Lithium-ion batteries have had a profound impact on our daily life, but inherent limitations make it difficult for Li-ion chemistries to meet the growing demands for portable electronics, electric vehicles and grid-scale energy storage. Therefore, chemistries beyond Li-ion are currently being investigated and need to be made viable for commercial applications. The use of metallic Li is one of the most favoured choices for next-generation Li batteries, especially Li-S and Li-air systems. After falling into oblivion for several decades because of safety concerns, metallic Li is now ready for a revival, thanks to the development of investigative tools and nanotechnology-based solutions. In this Review, we first summarize the current understanding on Li anodes, then highlight the recent key progress in materials design and advanced characterization techniques, and finally discuss the opportunities and possible directions for future development of Li anodes in applications.

Reviving the lithium metal anode for high-energy batteries

We have developed a transparent organic polymeric material that can repeatedly mend or "re-mend" itself under mild conditions. The material is a tough solid at room temperature and below with mechanical properties equaling those of commercial epoxy resins. At temperatures above 120 degrees C, approximately 30% (as determined by solid-state nuclear magnetic resonance spectroscopy) of "intermonomer" linkages disconnect but then reconnect upon cooling, This process is fully reversible and can be used to restore a fractured part of the polymer multiple times, and it does not require additional ingredients such as a catalyst, additional monomer, or special surface treatment of the fractured interface.

https://science.sciencemag.org/content/sci/295/5560/1698.full.pdf

A Thermally Re-mendable Cross-Linked Polymeric Material

Human skin is a remarkable organ. It consists of an integrated, stretchable network of sensors that relay information about tactile and thermal stimuli to the brain, allowing us to maneuver within our environment safely and effectively. Interest in large-area networks of electronic devices inspired by human skin is motivated by the promise of creating autonomous intelligent robots and biomimetic prosthetics, among other applications. The development of electronic networks comprised of flexible, stretchable, and robust devices that are compatible with large-area implementation and integrated with multiple functionalities is a testament to the progress in developing an electronic skin (e-skin) akin to human skin. E-skins are already capable of providing augmented performance over their organic counterpart, both in superior spatial resolution and thermal sensitivity. They could be further improved through the incorporation of additional functionalities (e.g., chemical and biological sensing) and desired properties (e.g., biodegradability and self-powering). Continued rapid progress in this area is promising for the development of a fully integrated e-skin in the near future.

25th Anniversary Article: The Evolution of Electronic Skin (E-Skin): A Brief History, Design Considerations, and Recent Progress

PEEK Biomaterials in Trauma, Orthopedic, and Spinal Implants

Hydrogenation is a core technology in chemical synthesis. High rates and selectivities are attainable only by the coordination of structurally well-designed catalysts and suitable reaction conditions. The newly devised [RuCl(2)(phosphane)(2)(1,2-diamine)] complexes are excellent precatalysts for homogeneous hydrogenation of simple ketones which lack any functionality capable of interacting with the metal center. This catalyst system allows for the preferential reduction of a C=O function over a coexisting C=C linkage in a 2-propanol solution containing an alkaline base. The hydrogenation tolerates many substituents including F, Cl, Br, I, CF(3), OCH(3), OCH(2)C(6)H(5), COOCH(CH(3))(2), NO(2), NH(2), and NRCOR as well as various electron-rich and -deficient heterocycles. Furthermore, stereoselectivity is easily controlled by the electronic and steric properties (bulkiness and chirality) of the ligands as well as the reaction conditions. Diastereoselectivities observed in the catalytic hydrogenation of cyclic and acyclic ketones with the standard triphenylphosphane/ethylenediamine combination compare well with the best conventional hydride reductions. The use of appropriate chiral diphosphanes, particularly BINAP compounds, and chiral diamines results in rapid and productive asymmetric hydrogenation of a range of aromatic and heteroaromatic ketones and gives a consistently high enantioselectivity. Certain amino and alkoxy ketones can be used as substrates. Cyclic and acyclic alpha,beta-unsaturated ketones can be converted into chiral allyl alcohols of high enantiomeric purity. Hydrogenation of configurationally labile ketones allows for the dynamic kinetic discrimination of diastereomers, epimers, and enantiomers. This new method shows promise in the practical synthesis of a wide variety of chiral alcohols from achiral and chiral ketone substrates. Its versatility is manifested by the asymmetric synthesis of some biologically significant chiral compounds. The high rate and carbonyl selectivity are based on nonclassical metal-ligand bifunctional catalysis involving an 18-electron amino ruthenium hydride complex and a 16-electron amido ruthenium species.

https://onlinelibrary.wiley.com/doi/pdf/10.1002/1521-3773%2820010105%2940%3A1%3C40%3A%3AAID-ANIE40%3E3.0.CO%3B2-5

