team in 2018
Team SoloMid (TSM) After another miserable group stage exit at Worlds, it was clear something had to change for NA'sMore

redpajama_set_name: RedPajamaCommonCrawl


The neighborhood surrounding the Shaikh Hamad Mosque is being redeveloped. One of the goals of this redevelopment is to return the existing buildings to their original footprint. The project by SeARCH aims to strengthen the ongoing revitalization of this neighborhood by offering a public library building. This new cultural space complements existing commercial facilities and is open to all members of society.
Located in the historical centre of Muharraq, the Khalifeyah Library was one of the first public libraries in Bahrain. The area surrounding the library suffered from a redevelopment in the 1980s, which considerably reshaped the urban silhouette of the area and destroyed its original scale. SeARCH has designed a library that subtly embeds itself in the existing neighborhood, but at the same time has a strong architectural presence that allows it to become a public focal point of the neighborhood. The boundary of the lower floor is shaped by the diagonal line from the adjacent building's footprint while the cantilevering volume of the two top floors take up again the original footprint of the library. This way the public space is kept intact and at the same time it creates a covered entrance for the library.
One of the main problems is regulating the indoor climate and minimizing direct sunlight. By overlaying the shadows created by the typical shapes of the cantilevers, an interesting pattern emerges which is used as a basis for the design. A diagonal grid of louvers is projected on the facade. Rather than being defined by structural logic or repetitive mathematic of traditional Arabic shapes, this pattern is used to regulate incoming sunlight by varying the density of the grid following the shading patterns. This leads to an abstract sculptural facade that changes its appearance under different viewing angles. Sometimes it seems solid and closed, but if passing by it opens up to the visitor.
The Khalifeyah Library houses a reading room, a research centre, an internet lab and office spaces, which are all open to the public. The cultural and public program focuses on the youth living in the heart of Muharaq.


At Cork & Fork, we are dedicated to supporting our local farmers by investing in fresh, Orlando-grown ingredients.
Minimum purchase of $30 at restaurant. Not valid for Thursday, Friday and Saturday. Not valid for alcohol. Special Term(s): Only one certificate per visit.
Sign up today to receive special offers for Cork & Fork American Grill and other restaurants in your area!


text:
Q: ASP.NET Website where to save generated files I have a ASP.Net website and in some cases it's generating .pdf-files and .csv files for users to download.
Now my question: What is the default directory for saving that files on the webserver? Is there any ASP.NET Folder like App_... or something like that?
What can you recommend?

A: If you don't want to reuse the files, stream the files directly without saving it to disk.
If you save it to disk you have to ask yourself if the content of the file is to be available to all users or if it's a bad idea that other users can access the files. If it's a bad idea, the folder you put the files in should be made unavailable to the users by setting access rights correspondingly. You can either do this by putting the folder outside of the web site directory or by setting security settings in the file system or on the web server.
You can basically put the files in any folder that is made writable for the user writing the file (typically the ASP.NET App Pool user). IIRC the App_data folder is writable by default for the ASP.NET user, so that could be a candidate.

A: You can create your proper folder for this need
Here list of specific Folder (But you don't need):
App_GlobalResources,
App_LocalResources,
App_Resources
App_Themes
App_WebReferences)
App_Code
App_Data
App_Browsers

Here MSDN link about project structure
Link : http://msdn.microsoft.com/en-us/library/ex526337%28v=vs.100%29.aspx

A: It's really up to you! I would recommend you put them in a sub folder of your solution so that they are self contained and you can easily control security without worrying about folders further down the tree.

A: Folder is anything you tell it to be.  If you have low volume you could just stream the files from memory so they're not stored on the server.

A: It is also important that you consider whether you are going to have more than one web server, and have servers in a cluster. To be ready for such a case, it is better not to keep the files under the web application folder, and not to access them relatively to the application path,  but keep the files in a separate folder that you could easily expose (there will still be security issues) as a network path.

redpajama_set_name: RedPajamaStackExchange


text:
Malimal: "Sept.Ember" – more than just a collection of songs
Malimal is Brooklyn-born emcee that learned his love for hip hop in the South. In the late 2000's he joined the BlazeUp Clique who put out the small hit "Teddy Overload". Growing mic skills and restlessness pushed Malimal to go for his solo career. The self-proclaimed 'Black Nerd Militant' began to perform all over NYC. With a solid playlist and a focused vision, Malimal released his debut mixtape "Sept.Ember" which featured the smashes, "Fresh One in The Building" , "Love Vs Money (The Hypocrite Dream)", and "Anytime".
Malimal loves both a simple hook and an advanced song structure. The oscillations of his songwriting are noticeable, from the confidence of the choruses to the millisecond contortions in his voice. Songs like "Anytime (Prod. Santana2k12)" is Malimal at his nonchalant best.
"Cigarette Ashes (Feat. The Star Roddy Rod) (Prod. By Sean Junior)" sees him ply all the gravelly aggression in his flow. All told, from his flows to his punchlines, he sounds totally well-rounded.
"All Day (Freestyle)" and "Fresh One In The Building (Prod. by Killing Spree)" showcases his best rapping skills, spitting lines so fast, internally rhyming and flowing faster than your ear can keep up, on par with any other emcee out there. It's brilliant, really.
Malimal makes you stick it out till the end on "Outside (Prod. By Charles Hamilton)", through all his hardcore imagery, anti-hater thinking and weird sampled production, which simply says "Fuck you. You can't stop me!"
In between, Malimal is capable of laying down some very smooth and soulful bangers like "Love Vs. Money (The Hypocrite's Dream)(Prod. By Sean J)" and "Exhibit M (Heaven's Gate)". Musically, the mixtape is a rich, cinematic arc that straddles a variety of beat styles and often finds itself a couple of steps removed from the overused deliveries by some contemporary rappers.
Over alternately lush, and even lusher production, and in collaboration with a number of different producers, Malimal sets a hectic and urgent tone to proceedings apart from the handful of more laid-back tracks.
All throughout "Sept.Ember", the raps are self-conscious; not pandering. They're overt; not obnoxious. They're cheeky; not annoying. As the mixtape forges ahead, more pieces of the puzzle are revealed, the extent to which "Sept.Ember" is more than just a collection of songs becomes increasingly apparent.
The screenplay, which is embedded into the songs makes everything a little clearer: Our society is fleeting, Malimal, like the rest of us, is so keenly aware that it's happening—he's just trying to hold on while everything around is collapsing – decaying relationships, crumbling cultures, and waning personal values are tackled head-on here. You should shut the fuck up and just listen to him!
OFFICIAL LINKS: REVERBNATION – SOUNDCLOUD – INSTAGRAM – TWITTER – FACEBOOK – YOUTUBE
Tagged: Brooklyn, hiphop, Malimal, Mixtape, Rap, Sept.Ember
Previous Post: Michael M Jeni: "Bye Bye" is overtly present both in mood and expression!
Next Post: Paul Barrere & Roger Cole: "Grain Of Sand" – only scratching the surface!


text:
AboutNewsResearchPublicationsTeam
NANOTECH LAB | YUSHIN GROUP
The Yushin Group leads six main areas of interest for energy storage: conversion electrodes, selective metal dealloying, aqueous-ion storage devices, nanocomposite materials, multifunctional electrodes, and solid-state electrolytes/batteries. For a complete listing of publications, please visit Google Scholar.
Battery Materials for Low-Cost Electric Transportation
Materials Today
K Turcheniuk, D Bondarev, G Amatucci, G Yushin
This review considers key parameters for affordable Li-ion battery (LIB)-powered electric transportation, such as mineral abundance for active material synthesis, raw materials' processing cost, cell performance characteristics, cell energy density, and the cost of cell manufacturing. It analyzes the scarcity of cobalt (Co) and nickel (Ni) resouces available for intercalation-type LIB cathode materials, estimates the demands for these metals by transportation and other industries, and discusses risk factors for their price increase within the next two decades. It also further contrasts perfromance and estimates costs of LIBs based on intercalation materials, such as lithium nicket cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), and other oxide-based cathodes and carbonaceous anodes, with those of LIBs based on conversion-type cathodes and silicon (Si)-based anodes.
Scalable, safe, high-rate supercapacitor separators based on the Al2O3 nanowire Polyvinyl butyral nonwoven membranes
Nano Energy
Mengting Liu, Kostiantyn Turcheniuk, Wenbin Fu, Yang Yang, Michael Liu, Gleb Yushin
High-performance supercapacitor nonwoven separators based on polyvinyl butyral (PVB) with uniformly distributed Al2O3 nanowires (NW) fillers (up to 40 wt %) have been developed using a low-cost casting (stir-pour-dry) technique utilized under ambient conditions for the first time. These novel nonwoven separators with highly porous network demonstrated tensile strength of >30 MPa, extremely high electrolyte absorption (>200 wt. %), low-to-no swelling behavior and stable electrochemical performance, substantially exceeding that of analogous cells with commercial separators. Thermal properties of the produced separators were also exceptional with >15 MPa of ultimate strength, high flexibility and minimal thermal shrinkage maintained at temperatures as high as 200 °C. The one-dimensional (1D) ceramic nanofillers improved PVB's mechanical and thermal properties and enabled formation of highly porous membranes with self-organized nanopores and high ionic conductivity of up to 13.5 mS/cm in 1 M Na2SO4 aqueous electrolyte. This simple and innovative method and separator design is attractive for manufacturing of high-strength, low-cost and flexible separators and suitable for various polymers-ceramic nonwoven compositions for fast charging, high-power and safe electrochemical capacitors, hybrid devices and batteries.
Understanding Li‐Ion Dynamics in Lithium Hydroxychloride (Li2OHCl) Solid State Electrolyte via Addressing the Role of Protons
Advanced Energy Materials
Ah‐Young Song, Kostiantyn Turcheniuk, Johannes Leisen, Yiran Xiao, Lamartine Meda, Oleg Borodin, Gleb Yushin
Low‐melting‐point solid‐state electrolytes (SSE) are critically important for low‐cost manufacturing of all‐solid‐state batteries. Lithium hydroxychloride (Li2OHCl) is a promising material within the SSE domain due to its low melting point (mp < 300 °C), cheap ingredients (Li, H, O, and Cl), and rapid synthesis. Another unique feature of this compound is the presence of Li vacancies and rotating hydroxyl groups which promote Li‐ion diffusion, yet the role of the protons in the ion transport remains poorly understood. To examine lithium and proton dynamics, a set of solid‐state NMR experiments are conducted, such as magic‐angle spinning 7Li NMR, static 7Li and 1H NMR, and spin‐lattice T1(7Li)/T1(1H) relaxation experiments. It is determined that only Li+ contributes to long‐range ion transport, while H+ dynamics is constrained to an incomplete isotropic rotation of the OH group. The results uncover detailed mechanistic understanding of the ion transport in Li2OHCl. It is shown that two distinct phases of ionic motions appear at low and elevated temperatures, and that the rotation of the OH group controls Li+ and H+ dynamics in both phases. The model based on the NMR experiments is fully consistent with crystallographic information, ionic conductivity measurements, and Born–Oppenheimer molecular dynamic simulations.
Conversion of Mg‐Li Bimetallic Alloys to Magnesium Alkoxide and Magnesium Oxide Ceramic Nanowires
Angewandte Chemie International Edition
Shunrui Luo, Kostiantyn Turcheniuk, Ah‐Young Song, Aashray Narla, Doyoub Kim, Alexandre Magasinsky, Gleb Yushin
Technologically important composites with enhanced thermal and mechanical properties rely on the reinforcement by the high specific strength ceramic nanofibers or nanowires (NWs) with high aspect ratios. However, conventional synthesis routes to produce such ceramic NWs have prohibitively high cost. Now, direct transformation of bulk Mg‐Li alloys into Mg alkoxide NWs is demonstrated without the use of catalysts, templates, expensive or toxic chemicals, or any external stimuli. This mechanism proceeds through the minimization of strain energy at the boundary of phase transformation front leading to the formation of ultra‐long NWs with tunable dimensions. Such alkoxide NWs can be easily converted in air into ceramic MgO NWs with similar dimensions. The impact of the alloy grain size and Li content, synthesis temperature, inductive and steric effects of alkoxide groups on the diameter, length, composition, ductility, and oxidation of the produced NWs is discussed.
A nanoconfined iron (iii) fluoride cathode in a NaDFOB electrolyte: towards high-performance sodium-ion batteries
Zifei Sun, Wenbin Fu, Michael Z Liu, Peilin Lu, Enbo Zhao, Alexandre Magasinski, Mengting Liu, Shunrui Luo, Jesse McDaniel, Gleb Yushin
Iron(III) fluoride (FeF3) is considered a potential cathode for sodium-ion batteries (SIBs) due to its high capacity and low cost. However, particle pulverization upon cycling generally results in rapid degradation of its structure and capacity. Here, we introduce a free-standing nanoconfined FeF3 cathode and a novel electrolyte salt, sodium-difluoro(oxalato)borate (NaDFOB), for SIBs. The assembled cells show a high discharge capacity up to ∼230 mA h g−1 at a rate of 20 mA g−1 (∼200 mA h g−1 at 100 mA g−1) and a capacity retention up to ∼70% after 100 cycles, which represent the best results reported for FeF3 in Na-ion electrolytes. The achieved high performance can be attributed to the synergic protection provided by the nanoconfined FeF3 electrode and the NaDFOB electrolyte. Post-mortem analysis and quantum mechanics show that DFOB anions facilitated the formation of a thin cathode electrolyte interphase (CEI) on the surface of FeF3-carbon nanofibers (CNFs) via oligomerization.
Anatase TiO2 Confined in Carbon Nanopores for High‐Energy Li‐Ion Hybrid Supercapacitors Operating at High Rates and Subzero Temperatures
Wenbin Fu, Enbo Zhao, Ruiying Ma, Zifei Sun, Yang Yang, Marta Sevilla, Antonio B Fuertes, Alexandre Magasinski, Gleb Yushin
Li‐ion hybrid supercapacitors (Li‐HSCs) hold great promise in future electrical energy storage due to their relatively high power and energy density. However, a major challenge lies in the slow kinetics of Li‐ion intercalation/extraction within metal‐oxide electrodes. Here, it is shown that ultrafast charge storage is realized by confining anatase TiO2 nanoparticles in carbon nanopores to enable a high‐rate anode for Li‐HSCs. The porous carbon with interconnected pore walls and open channels not only works as a conductive host to protect TiO2 from structural degradation but also provides fast pathways for ion/electron transport. As a result, the assembled cells exhibit remarkable rate capabilities with a specific capacity of ≈140 mAh g−1 at a slow charge and ≈60 mAh g−1 at a 3.5 s fast charge. While the charge/discharge process can be completed as fast as that of state‐of‐the‐art electrical double‐layer capacitors (EDLCs), the produced nanocomposites show three to seven times higher volumetric capacitance than activated carbons used in commercial EDLCs with acetonitrile‐based electrolytes. Equally important for some applications in cold climates or the space, the Li‐HSCs can operate at subzero temperatures as low as −40 °C, which is likely only limited by thermal properties of the acetonitrile (melting point of −45 °C).
Cycle stability of conversion-type iron fluoride lithium battery cathode at elevated temperatures in polymer electrolyte composites
Qiao Huang, Kostiantyn Turcheniuk, Xiaolei Ren, Alexandre Magasinski, Ah-Young Song, Yiran Xiao, Doyoub Kim, Gleb Yushin
Metal fluoride conversion cathodes offer a pathway towards developing lower-cost Li-ion batteries. Unfortunately, such cathodes suffer from extremely poor performance at elevated temperatures, which may prevent their use in large-scale energy storage applications. Here we report that replacing commonly used organic electrolytes with solid polymer electrolytes may overcome this hurdle. We demonstrate long-cycle stability for over 300 cycles at 50 °C attained in high-capacity (>450 mAh g−1) FeF2 cathodes. The absence of liquid solvents reduced electrolyte decomposition, while mechanical properties of the solid polymer electrolyte enhanced cathode structural stability. Our findings suggest that the formation of an elastic, thin and homogeneous cathode electrolyte interphase layer on active particles is a key for stable performance. The successful operation of metal fluorides at elevated temperatures opens a new avenue for their practical applications and future successful commercialization.
Flexible Nanofiber‐Reinforced Solid Polymer Lithium‐Ion Battery
Xiaolei Ren, Kostiantyn Turcheniuk, Fujia Wang, Ah-Young Song, Qiao Huang, Yiran Xiao, Kyounghwa Kim, Gleb Yushin
Herein, the new concept of an all‐nanofiber‐reinforced multifunctional battery is developed and demonstrated. The conventional liquid electrolyte, polymer separator, and powder‐based cathode are replaced by a nanofiber‐enhanced solid polymer electrolyte and carbon nanotube (CNT) fabric conformably coated with an active cathode material. Chemical vapor deposition (CVD) of iron phosphate (FePO4) is selected for the cathode fabrication in this first demonstration. Oxide nanofibers in the polymer electrolyte greatly enhance the electrochemical stability of the electrolyte and resistance to Li dendrite shortening at higher current densities. In addition, the oxide nanofibers increase the polymer mechanical strength and strain by 20–30%. The stand‐alone CNT@FePO4 cathode infiltrated with the polymer electrolyte exhibits more than five times higher modulus of toughness than that of the Al current collector. The as‐produced structural battery based on these fabricated components exhibits exceptional stability with no signs of performance decay at 50 °C, thus demonstrating great promise of the new architecture for a broad range of multifunctional and flexible battery applications.
Insights into the Effects of Electrolyte Composition on the Performance and Stability of FeF2 Conversion‐Type Cathodes
Qiao Huang, Kostiantyn Turcheniuk, Xiaolei Ren, Alexandre Magasinski, Daniel Gordon, Nasr Bensalah, Gleb Yushin
As an alternative to commercial Ni‐ and Co‐based intercalation‐type cathode materials, conversion‐type metal fluoride (MFx) cathodes are attracting more interest due to their promises to increase cell‐level energy density when coupled with lithium (Li) or silicon (Si)‐based anodes. Among metal fluorides, iron fluorides (FeF2 and FeF3) are regarded as some of the most promising candidates due to their high capacity, moderately high potential and the very low cost of Fe. In this study, the impacts of electrolyte composition on the performance and stability of nanostructured FeF2 cathodes are systematically investigated. Dramatic impacts of Li salt composition, Li salt concentration, solvent composition, and cycling potential range on the cathode's most critical performance parameters—stability, capacity, rate, and voltage hysteresis are discovered. In contrast to previous beliefs, it is observed that even if the Fe2+ cation dissolution could be avoided, the dissolution of F− anions may still negatively affect cathode performance. Formation of the more favorable cathode solid electrolyte interface (CEI) is found to minimize both processes.
Fading Mechanisms and Voltage Hysteresis in FeF2–NiF2 Solid Solution Cathodes for Lithium and Lithium‐Ion Batteries
Qiao Huang, Travis P Pollard, Xiaolei Ren, Doyoub Kim, Alexandre Magasinski, Oleg Borodin, Gleb Yushin
The rapid development of ultrahigh‐capacity alloying or conversion‐type anodes in rechargeable lithium (Li)‐ion batteries calls for matching cathodes for next‐generation energy storage devices. The high volumetric and gravimetric capacities, low cost, and abundance of iron (Fe) make conversion‐type iron fluoride (FeF2 and FeF3)‐based cathodes extremely promising candidates for high specific energy cells. Here, the substantial boost in the capacity of FeF2 achieved with the addition of NiF2 is reported. A systematic study of a series of FeF2–NiF2 solid solution cathodes with precisely controlled morphology and composition reveals that the presence of Ni may undesirably accelerate capacity fading. Using a powerful combination of state‐of‐the‐art analytical techniques in combination with the density functional theory calculations, fundamental mechanisms responsible for such a behavior are uncovered. The unique insights reported in this study highlight the importance of careful selection of metals and electrolytes for optimizing electrochemical properties of metal fluoride cathodes.
Aluminum oxide nanowires as safe and effective adjuvants for next-generation vaccines
R Bilyy, S Paryzhak, K Turcheniuk, T Dumych, A Barras, R Boukherroub, F Wang, G Yushin, S Szunerits
Improving efficiency of an adjuvant, material that enhances the body's immune response to an antigen, has become vital for the development of safer, cheaper, and more effective next-generation vaccines. Commercial vaccines typically use aluminum salt-based adjuvant particles, most commonly aluminum oxyhydroxide (AlOOH) and aluminum hydroxide (Al(OH)3) based, often referred to as "alum". Despite their broad use, their adjuvant properties are rather moderate. This is even worse in the case of aluminum oxide (Al2O3)-based adjuvant. While being more robust and less cytotoxic, Al2O3 is a significantly less effective adjuvant than above-mentioned Al compounds and is consequently not commonly used. Here, we report on the remarkably enhanced adjuvant properties of Al2O3 when produced in the form of nanowires (NWs). Based on recent advances in understanding neutrophil activation by inert nanoscaffolds, we have created ultra-long Al2O3 NWs with a high aspect ratio of ∼1000. These NWs showed strong humoral immune response with no damaging effect on the microvasculature. Since only the change of shape of Al adjuvants is responsible for the excellent adjuvant properties, our finding holds great promise for rapid implementation as safer and more effective adjuvant alternative for human vaccines. The mechanism behind human blood-derived neutrophil activation with Al2O3 NWs was found to be sequestering of Al2O3 NWs by neutrophils via formation of neutrophil extracellular traps (NETs).
Robust and Flexible Micropatterned Electrodes and Micro-Supercapacitors in Graphene–Silk Biopapers
R Ma, D Gordon, G Yushin, VV Tsukruk
Robust and flexible micro‐supercapacitors based upon a graphene oxide–silk layered bionanocomposite is reported. Generation of micropatterned electrodes with sub‐micrometer spatial resolution is accomplished using a novel resist‐stenciling technique, enabling the transfer of complex microcircuit designs to a graphene oxide–silk layered substrate as chemically reduced features microfeatures across wafer‐length scales. Resist‐stenciling can produce micropatterned reduction features with over ten times the feature density compared to techniques such as laser‐scribing or screen printing. As a proof‐of‐concept, resist‐stenciling is used to fabricate the first 2D micro‐supercapacitors integrated into a layered graphene bionanocomposite. These demonstrate a specific capacitance of ≈128 F g−1, good capacitance retention under charge cycling (87.5% after 2000 cycles), and repeated mechanical bending without failure. Resist‐stenciling leverages tools currently in use by the microelectronics industry to enable the scalable, high‐resolution conversion of layered nanocomposites into microelectronic circuit, storage, and sensing elements.
Morphology and Phase Changes in Iron Anodes Affecting their Capacity and Stability in Rechargeable Alkaline Batteries
ACS Energy Letters
DC Lee, D Lei, G Yushin
Rechargeable alkaline batteries may become attractive nonflammable alternatives to lithium-ion (Li-ion) batteries for applications where achieving the highest energy density is less critical than safety, environmental friendliness, and low cost of energy storage. The broad abundance and low price of iron (Fe) make it attractive as a rechargeable anode material for aqueous batteries. Through cyclic voltammetry and post-mortem analysis, we revealed four distinct stages of Fe anode evolution: development, retention, fading, and failure, where each stage is associated with very specific changes in the morphology and phase of Fe anodes. We observed the Fe particle fragmentation resulted in the capacity increase during the initial cycles of charge−discharge. Most importantly, we discovered the irreversible formation of maghemite (γ-Fe2O3) with low reactivity is responsible for the eventual Fe anode capacity fading. This unexpected discovery changes the paradigm on possible routes to stabilize Fe anodes and contributes to future development of low-cost alkaline cells.
Mechanisms of Transformation of Bulk Aluminum–Lithium Alloys to Aluminum Metal–Organic Nanowires
F Wang, K Turcheniuk, B Wang, AY Song, X Ren, A Vallamattam, A Park, K Hanley, T Zhu, G Yushin
Fabrication and applications of lightweight, high load-bearing, thermally stable composite materials would benefit greatly from leveraging the high mechanical strength of ceramic nanowires (NWs) over conventional particles or micrometer-scale fibers. However, conventional synthesis routes to produce NWs are rather expensive. Recently we discovered a novel method to directly convert certain bulk bimetallic alloys to metal–organic NWs at ambient temperature and pressure. This method was demonstrated by a facile transformation of polycrystalline aluminum–lithium (AlLi) alloy particles to aluminum alkoxide NWs, which can be further transformed to mechanically robust aluminum oxide (Al2O3) NWs. However, the transformation mechanisms have not been clearly understood. Here, we conducted advanced materials characterization (via electron microscopy and nuclear magnetic resonance spectroscopies) and chemo-mechanical modeling to elucidate key physical and chemical mechanisms responsible for NWs formation. We further demonstrated that the content of Li metal in the AlLi alloy could be reduced to about 4 wt % without compromising the success of the NWs synthesis. This new mechanistic understanding may open new avenues for large-scale, low-cost manufacturing of NWs and nanofibers for a broad range of composites and flexible ceramic membranes.
Iron oxide nanoconfined in carbon nanopores as high capacity anode for rechargeable alkaline batteries
D Lei, DC Lee, E Zhao, A Magasinski, HR Jung, G Berdichevsky, D Steingart, G Yushin
Rechargeable aqueous batteries are attracting renewed attention due to flammability and high cost of lithium-ion cells. Extremely low cost, very high abundance and eco-friendliness of iron (Fe) anodes make them parti-cularly attractive for aqueous chemistries. Unfortunately, traditional Fe anodes suffer from low capacity utili-zation, the need for formation pre-cycling and dissolution of active material when fully discharged. Knownmethods for synthesis of nanocomposite Fe anode are expensive and offer poor control over material propertiesand uniformity. We report on a novel low-cost synthesis route to produce nanocomposites with crystalline FeOxnanoparticles very uniformly distributed within individual nanoporous carbon particles. The conductivity en-hancement and a very small size of FeOxparticles (< 5 nm) effectively enhance the discharge capacity of Feanodes up to 600 mAh g−1. In contrast to graphene-FeOxor carbon nanotube-FeOx, the large size of the pro-duced nanocomposite particles allows them to be processed into electrodes the same way as supercapacitorelectrodes are mass-produced by industry. The nanoconfinement suppresses side reactions, such as nanoFedissolution and hydrogen evolution, resulting in capacity retention of up to ~85% after 200 cycles. When used incombination with novel In-based additives, reported anodes uniquely exhibited a single high-voltage dischargeprofile in full cells, which improves energy density of cells and simplifies battery management system
Lithium–Iron (III) Fluoride Battery with Double Surface Protection
E Zhao, O Borodin, X Gao, D Lei, Y Xiao, X Ren, W Fu, A Magasinski, K Turcheniuk, G Yushin
Lithium–metal fluoride batteries promise significantly higher energy density than the state-of-the-art lithium-ion batteries and lithium–sulfur batteries. Unfortunately, commercialization of metal fluoride cathodes is prevented by their high resistance, irreversible structural change, and rapid degradation. In this study, a substantial boost in metal fluoride (MF) cathode stability by designing nanostructure with two layers of protective shells—one deposited ex situ and the other in situ is demonstrated. Such methodology achieves over 90% capacity retention after 300 charge–discharge cycles, producing the first report on FeF3 as a cathode material, where a very high capacity utilization in combination with excellent stability is approaching the level needed for practical applications of FeF3. The cathode solid electrolyte interphase (CEI) containing lithium oxalate and BF bond containing anions is found to effectively protect the cathode material from direct contact with electrolytes, thus greatly suppressing the dissolution of Fe. Quantum chemistry and molecular dynamics calculations provide unique insights into the mechanisms of CEI layer formation. As a result, this work not only demonstrates unprecedented performance, but also provides the reader with a better fundamental understanding of electrochemical behavior of MF cathodes and the positive impact observed with the application of a lithium bis(oxalato)borate salt in the electrolyte.
Conformal vapor deposition of iron phosphate onto carbon nanotubes for flexible high-rate cathodes
Materials Today Energy
X Ren, K Turcheniuk, D Lewis, W Fu, A Magasinski, M Zhang, G Yushin
Amorphous iron (III) phosphate (FePO4or FP) is an environmentally friendly cathode material that maybe produced at very low temperatures and exhibits capacities approaching that of olivine lithium ironphosphate (LiFePO4or LFP). The only known route to produce conformal coatings of FP for three-dimensional (3D) or flexible batteries proceeds via atomic layer deposition (ALD), which suffers fromvery low deposition rates and high cost. Herein, we report for the first time a very uniform FP depositionby simpler and faster chemical vapor deposition (CVD). In our proof-of-concept experiments, wedeposited conformal FP layers onto the surface of flexible carbon nanotubes (CNT). The precise controlenabled by CVD allowed systematic studies of the influence of FP coating thickness on electrochemicalperformance characteristics. An open-porosity and high surface area of CNT@FP nanocomposites lead toa high rate capability and exceptional cycle stability with a 71% retention of initial capacity after 2000cycles at a 5C rate. Reported FP CVD technology opens new avenues towards designing, manufacturingand tuning high-performance nanostructured energy storage materials
Iron Phosphate Coated Flexible Carbon Nanotube Fabric as a Multifunctional Cathode for Na‐Ion Batteries
X Ren, K Turcheniuk, D Lewis, W Fu, A Magasinski, M W Schauer, G Yushin
Conventional slurry casted electrodes cannot stand high loads or be repeatedly flexed or bent without being fractured, which inhibits their use in flexible batteries. Carbon nanotube (CNT) fabric exhibits a paramount mechanical stability and, due to its porosity, can additionally accommodate an active material within its structure. While solution-based protocols cannot achieve conformal coatings of active materials, chemical vapor deposition (CVD) gives a unique opportunity to control and vary the thickness and homogeneity of the coating. Herein, a conformal CVD coating of amorphous iron (III) phosphate (a-FePO4, FP) on flexible CNT fabric and its ability to reversibly accommodate large radius Na ions is reported. The freestanding binder-free CNT@FP electrodes exhibit highrate capabilities and exceptional cycle stabilities with 98% of retention of initial capacity after 100 cycles. Such electrodes additionally demonstrate high mechanical stability under high loads, remarkable bending characteristics, and modulus of toughness (12 MJ m−3) exceeding that of Al. The presented concept of flexible CNT@FePO4 electrodes with high load-bearing characteristics opens new perspectives toward the formation of light-weight, flexible, multifunctional Na-ion battery electrodes based on abundant materials.
Materials for supercapacitors: When Li-ion battery power is not enough
Z Lin, E Goikolea, A Balducci, K Naoi, PL Taberna, M Salanne, G Yushin, P Simon
Supercapacitors, also known as electrochemical capacitors, have witnessed a fast evolution in the recent years, but challenges remain. This review covers the fundamentals and state-of-the-art developments of supercapacitors. Conventional and novel electrode materials, including high surface area porous carbons for electrical double layer capacitors (EDLCs) and transition metal oxides, carbides, nitrides and their various nanocomposites for pseudocapacitors–are described. Latest characterization techniques help to better understand the charge storage mechanisms in such supercapacitors and recognize their current limitations, while recently proposed synthesis approaches enable various breakthroughs in this field. Z. Lin et al., Materials Today 2018 (in press) [https://doi.org/10.1016/j.mattod.2018.01.035](https://doi.org/10.1016/j.mattod.2018.01.035)
Hierarchical Fabric Decorated with Carbon Nanowire/Metal Oxide Nanocomposites for 1.6 V Wearable Aqueous Supercapacitors
W Fu, E Zhao, X Ren, A Magasinski, G Yushin
Aqueous asymmetric supercapacitors (ASCs) may offer comparable or higher energy density than electric double-layer capacitors (EDLCs) based on organic electrolytes. As such, ASCs may be more suitable for integration into smart textiles, where the use of flammable organic solvents is not acceptable. However, reported ASC devices typically suffer from poor rate capability and low areal loadings. This study demonstrates the development of nitrogen-doped carbon (N-C) nanowire/metal oxide (Fe2O3 and MnO2) nanocomposite electrodes directly produced on the internal surface of a conductive fabric for use as high-rate electrodes for solid-state ASCs. The N-C nanowires provide fast and efficient pathways for electrons, while short diffusion paths within nanosized metal oxides enable fast ion transport, leading to greatly enhanced performance at high rates. The porous structure of the fabric enables high areal capacitance loading in each electrode (≈150 mF cm−2). Both electrodes show high specific capacitance of ≈180 F g−1 (Fe2O3) and ≈250 F g−1 (MnO2) and excellent rate capability. Solid-state ASCs assembled by using an aqueous gel electrolyte operate at 1.6 V and deliver over 60 mF cm−2 during ≈50 s charging/discharging time and over 30 mF cm−2 for ≈5 s discharge. W Fu et al., Adv. Energy Mater. 2018, 1703454 [https://doi.org/10.1002/aenm.201703454](https://doi.org/10.1002/aenm.201703454)
Protons Enhance Conductivities in Lithium Halide Hydroxide/Lithium Oxyhalide Solid Electrolytes by Forming Rotating Hydroxy Groups
A.-Y. Song, Y Xiao, K Turcheniuk, P Upadhya, A Ramanujapuram, J Benson, A Magasinski, M Olguin, L Meda, O Borodin, G Yushin
Li-halide hydroxides (Li2OHX) and Li-oxyhalides (Li3OX) have emerged as new classes of low-cost, lightweight solid state electrolytes (SSE) showing promising Li-ion conductivities. The similarity in the lattice parameters between them, careless synthesis, and insufficient rigor in characterization often lead to erroneous interpretations of their compositions. Finally, moisture remaining in the synthesis or cell assembling environment and variability in the equivalent circuit models additionally contribute to significant errors in their properties. Thus, there remains a controversy about the real values of Li-ion conductivities in such SSEs. Here an ultra-fast synthesis and comprehensive material characterization is utilized to report on the ionic conductivities of contaminant-free Li2+xOH1−xCl (x=0-0.7), and Li2OHBr not exceeding 10-4 S cm-1 at 110 °C. Using powerful combination of experimental and numerical approaches, it is demonstrated that the presence of H in these SSEs yields significantly higher Li+ -ionic conductivity. Born-Oppenheimer molecular dynamics simulations show excellent agreement with experimental results and reveal an unexpected mechanism for faster Li+ transport. It involves rotation of a short OH-group in SSEs, which opens lower-energy pathways for the formation of Frenkel defects and highly-correlated Li+ jumps. These findings will reduce the existing confusions and show new avenues for tuning SSE compositions for further improved Li-ion conductivities. A.Y Song et al., Advanced Energy Mat. 2018, [https://doi.org/10.1002/aenm.201700971 ](https://doi.org/10.1002/aenm.201700971)
Conversion cathodes for rechargeable lithium and lithium-ion batteries
Energy & Environmental Science
F Wu, G Yushin
Commercial lithium-ion (Li-ion) batteries built with Ni- and Co-based intercalation-type cathodes suffer from low specific energy, high toxicity and high cost. A further increase in the energy storage characteristics of such cells is challenging because capacities of such intercalation compounds approach their theoretical values and a further increase in their maximum voltage induces serious safety concerns. The growing market for portable energy storage is undergoing a rapid expansion as new applications demand lighter, smaller, safer and lower cost batteries to enable broader use of plug-in hybrid and pure-electric vehicles (PHEVs and EVs), drones and renewable energy sources, such as solar and wind. Conversion-type cathode materials are some of the key candidates for the next-generation of rechargeable Li and Li-ion batteries. Continuous rapid progress in performance improvements of such cathodes is essential to utilize them in future applications. In this review we consider price, abundance and safety of the elements in the periodic table for their use in conversion cathodes. We further compare specific and volumetric capacities of a broad range of conversion materials. By offering a model for practically achievable volumetric energy density and specific energy of Li cells with graphite, silicon (Si) and lithium (Li) anodes, we observe the impact of cathode chemistry directly. This allows us to estimate potentials of different conversion cathodes for exceeding the energy characteristics of cells built with state of the art intercalation compounds. We additionally review the key challenges faced when using conversion-type active materials in cells and general strategies to overcome them. Finally, we discuss future trends and perspectives for cost reduction and performance enhancement. F Wu et al., Energy & Environmental Science 10 (2), 2017, 435-459 [https://doi.org/10.1039/C6EE02326F](https://doi.org/10.1039/C6EE02326F)
Transformation of bulk alloys to oxide nanowires
D Lei, J Benson, A Magasinski, G Berdichevsky, G Yushin
One dimensional (1D) nanostructures offer prospects for enhancing the electrical, thermal, and mechanical properties of a broad range of functional materials and composites, but their synthesis methods are typically elaborate and expensive. We demonstrate a direct transformation of bulk materials into nanowires under ambient conditions without the use of catalysts or any external stimuli. The nanowires form via minimization of strain energy at the boundary of a chemical reaction front. We show the transformation of multimicrometer-sized particles of aluminum or magnesium alloys into alkoxide nanowires of tunable dimensions, which are converted into oxide nanowires upon heating in air. Fabricated separators based on aluminum oxide nanowires enhanced the safety and rate capabilities of lithium-ion batteries. The reported approach allows ultralow-cost scalable synthesis of 1D materials and membranes. D Lei et al, Science 355 (6322), 2017, 267-271, [https://doi.org/10.1126/science.aal2239](https://doi.org/10.1126/science.aal2239)
A stable lithiated silicon–chalcogen battery via synergetic chemical coupling between silicon and selenium
KS Eom, JT Lee, M Oschatz, F Wu, S Kaskel, G Yushin, TF Fuller
Li-ion batteries dominate portable energy storage due to their exceptional power and energy characteristics. Yet, various consumer devices and electric vehicles demand higher specific energy and power with longer cycle life. Here we report a full-cell battery that contains a lithiated Si/graphene anode paired with a selenium disulfide (SeS2) cathode with high capacity and long-term stability. Selenium, which dissolves from the SeS2 cathode, was found to become a component of the anode solid electrolyte interphase (SEI), leading to a significant increase of the SEI conductivity and stability. Moreover, the replacement of lithium metal anode impedes unwanted side reactions between the dissolved intermediate products from the SeS2 cathode and lithium metal and eliminates lithium dendrite formation. As a result, the capacity retention of the lithiated silicon/graphene—SeS2 full cell is 81% after 1,500 cycles at 268 mA gSeS2−1. The achieved cathode capacity is 403 mAh gSeS2−1 (1,209 mAh cmSeS2−3). KS Eom et al., Nature communications 8, 2017, 13888 [https://doi.org/10.1038/ncomms13888](https://doi.org/10.1038/ncomms13888)
Carbide-derived carbon aerogels with tunable pore structure as versatile electrode material in high power supercapacitors
M Oschatz, S Boukhalfa, W Nickel, JP Hofmann, C Fischer, G Yushin, S Kaskel
Carbide-derived carbon (CDC) aerogels with hierarchical porosity are prepared from cross-linked polycarbosilane aerogels by pyrolysis and chlorine treatment at 700 and 1000 °C. The low-temperature sample is further activated with carbon dioxide to introduce additional micropores. The influence of the micropore structures resulting from the different synthesis conditions and the effect of the combination of high specific surface areas of more than 2400 m2/g with the aerogel-type texture on the electrochemical properties of the carbons are investigated. Electrical double-layer capacitors (EDLCs) are assembled with 1 M aqueous (H2SO4, Li2SO4, LiCl, HCl), organic (1 M tetraethylammoniumtetrafluoroborate in acetonitrile), and ionic liquid (1-ethyl-3-methylimidazoliumtetrafluoroborate) electrolytes. The larger micropores and higher surface area of the CDC aerogel prepared at 700 °C lead to higher capacitance compared to the material prepared at 1000 °C. Carbon dioxide activation leads to extremely high capacitance retentions at high current densities up to 60 A/g, which is critical for high power applications. High gravimetric specific capacitances with stable cycling and high capacitance retentions are achieved in all the studied electrolytes. This renders CDC aerogels versatile electrode materials for EDLCs with various electrolytes. M Oschatz et al., Carbon 113, 2017, 283-291 [https://doi.org/10.1016/j.carbon.2016.11.050](https://doi.org/10.1016/j.carbon.2016.11.050)
Chapter 5: Capacitive Energy Storage
Energy Storage 4
W Gu, L Wei, G Yushin
Capacitors are electrical devices for electrostatic energy storage. There are several types of capacitors developed and available commercially. Conventional dielectric and electrolytic capacitors store charge on parallel conductive plates with a relatively low surface area, and therefore, deliver limited capacitance. However, they can be operated at high voltages. As an alternative, electrochemical capacitors (ECs) (also called supercapacitors) store charge in electric double layers or at surface reduction–oxidation (Faradaic) sites. Thanks to the large surface area of the electrode and the nanoscale charge separation, electrochemical capacitors provide much higher capacitance, filling in the gap in the energy and power characteristics between batteries and conventional capacitors. However, they offer a lower energy density than batteries and commonly lower power than traditional capacitors. In the past decade, intensive research on ECs brought about the discovery of new electrode materials and in-depth understanding of ion behavior in small pores, as well as the design of new hybrid systems combining Faradaic and capacitive electrodes, which are essential for the enhancement of the performance of ECs. W Gu et al., Energy Storage, 2017 [https://doi.org/10.1142/9789813208964_0005](https://doi.org/10.1142/9789813208964_0005)
Toward a Long-Chain Perfluoroalkyl Replacement: Water and Oil Repellency of Polyethylene Terephthalate (PET) Films Modified with Perfluoropolyether-Based Polyesters
ACS applied materials & interfaces
T Demir, L Wei, N Nitta, G Yushin, PJ Brown, I Luzinov
Original perfluoropolyethers (PFPE)-based oligomeric polyesters (FOPs) of different macromolecular architecture were synthesized via polycondensation as low surface energy additives to engineering thermoplastics. The oligomers do not contain long-chain perfluoroalkyl segments, which are known to yield environmentally unsafe perfluoroalkyl carboxylic acids. To improve the compatibility of the materials with polyethylene terephthalate (PET) we introduced isophthalate segments into the polyesters and targeted the synthesis of lower molecular weight oligomeric macromolecules. The surface properties such as morphology, composition, and wettability of PET/FOP films fabricated from solution were investigated using atomic force microscopy, X-ray photoelectron spectroscopy, and contact angle measurements. It was demonstrated that FOPs, when added to PET film, readily migrate to the film surface and bring significant water and oil repellency to the thermoplastic boundary. We have established that the wettability of PET/FOP films depends on three main parameters: (i) end-groups of fluorinated polyesters, (ii) the concentration of fluorinated polyesters in the films, and (iii) equilibration via annealing. The most effective water/oil repellency FOP has two C4F9–PFPE-tails. The addition of this oligomeric polyester to PET allows (even at relatively low concentrations) reaching a level of oil repellency and surface energy comparable to that of polytetrafluorethylene (PTFE/Teflon). Therefore, the materials can be considered suitable replacements for additives containing long-chain perfluoroalkyl substances. T Demir et al., ACS applied materials & interfaces 9 (28), 24318-24330 [https://doi.org/10.1021/acsami.7b05799](https://doi.org/10.1021/acsami.7b05799)
Toward in-situ protected sulfur cathodes by using lithium bromide and pre-charge
F Wu, S Thieme, A Ramanujapuram, E Zhao, C Weller, H Althues, S Kaskel, O Borodin, G Yushin
Lithium-sulfur (Li-S) batteries suffer from the dissolution of its intermediate charge products (polysulfides) in organic electrolytes, which limits the utilization, rate performance and cycling stability of S cathode materials. Formation of protective surface coatings on S cathodes may effectively overcome such a challenge. Here, we explored a simple, low cost, and widely applicable method that offers in-situ formation of a protective coating on the S-based cathode by using lithium bromide (LiBr) as a novel electrolyte additive. Quantum chemical (QC) studies suggested that pre-cycling a S cathode at high potentials is needed to oxidize the Br- and induce formation of DME(-H) radicals, which are involved in the formation of a polymerized protective layer of a solid electrolyte interphase (SEI) on a S cathode at high potentials. Experimental studies with a LiBr additive confirmed that 3 pre-cycles in a voltage range of 2.5–3.6 V are sufficient to achieve the formation of a robust Li ion permeable SEI on the cathode, effectively preventing the dissolution of polysulfides into electrolyte. As a result, almost no degradation was observed within 200 cycles, compared to more than 40% of capacity loss in the benchmark control cells without LiBr or the pre-cycles. Post-mortem analysis on both the cathode and anode sides of the LiBr-comprising cells further provided evidence for the in-situ SEI formation on the cathode and the lack of polysulfides' re-precipitation. In addition, such studies showed smooth surface on the cycled Li metal anode, in contrast to the rough Li SEI with dendrites and polysulfides in the benchmark cells. F Wu et al., Nano Energy 40, 170-179 [https://doi.org/10.1016/j.nanoen.2017.08.012](https://doi.org/10.1016/j.nanoen.2017.08.012)
Enhancing electrochemical performance of LiFePO4 by vacuum-infiltration into expanded graphite for aqueous Li-ion capacitors
Electrochimica Acta
C Qin, Y Li, S Lv, J Xiang, C Wang, X Zhang, S Qiu, G Yushin
Olivine-type LiFePO4 (LFP) is one of the most widely utilized cathode materials for high power Li-ion batteries (LIBs). In spite of rapidly growing popularity of LIBs, the rate performance of the highest power LFP cells is still insufficiently high for some high-power applications. In this work we demonstrate that vacuum-infiltration of LFP precursors into pores of low-cost expanded graphite (EG), an in-situ sol-gel process, followed by calcination, allows formation of LFP/EG nanocomposites that demonstrate remarkable performance in higher power Li-ion capacitor (LIC) applications. Such composites comprise spherical LFP particles embedded into EG pores and additionally wrapped by EG films, forming a highly efficient and stable conducting network. Such a morphology greatly accelerates Li-ion diffusion and improves Li-ion exchange between LFP and electrolyte. As a result, compared to commercial LFP particles of comparable size, the optimized LFP/EG nanocomposite shows significantly higher rate performance, dramatically better stability and higher specific capacitance of up to about 1200 F g−1. The use of environmentally friendly, safe and low-cost aqueous electrolyte is particularly advantageous for LIC applications that are cost-sensitive and require enhanced safety. Our results demonstrate a great promise of our approach, which is additionally applicable for a broad range of other intercalation chemistries. C Qin et al., Electrochimica Acta 253, 2017, 413–42 [https://doi.org/10.1016/j.electacta.2017.09.069](https://doi.org/10.1016/j.electacta.2017.09.069)
Enhancing Cycle Stability of Lithium Iron Phosphate in Aqueous Electrolytes by Increasing Electrolyte Molarity
D Gordon, MY Wu, A Ramanujapuram, J Benson, JT Lee, A Magasinski, N Nitta, C Huang, G Yushin
Aqueous lithium ion batteries (ALIBs) exhibit great potential to reduce the cost and improve the safety of rechargeable energy storage technologies. Lithium iron phosphate (LFP) cathodes have become a material of choice for many conventional, high power LIBs. However, experimental studies on LFP in aqueous lithium (Li) ion electrolytes are limited. Here, results of systematic studies are shown where it is demonstrated that the Li salt concentration of the aqueous electrolyte can signifi cantly improve discharge capacity retention while minimally impacting rate capability, for electrodes made with a typical commercial sub-micron sized LFP powder. Based on the postmortem analysis and the results of electrochemical characterization it is proposed that unde-sirable side reactions of aqueous electrolytes with LFP induce electrochemical separation of individual particles within the electrode, leading to the observed capacity fading. Increasing the salt concentration in aqueous solutions effec-tively reduces the concentration of water molecules in the electrolyte, which are mostly responsible for these undesirable side reactions. Similar trends observed with other cathode materials suggest that the use of concentrated aqueous electrolyte solutions offers an effective route to improve stability of aqueous Li ion batteries. D Gordon et al., Advanced Energy Materials 6 (2), 2016 [https://doi.org/10.1002/aenm.201501805](https://doi.org/10.1002/aenm.201501805)
Degradation and stabilization of lithium cobalt oxide in aqueous electrolytes
A Ramanujapuram, D Gordon, A Magasinski, B Ward, N Nitta, C Huang, G Yushin
We report herein the exceptional cycle stability of lithium cobalt oxide (LCO) in aqueous electrolytes of high lithium salt concentrations. We demonstrate retention of up to 87% of the initial discharge capacity after 1500 cycles at a 1C charge–discharge rate. We also demonstrate that LCO, when in contact with each of the aqueous electrolytes tested, exhibits a high electrode potential and a large initial discharge capacity, similar to that of LCO electrochemically cycled in conventional organic electrolytes. More importantly, our systematic studies and post-mortem analyses of LCO cells reveal that the primary mechanism of LCO degradation in aqueous electrolytes is the formation of a resistive layer of cobalt(II) oxide on the particles' surfaces. We show that higher electrolyte molarity and certain salt compositions may significantly reduce the layer thickness and dramatically improve LCO stability. These findings constitute a substantial step towards development of gravimetrically and volumetrically energy dense aqueous lithium ion batteries. A Ramanujapuram et al., Energy & Environmental Science 9 (5), 2016, 1841-1848 [https://doi.org/10.1039/C6EE00093B](https://doi.org/10.1039/C6EE00093B)
Performance enhancement and side reactions in rechargeable nickel–iron batteries with nanostructured electrodes
D Lei, DC Lee, A Magasinski, E Zhao, D Steingart, G Yushin
We report for the first time a solution-based synthesis of strongly coupled nanoFe/multiwalled carbon nanotube (MWCNT) and nanoNiO/MWCNT nanocomposite materials for use as anodes and cathodes in rechargeable alkaline Ni–Fe batteries. The produced aqueous batteries demonstrate very high discharge capacities (800 mAh gFe–1 at 200 mA g–1 current density), which exceed that of commercial Ni–Fe cells by nearly 1 order of magnitude at comparable current densities. These cells also showed the lack of any "activation", typical in commercial batteries, where low initial capacity slowly increases during the initial 20–50 cycles. The use of a highly conductive MWCNT network allows for high-capacity utilization because of rapid and efficient electron transport to active metal nanoparticles in oxidized (such as Fe(OH)2 or Fe3O4) states. The flexible nature of MWCNTs accommodates significant volume changes taking place during phase transformation accompanying reduction–oxidation reactions in metal electrodes. At the same time, we report and discuss that high surface areas of active nanoparticles lead to multiple side reactions. Dissolution of Fe anodes leads to reprecipitation of significantly larger anode particles. Dissolution of Ni cathodes leads to precipitation of Ni metal on the anode, thus blocking transport of OH– anions. The electrolyte molarity and composition have a significant impact on the capacity utilization and cycling stability. D Lei et al., ACS applied materials & interfaces 8 (3), 2016, 2088-2096 [https://doi.org/10.1021/acsami.5b10547](https://doi.org/10.1021/acsami.5b10547)
Conversion Cathodes: Lithium–Iron Fluoride Battery with In Situ Surface Protection
Advanced Functional Materials
W Gu, O Borodin, B Zdyrko, HT Lin, H Kim, N Nitta, J Huang, A Magasinski, Z Milicev, G Berdichevsky, G Yushin
Lithium–metal fluoride (MF) batteries offer the highest theoretical energy density, exceeding that of the sulfur–lithium cells. However, conversion-type MF cathodes suffer from high resistance, small capacity utilization at room temperature, irreversible structural changes, and rapid capacity fading with cycling. In this study, the successful application of the approach to overcome such limitations and dramatically enhance electrochemical performance of Li–MF cells is reported. By using iron fluoride (FeF2) as an example, Li–MF cells capable of achieving near-theoretical capacity utilization are shown when MF is infiltrated into the carbon mesopores. Most importantly, the ability of electrolytes based on the lithium bis(fluorosulfonyl)imide (LiFSI) salt is presented to successfully prevent the cathode dissolution and leaching via in situ formation of a Li ion permeable protective surface layer. This layer forms as a result of electrolyte reduction/oxidation reactions during the first cycle of the conversion reaction, thus minimizing the capacity losses during cycling. Postmortem analysis shows the absence of Li dendrites, which is important for safer use of Li metal anodes. As a result, Li–FeF2 cells demonstrate over 1000 stable cycles. Quantum chemistry calculations and postmortem analysis provide insights into the mechanisms of the passivation layer formation and the performance boost. W Gu et al., Advanced Functional Materials 26 (10), 2016, 1507-1516 [https://doi.org/10.1002/adfm.201504848](https://doi.org/10.1002/adfm.201504848)
Lithium Titanate Confined in Carbon Nanopores for Asymmetric Supercapacitors
ACS nano
E Zhao, C Qin, HR Jung, G Berdichevsky, A Nese, S Marder, G Yushin
Porous carbons suffer from low specific capacitance, while intercalation-type active materials suffer from limited rate when used in asymmetric supercapacitors. We demonstrate that nanoconfinement of intercalation-type lithium titanate (Li4Ti5O12) nanoparticles in carbon nanopores yielded nanocomposite materials that offer both high ion storage density and rapid ion transport through open and interconnected pore channels. The use of titanate increased both the gravimetric and volumetric capacity of porous carbons by more than an order of magnitude. High electrical conductivity of carbon and the small size of titanate crystals allowed the composite electrodes to achieve characteristic charge and discharge times comparable to that of the electric double-layer capacitors. The proposed composite synthesis methodology is simple, scalable, and applicable for a broad range of active intercalation materials, while the produced composite powders are compatible with commercial electrode fabrication processes. E Zhao et al., ACS Nano, 2016, 10 (4), 3977–3984 [https://doi.org/10.1021/acsnano.6b00479](https://doi.org/10.1021/acsnano.6b00479)
Revealing Rate Limitations in Nanocrystalline Li4Ti5O12 Anodes for High‐Power Lithium Ion Batteries
Advanced Materials Interfaces
J Wang, H Zhao, Z Li, Y Wen, Q Xia, Y Zhang, G Yushin
Li4Ti5O12 is a promising anode material for lithium ion batteries due to its high safety, excellent cycling stability, environmental friendliness, and low cost. Strategies of incorporation with a conductive component (such as carbon) and constructing nano-structure are frequently adopted to improve the rate-capability of Li4Ti5O12 by means of enhancing the electronic conductivity and promoting the lithium ion transport within electrodes, respectively. However, which charge carrier transport process is the limiting step for Li4Ti5O12 electrode reactions still remains unclear, and this limits the abilities to rationally design high performance Li4Ti5O12 materials. In this work, the nanosized Li4Ti5O12 and Li4Ti5O12/C materials are prepared with nearly identical particle size and morphology. The results demonstrate that the synthesized single phase Li4Ti5O12 delivers a higher specific capacity and superior rate-capability than Li4Ti5O12/C composite. As such, in contrast to a popular belief, it is lithium ion transport that restricts kinetics of the electrochemical reactions on Li4Ti5O12. The synthesized single phase Li4Ti5O12 shows a specific capacity of ≈160 mAh g−1 at 0.5 C and 130 mAhg−1 at 50 C rates, respectively. This rate-capability is the best reported for Li4Ti5O12 anodes. The single phase Li4Ti5O12 also demonstrated remarkable stability at high-temperature (50 °C), showing cycling life of over 4000 cycles at 1 C. J Wang et al., Advanced Materials Interfaces 3 (13), 2016 [https://doi.org/10.1002/admi.201600003](https://doi.org/10.1002/admi.201600003)
Enhancing the stability of sulfur cathodes in Li–S cells via in situ formation of a solid electrolyte layer
JT Lee, KS Eom, F Wu, H Kim, DC Lee, B Zdyrko, G Yushin
Enhancing the performance of rechargeable lithium (Li)–sulfur (S) batteries is one of most popular topics in a battery field because of their low cost and high specific energy. However, S experiences dissolution during its electrochemical reactions; hence, maintaining its initial capacity is challenging. Protecting the S cathode with a Li ion conducting layer that acts as a barrier for polysulfide transport is an attractive strategy, but formation of such protective layers typically involves significant effort and cost. Here, we report a facile route to form a conformal solid electrolyte layer on S cathodes in situ using a carbonate solvent. The chemically and mechanically stable and Li ion conducting protective layer is formed by inducing electrolyte reduction and polymerization reactions on the cathode surface. The layer serves as a polysulfide's barrier, successfully helping to retain S active material in the carbon pores. In addition, it helps to improve the performance of Li anodes. JT Lee et al., ACS Energy Letters 1 (2), 2016, 373-379 [https://doi.org/10.1021/acsenergylett.6b00163](https://doi.org/10.1021/acsenergylett.6b00163)
Infiltrated Porous Polymer Sheets as Free‐Standing Flexible Lithium‐Sulfur Battery Electrodes
F Wu, E Zhao, D Gordon, Y Xiao, C Hu, G Yushin
Free-standing high capacity Li2 S electrodes with capacity loadings in the range from 1.5 to 3.8 mAh cm(-2) have been produced by using infiltration of active materials into porous carbonized biomass sheets. The proposed electrode design can be effectively utilized for the low-cost fabrication of flexible lithium batteries with high specific energy. F Wu et al., Advanced Materials 28 (30), 2016, 6365-6371 [https://doi.org/10.1002/adma.201600757](https://doi.org/10.1002/adma.201600757)
Nanostructured Li2Se cathodes for high performance lithium-selenium batteries
F Wu, JT Lee, Y Xiao, G Yushin
We report on a simple and fast route to prepare lithium selenide (Li2Se) nanoparticles and show a versatile solution-based method to form uniform nanostructured carbon (C)-Li2Se composites with and without additional carbon shell. We systematically compare electrochemical performance characteristics of 50–100 nm high purity Li2Se nanoparticles with that of the C-Li2Se nanocomposites for rechargeable Li battery applications. While Li2Se nanopowder show high initial capacity, it suffers from active material loss and shuttle of dissolved polyselenides, resulting in low cycling stability and resistance growth, additionally aggravated by mechanical cathode degradation induced by repetitive volume changes during cycling. By embedding Li2Se nanoparticles into a conductive carbon matrix, mechanical stability of electrodes was greatly enhanced. More importantly, the dissolution and shuttle of polyselenides was suppressed significantly even for smaller (~20 nm) and thus more reactive Li2Se nanoparticles. As a result, C-Li2Se nanocomposite cathodes showed high rate capability and promising cycling stability with carbon-shell protected C-Li2Se showing virtually no degradation in 100 cycles. When compared with somewhat similar lithium sulfide (Li2S) nanoparticles and C-Li2S electrodes, we observe lower over-potential at different C-rates in case of Li2Se and C-Li2Se materials, which is advantageous for battery applications. Based on the postmortem analysis, significant Li dendrite growth observed in Li2Se/Li cells did not take place in C-Li2Se/Li and C-Li2Se@C/Li cells, suggesting that polyselenide shuttle may affect Li plating morphology. Beyond the organic electrolyte-based Li-Se batteries, all-solid Li-Se batteries based on the produced C-Li2Se nanocomposite cathode were built for the first time using conventional Li2S-P2S5 solid state electrolyte. These solid state cells showed very promising cycling stability, a single flat plateau and very small voltage hysteresis in the range of 0.1–0.4 V when tested at 60 and 80 °C. F Wu et al., Nano energy 27, 2016, 238-246 [https://doi.org/10.1016/j.nanoen.2016.07.012](https://doi.org/10.1016/j.nanoen.2016.07.012)
Aqueous solutions of acidic ionic liquids for enhanced stability of polyoxometalate-carbon supercapacitor electrodes
Journal of Power Sources
C Hu, E Zhao, N Nitta, A Magasinski, G Berdichevsky, G Yushin
Nanocomposites based on polyoxometalates (POMs) nanoconfined in microporous carbons have been synthesized and used as electrodes for supercapacitors. The addition of the pseudocapacitance from highly reversible redox reaction of POMs to the electric double-layer capacitance of carbon lead to an increase in specific capacitance of ∼90% at 1 mV s−1. However, high solubility of POM in traditional aqueous electrolytes leads to rapid capacity fading. Here we demonstrate that the use of aqueous solutions of protic ionic liquids (P-IL) as electrolyte instead of aqueous sulfuric acid solutions offers an opportunity to significantly improve POM cycling stability. Virtually no degradation in capacitance was observed in POM-based positive electrode after 10,000 cycles in an asymmetric capacitor with P-IL aqueous electrolyte. As such, POM-based carbon composites may now present a viable solution for enhancing energy density of electrical double layer capacitors (EDLC) based on pure carbon electrodes. C Hu et al., Journal of Power Sources 326, 2016, 569-574 [https://doi.org/10.1016/j.jpowsour.2016.04.036](https://doi.org/10.1016/j.jpowsour.2016.04.036)
Charge storage at the nanoscale: understanding the trends from the molecular scale perspective
J Vatamanu, O Borodin, M Olguin, G Yushin, D Bedrov
Supercapacitors or electrical double layer (EDL) capacitors store charge via rearrangement of ions in electrolytes and their adsorption on electrode surfaces. They are actively researched for multiple applications requiring longer cycling life, broader operational temperature ranges, and higher power density compared to batteries. Recent developments in nanostructured carbon-based electrodes with a high specific surface area have demonstrated the potential to significantly increase the energy density of supercapacitors. Molecular modeling of electrolytes near charged electrode surfaces has provided key insights into the fundamental aspects of charge storage at the nanoscale, including an understanding of the mechanisms of ion adsorption and dynamics at flat surfaces and inside nanopores, and the influence of curvature, roughness, and electronic structure of electrode surfaces. Here we review these molecular modeling findings for EDL capacitors, dual ion batteries and pseudo-capacitors together with available experimental observations and put this analysis into the perspective of future developments in this field. Current research trends and future directions are discussed. J Vatamanu et al., Journal of Materials Chemistry A 5 (40), 2016, 21049-21076 [https://doi.org/10.1039/C7TA05153K](https://doi.org/10.1039/C7TA05153K)
Influence of binders, carbons, and solvents on the stability of phosphorus anodes for Li-ion batteries
N Nitta, D Lei, HR Jung, D Gordon, E Zhao, G Gresham, J Cai, I Luzinov, G Yushin
Phosphorus (P) is an abundant element that exhibits one of the highest gravimetric and volumetric capacities for Li storage, making it a potentially attractive anode material for high capacity Li-ion batteries. However, while phosphorus carbon composite anodes have been previously explored, the influence of the inactive materials on electrode cycle performance is still poorly understood. Here, we report and explain the significant impacts of polymer binder chemistry, carbon conductive additives, and an under-layer between the Al current collector and ball milled P electrodes on cell stability. We focused our study on the commonly used polyvinylidene fluoride (PVDF) and poly(acrylic acid) (PAA) binders as well as exfoliated graphite (ExG) and carbon nanotube (CNT) additives. The mechanical properties of the binders were found to change drastically because of interactions with both the slurry and electrolyte solvents, significantly effecting the electrochemical cycle stability of the electrodes. Binder adhesion was also found to be critical in achieving stable electrochemical cycling. The best anodes demonstrated ∼1400 mAh/g-P gravimetric capacity after 200 cycles at C/2 rates in Li half cells. N Nitta et al. ACS applied materials & interfaces 8 (39), 25991-26001 [https://doi.org/10.1021/acsami.6b07931](https://doi.org/10.1021/acsami.6b07931)
In Situ Formation of Protective Coatings on Sulfur Cathodes in Lithium Batteries with LiFSI-Based Organic Electrolytes
H Kim, F Wu, J T Lee, N Nitta, HT Lin, M Oschatz, W Cho, S Kaskel, O Borodin, G Yushin
Development of sulfur cathodes with 100% coulombic efficiency (CE) and good cycle stability remains challenging due to the polysulfide dissolution in electrolytes. Here, it is demonstrated that electrochemical reduction of lithium bis(fluorosulfonyl)imide (LiFSI) based electrolytes at a potential close to the sulfur cathode operation forms in situ protective coating on both cathode and anode surfaces. Quantum chemistry studies suggest the coating formation is initiated by the FSI(-F) anion radicals generated during electrolyte reduction. Such a reduction additionally results in the formation of LiF. Accelerated cycle stability tests at 60 °C in a very simple electrolyte (LiFSI in dimethoxyethane with no additives) show an average CE approaching 100.0% over 1000 cycles with a capacity decay less than 0.013% per cycle after stabilization. Such a remarkable performance suggests a great promise of both an in situ formation of protective solid electrolyte coatings to avoid unwanted side reactions and the use of a LiFSI salt for this purpose.
A Hierarchical Particle–Shell Architecture for Long-Term Cycle Stability of Li2S Cathodes
F Wu, J T Lee, F Fan, NNitta, H Kim, T Zhu, G Yushin
A hierarchical particle–shell architecture for long-term cycle stability of Li2S cathodes is described. Multiscale and multilevel protection prevents mechanical degradation and polysulfide dissolution in lithium–sulfur battery chemistries.
Chemical Vapor Deposition and Atomic Layer Deposition for Advanced Lithium Ion Batteries and Supercapacitors
X Wang and G Yushin
Applications of the non-line-of-sight vapor deposition techniques, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD), offer unique opportunities to produce well-defined high surface area current collectors, thin films or various nanostructures of active (ion-storage) materials, protective coatings, solid electrolytes and improved separators. These features hold significant promise for solving emerging issues in advanced LiBs and supercapacitors. This paper reviews recent developments and applications of CVD and ALD for these energy storage devices, providing selected examples and outlining critical challenges for further exploration.
Li-ion Battery Materials: Present and Future
Naoki Nitta, Feixiang Wu, Jung Tae Lee and Gleb Yushin
This review covers key technological developments and scientific challenges for a broad range of Li-ion battery electrodes. Periodic table and potential/capacity plots are used to compare many families of suitable materials. Performance characteristics, current limitations, and recent breakthroughs in the development of commercial intercalation materials such as lithium cobalt oxide (LCO), lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), lithium titanium oxide (LTO) and others are contrasted with that of conversion materials, such as alloying anodes (Si, Ge, Sn, etc.), chalcogenides (S, Se, Te), and metal halides (F, Cl, Br, I). New polyanion cathode materials are also discussed. The cost, abundance, safety, Li and electron transport, volumetric expansion, material dissolution, and surface reactions for each type of electrode materials are described. Both general and specific strategies to overcome the current challenges are covered and categorized.
Increasing capacitance of zeolite-templated carbons in electric double layer capacitors
Journal of The Electrochemical Society
JS Moon, H Kim, DC Lee, JT Lee, G Yushin
Enhancement of the specific capacitance in electrochemical double layer capacitors (EDLCs) is of high interest due to the ever increasing demand for high power density energy storage devices. Zeolite templated carbon (ZTC) is a promising EDLC electrode material with large specific surface area and straight, ordered well-defined micropores. In this study, ZTC samples were synthesized using a low pressure chemical vapor deposition (LP CVD) of carbon on sacrificial zeolite Y powder using acetylene gas as a precursor. We demonstrate for the first time how various post-treatments of the produced samples can affect the ZTC microstructure and porosity and how such modifications may significantly improve electrochemical performance characteristics of the ZTC-based EDLC electrodes. The effects of CO2 activation, ball milling and high temperature annealing process were systematically studied. The best performing samples achieved very large capacitance of over 240 Fg−1 at 1 mVs−1 in 1 M solution of tetraethylammonium tetrafluoroborate in acetonitrile and stable performance in symmetric EDLC devices with no noticeable degradation for over 20,000 cycles at a very high current density of 20 Ag−1. JS Moon et al., Journal of The Electrochemical Society 162 (5), 2015, A5070-A5076 [https://doi.org/10.1149/2.0131505jes](https://doi.org/10.1149/2.0131505jes)
Lithium iodide as a promising electrolyte additive for lithium–sulfur batteries: mechanisms of performance enhancement
F Wu, JT Lee, N Nitta, H Kim, O Borodin, G Yushin
Lithium Iodide (LiI) is reported as a promising electrolyte additive for lithium–sulfur batteries. It induces formation of Li-ion-permeable protective coatings on both positive and negative electrodes, which prevent the dissolution of polysulfides on the cathode and reduction of polysulfides on the anode. In addition to enhancing the cell cycle stability, LiI addition also decreases the cell overpotential and voltage hysteresis. F Wu et al., Advanced Materials 27 (1), 2015, 101-108 [https://doi.org/10.1002/adma.201404194](https://doi.org/10.1002/adma.201404194)
Metal Fluorides Nanoconfined in Carbon Nanopores as Reversible High Capacity Cathodes for Li and Li-Ion Rechargeable Batteries: FeF2 as an Example
Wentian Gu, Marta Sevilla, Alexandre Magasinski, Bogdan Zdyrko and Gleb Yushin
Highly uniform nanocomposites with nanoconfined iron fluoride (FeF2) are successfully produced using vacuum impregnation of activated carbon powder with a fluoride precursor and subsequent precursor transformation. When confined in carbon nanopores, metal fluoride nanoparticles exhibit dramatically enhanced performance characteristics and cycle life in Li ion batteries. Carbon pore walls accommodate fluoride volume changes during lithiation, prevent physical separation of fluoride particles, and deliver electrons or holes to the electrochemical reaction sites during cell operation.
Micro‐and Mesoporous Carbide‐Derived Carbon–Selenium Cathodes for High‐Performance Lithium Selenium Batteries
JT Lee, H Kim, M Oschatz, DC Lee, F Wu, HT Lin, B Zdyrko, WI Cho,
Nanocomposites of selenium (Se) and ordered mesoporous silicon carbide-derived carbon (OM-SiC-CDC) are prepared for the first time and studied as cathodes for lithium-selenium (Li-Se) batteries. The higher concentration of Li salt in the electrolytes greatly improves Se utilization and cell cycle stability. Se-CDC shows significantly better performance characteristics than Se-activated carbon nanocomposites with similar physical properties. Se-CDC also exhibits better rate performance and cycle stability compared to similarly produced sulfur (S)–CDC for Li/S batteries. JT Lee et al., Advanced Energy Materials 5 (1), 2015 [https://doi.org/10.1002/aenm.201400981](https://doi.org/10.1002/aenm.201400981)
X Wang, G Yushin
Applications of the non-line-of-sight vapor deposition techniques, such as chemical vapor deposition (CVD) and atomic layer deposition (ALD), offer unique opportunities to produce well-defined high surface area current collectors, thin films or various nanostructures of active (ion-storage) materials, protective coatings, solid electrolytes and improved separators. These features hold significant promise for solving emerging issues in advanced LiBs and supercapacitors. This paper reviews recent developments and applications of CVD and ALD for these energy storage devices, providing selected examples and outlining critical challenges for further exploration. Energy & Environmental Science 8 (7), 2015, 1889-1904 [https://doi.org/10.1039/C5EE01254F](https://doi.org/10.1039/C5EE01254F)
Metal Fluorides Nanoconfined in Carbon Nanopores as Reversible High Capacity Cathodes for Li and Li‐Ion Rechargeable Batteries: FeF2 as an Example
W Gu, A Magasinski, B Zdyrko, G Yushin
Highly uniform nanocomposites with nanoconfined iron fluoride (FeF2) are successfully produced using vacuum impregnation of activated carbon powder with a fluoride precursor and subsequent precursor transformation. When confined in carbon nanopores, metal fluoride nanoparticles exhibit dramatically enhanced performance characteristics and cycle life in Li ion batteries. Carbon pore walls accommodate fluoride volume changes during lithiation, prevent physical separation of fluoride particles, and deliver electrons or holes to the electrochemical reaction sites during cell operation. W Gu, Advanced Energy Materials 5 (4), 2015 [https://doi.org/10.1002/aenm.201401148](https://doi.org/10.1002/aenm.201401148)
In Situ Formation of Protective Coatings on Sulfur Cathodes in Lithium Batteries with LiFSI‐Based Organic Electrolytes
H Kim, F Wu, JT Lee, N Nitta, HT Lin, M Oschatz, WI Cho, S Kaskel, O Borodin, G Yushin
Development of sulfur cathodes with 100% coulombic efficiency (CE) and good cycle stability remains challenging due to the polysulfide dissolution in electrolytes. Here, it is demonstrated that electrochemical reduction of lithium bis(fluorosulfonyl)imide (LiFSI) based electrolytes at a potential close to the sulfur cathode operation forms in situ protective coating on both cathode and anode surfaces. Quantum chemistry studies suggest the coating formation is initiated by the FSI(-F) anion radicals generated during electrolyte reduction. Such a reduction additionally results in the formation of LiF. Accelerated cycle stability tests at 60 °C in a very simple electrolyte (LiFSI in dimethoxyethane with no additives) show an average CE approaching 100.0% over 1000 cycles with a capacity decay less than 0.013% per cycle after stabilization. Such a remarkable performance suggests a great promise of both an in situ formation of protective solid electrolyte coatings to avoid unwanted side reactions and the use of a LiFSI salt for this purpose. H Kim, Advanced Energy Materials 5 (6), 2015 [https://doi.org/10.1002/aenm.201401792](https://doi.org/10.1002/aenm.201401792)
N Nitta, F Wu, JT Lee, G Yushin
This review covers key technological developments and scientific challenges for a broad range of Li-ion battery electrodes. Periodic table and potential/capacity plots are used to compare many families of suitable materials. Performance characteristics, current limitations, and recent breakthroughs in the development of commercial intercalation materials such as lithium cobalt oxide (LCO), lithium nickel cobalt manganese oxide (NCM), lithium nickel cobalt aluminum oxide (NCA), lithium iron phosphate (LFP), lithium titanium oxide (LTO) and others are contrasted with that of conversion materials, such as alloying anodes (Si, Ge, Sn, etc.), chalcogenides (S, Se, Te), and metal halides (F, Cl, Br, I). New polyanion cathode materials are also discussed. The cost, abundance, safety, Li and electron transport, volumetric expansion, material dissolution, and surface reactions for each type of electrode materials are described. Both general and specific strategies to overcome the current challenges are covered and categorized. N Nitta et al., Materials today 18 (5), 2015, 252-264 [https://doi.org/10.1016/j.mattod.2014.10.040](https://doi.org/10.1016/j.mattod.2014.10.040)
Carbon nanotube–CoF2 multifunctional cathode for lithium ion batteries: Effect of electrolyte on cycle stability
X Wang, W Gu, JT Lee, N Nitta, J Benson, A Magasinski, MW Schauer, G Yushin
Transition metal fluorides (MFx) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion-type cathode materials for lithium ion batteries. Here, a scalable and low-cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near-theoretical, math formula) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MFx-based materials in batteries with load-bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g−1 and over 50% after 10 000 cycles at the current density of 1000 mA g−1. X Wang et al., Small 11 (38), 2015, 5164-5173 [https://doi.org/10.1002/smll.201501139](https://doi.org/10.1002/smll.201501139)
A Hierarchical Particle–Shell Architecture for Long‐Term Cycle Stability of Li2S Cathodes
F Wu, JT Lee, F Fan, N Nitta, H Kim, T Zhu, G Yushin
A hierarchical particle–shell architecture for long-term cycle stability of Li2S cathodes is described. Multiscale and multilevel protection prevents mechanical degradation and polysulfide dissolution in lithium–sulfur battery chemistries. F Wu et al., Advanced Materials 27 (37), 2015, 5579-5586 [https://doi.org/10.1002/adma.201502289](https://doi.org/10.1002/adma.201502289)
Influence of annealing on ionic transfer and storage stability of Li2S–P2S5 solid electrolyte
J Wei, H Kim, DC Lee, R Hu, FX Wu, H Zhao, FM Alamgir, G Yushin
In this study, the impact of annealing treatment on the ionic transfer and storage stability of 70Li2S–30P2S5 glass-ceramic solid electrolyte (SE) pellets are investigated. The ionic conductivity is enhanced from 1 to 1.5 mS cm−1, while the total interfacial resistance of Li/SE/Li cell is reduced by over an order of magnitude with increasing annealing temperature up to 250 °C. Higher annealing temperature induced formation of a low conductivity Li4P2S6 phase, which increased ionic and interfacial resistances. Storage stability is also improved by annealing treatments. Preparation of exemplary Li4Ti5O12 (LTO) electrodes involving mechanical milling with SE particles undesirably induces formation of a TiS2 phase at the interfaces. Annealing the cells at 250 °C induces further reaction between LTO and SE, increasing TiS2 content and reducing cell rate performance. High reactivity between metal oxides and sulfide-based SE may be an obstacle for the preparation of high performance rechargeable solid state Li ion batteries. J Wei et al., Journal of Power Sources 294, 2015, 494-500 [https://doi.org/10.1016/j.jpowsour.2015.06.074](https://doi.org/10.1016/j.jpowsour.2015.06.074)
In situ TEM observation of electrochemical lithiation of sulfur confined within inner cylindrical pores of carbon nanotubes
H Kim, JT Lee, A Magasinski, K Zhao, Y Liu, G Yushin
Lithium insertion into sulfur confined within 200 nm cylindrical inner pores of individual carbon nanotubes (CNTs) was monitored in situ in a transmission electron microscope (TEM). This electrochemical reaction was initiated at one end of the S-filled CNTs. The material expansion during lithiation was accommodated by the expansion into the remaining empty pore volume and no fracture of the CNT walls was detected. A sharp interface between the initial and lithiated S was observed. The reaction front was flat, oriented perpendicular to the confined S cylinder, and propagated along the cylinder length. Lithiation of S in the proximity of conductive carbon proceeded at the same rate as the one in the center of the pore, suggesting the presence of electron pathways at the Li2S/S interface. Density of states calculations further confirmed this hypothesis. In situ electron diffraction showed a direct phase transformation of S into nanocrystalline Li2S without detectable formation of any intermediates, such as polysulfides and LiS. These important insights may elucidate some of the reaction mechanisms and guide the improvements in the design of C–S nanocomposites for high specific energy Li–S batteries. The proposed use of conductive CNTs with tunable pore diameter as cylindrical reaction vessels for in situ TEM studies of electrochemical reactions proved to be highly advantageous and may help to resolve the ongoing problems in battery technology. H Kim et al., Advanced Energy Materials 5 (24), 2015 [https://doi.org/10.1002/aenm.201501306](https://doi.org/10.1002/aenm.201501306)
Graphene–Li2S–carbon nanocomposite for lithium–sulfur batteries
F Wu, JT Lee, E Zhao, B Zhang, G Yushin
Lithium sulfide (Li2S) with a high theoretical specific capacity of 1166mAh g–1 is a promising cathode material for next-generation Li–S batteries with high specific energy. However, low conductivity of Li2S and polysulfide dissolution during cycling are known to limit the rate performance and cycle life of these batteries. Here, we report on the successful development and application of a nanocomposite cathode comprising graphene covered by Li2S nanoparticles and protected from undesirable interactions with electrolytes. We used a modification of our previously reported low cost, scalable, and high-throughput solution-based method to deposit Li2S on graphene. A dropwise infiltration allowed us to keep the size of the heterogeneously nucleated Li2S particles smaller and more uniform than what we previously achieved. This, in turn, increased capacity utilization and contributed to improved rate performance and stability. The use of a highly conductive graphene backbone further increased cell rate performance. A synergetic combination of a protective layer vapor-deposited on the material during synthesis and in situ formed protective surface layer allowed us to retain ∼97% of the initial capacity of ∼1040 mAh gs–1 at C/2 after over 700 cycles in the assembled cells. The achieved combination of high rate performance and ultrahigh stability is very promising. ACS nano 10 (1), 2015, 1333-1340 [https://doi.org/10.1021/acsnano.5b06716](https://doi.org/10.1021/acsnano.5b06716)
School of Materials Science and Engineering
771 Ferst Dr. NW


text:
Ethnic Favoritism: An Axiom of Politics?
35 Pages Posted: 5 Mar 2015
See all articles by Giacomo De Luca
Giacomo De Luca
Free University of Bozen-Bolzano - Free University of Bozen-Bolzano, Faculty of Economics and Management, Students
Roland Hodler
University of Lucerne
Paul Raschky
Monash University - Department of Economics
Michele Valsecchi
University of Gothenburg - School of Business, Economics and Law
Number of pages: 43 Posted: 27 Jun 2016
Date Written: February 26, 2015
We investigate the prevalence and determinants of ethnic favoritism, i.e., preferential public policies targeted at the political leader's ethnic group. We construct a panel dataset of 2,022 ethnographic regions from 139 countries with annual observations from 1992 to 2012, and use nighttime light intensity as output measure to capture the distributive effects of a wide range of policies. We find robust evidence for ethnic favoritism: the political leaders' ethnographic regions enjoy 10% higher nighttime light intensity. We further find that ethnic favoritism is a global rather than Sub-Saharan African phenomenon, which is present in poor as well as rich countries; that political institutions have a weak effect on ethnic favoritism; that ethnic favoritism is most prevalent in ethnically fractionalized and segregated countries with long established polities; and that ethnic favoritism does not contribute to sustainable development.
Keywords: ethnic favoritism, political leaders, institutions
JEL Classification: D720, R110, J150, O430
De Luca, Giacomo and Hodler, Roland and Raschky, Paul and Valsecchi, Michele, Ethnic Favoritism: An Axiom of Politics? (February 26, 2015). Available at SSRN: https://ssrn.com/abstract=2573621 or http://dx.doi.org/10.2139/ssrn.2573621
Free University of Bozen-Bolzano - Free University of Bozen-Bolzano, Faculty of Economics and Management, Students ( email )
Via Sernesi 1
Bozen-Bolzano (BZ), 39100
Roland Hodler (Contact Author)
University of Lucerne ( email )
Luzern 7, CH - 6000
Monash University - Department of Economics ( email )
Wellington Road
Clayton, Victoria 3
University of Gothenburg - School of Business, Economics and Law ( email )
Vasagatan 1
Goteborg, 40530


text:
package com.miscitems.MiscItemsAndBlocks.Gui.Computer.Programs.Utils.ChatPackets;

import MiscUtils.Network.AbstractPacket;
import MiscUtils.Network.PacketHandler;
import com.miscitems.MiscItemsAndBlocks.Gui.Computer.Programs.Utils.ChannelUtils;
import com.miscitems.MiscItemsAndBlocks.Gui.Computer.Programs.Utils.ChatChannel;
import com.miscitems.MiscItemsAndBlocks.Main.Main;
import cpw.mods.fml.common.network.ByteBufUtils;
import cpw.mods.fml.relauncher.Side;
import io.netty.buffer.ByteBuf;
import net.minecraft.entity.player.EntityPlayer;

public class CloseChannel extends AbstractPacket {

    String name;

    public CloseChannel(){}
    public CloseChannel(String name){
        this.name = name;
    }

    @Override
    public void toBytes(ByteBuf buffer, Side side) {
        ByteBufUtils.writeUTF8String(buffer, name);

    }

    @Override
    public void fromBytes(ByteBuf buffer, Side side) {
        name = ByteBufUtils.readUTF8String(buffer);

    }

    @Override
    public void onMessage(Side side, EntityPlayer player) {

        ChatChannel channel = ChannelUtils.GetChannel(name);

        if(channel.Close){
            ChannelUtils.Channels.remove(channel);
            ChannelUtils.ChannelIds.remove(channel.ChannelId);
        }

        if(side == Side.SERVER){
            PacketHandler.sendToAll(new CloseChannel(name), Main.Utils.channels);
        }

    }
}

redpajama_set_name: RedPajamaGithub