Asymmetric Catalysis by Architectural and Functional Molecular Engineering: Practical Chemo‐ and Stereoselective Hydrogenation of Ketones

Structural polymers are susceptible to damage in the form of cracks, which form deep within the structure where detection is difficult and repair is almost impossible. Cracking leads to mechanical degradation of fibre-reinforced polymer composites; in microelectronic polymeric components it can also lead to electrical failure. Microcracking induced by thermal and mechanical fatigue is also a long-standing problem in polymer adhesives. Regardless of the application, once cracks have formed within polymeric materials, the integrity of the structure is significantly compromised. Experiments exploring the concept of self-repair have been previously reported, but the only successful crack-healing methods that have been reported so far require some form of manual intervention. Here we report a structural polymeric material with the ability to autonomically heal cracks. The material incorporates a microencapsulated healing agent that is released upon crack intrusion. Polymerization of the healing agent is then triggered by contact with an embedded catalyst, bonding the crack faces. Our fracture experiments yield as much as 75% recovery in toughness, and we expect that our approach will be applicable to other brittle materials systems (including ceramics and glasses).

Autonomic healing of polymer composites

Microencapsulated healing agents that possess adequate strength, long shelf-life and excellent bonding to the host material are required for self-healing materials. Urea-formaldehyde microcapsules containing dicyclopentadiene were prepared by in situ polymerization in an oil-in-water emulsion that meet these requirements for self-healing epoxy. Microcapsules of 10-1000 microm in diameter were produced by appropriate selection of agitation rate in the range of 200-2000 rpm. A linear relation exists between log(mean diameter) and log(agitation rate). Surface morphology and shell wall thickness were investigated by optical and electron microscopy. Microcapsules are composed of a smooth 160-220 nm inner membrane and a rough, porous outer surface of agglomerated urea-formaldehyde nanoparticles. Surface morphology is influenced by pH of the reacting emulsion and interfacial surface area at the core-water interface. High yields (80-90%) of a free flowing powder of spherical microcapsules were produced with a fill content of 83-92 wt% as determined by CHN analysis.

/pdf/in-situ-poly-urea-formaldehyde-microencapsulation-of-4p1ii8jlau.pdf

In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Microencapsulated dicyclopentadiene (DCPD) healing agent and Grubbs' Ru catalyst are incorporated into an epoxy matrix to produce a polymer composite capable of self-healing. The fracture toughness and healing efficiency of this composite are measured using a tapered double-cantilever beam (TDCB) specimen. Both the virgin and healed fracture toughness depend strongly on the size and concentration of microcapsules added to the epoxy. Fracture of the neat epoxy is brittle, exhibiting a mirror fracture surface. Addition of DCPD-filled urea-formaldehyde (UF) microcapsules yields up to 127% increase in fracture toughness and induces a change in the fracture plane morphology to hackle markings. The fracture toughness of epoxy with embedded microcapsules is much greater than epoxy samples with similar concentrations of silica microspheres or solid UF polymer particles. The increased toughening associated with fluid-filled microcapsules is attributed to increased hackle markings as well as subsurface microcracking not observed for solid particle fillers. Overall the embedded microcapsules provide two independent effects: the increase in virgin fracture toughness from general toughening and the ability to self-heal the virgin fracture event.

/pdf/microcapsule-induced-toughening-in-a-self-healing-polymer-575cwdd9r2.pdf

Microcapsule induced toughening in a self-healing polymer composite

Microencapsulated healing agents that possess adequate strength, long shelf-life and excellent bonding to the host material are required for self-healing materials. Urea-formaldehyde microcapsules containing dicyclopentadiene were prepared by in situ polymerization in an oil-in-water emulsion that meet these requirements for self-healing epoxy. Microcapsules of 10–1000 μm in diameter were produced by appropriate selection of agitation rate in the range of 200–2000 rpm. A linear relation exists between log(mean diameter) and log(agitation rate). Surface morphology and shell wall thickness were investigated by optical and electron microscopy. Microcapsules are composed of a smooth 160–220 nm inner membrane and a rough, porous outer surface of agglomerated urea-formaldehyde nanoparticles. Surface morphology is influenced by pH of the reacting emulsion and interfacial surface area at the core-water interface. High yields (80–90%) of a free flowing powder of spherical microcapsules were produced with a fill content of 83–92 wt% as determined by CHN analysis.

/pdf/in-situpoly-urea-formaldehyde-microencapsulation-of-466boorzzt.pdf

In situpoly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Inspired by biological systems in which damage triggers an autonomic healing response, a polymer composite material that can heal itself when cracked has been developed. In this paper we summarize the self-healing concept for polymeric composite materials and we investigate fracture mechanics issues consequential to the development and optimization of this new class of material. The self-healing material under investigation is an epoxy matrix composite, which incorporates a microencapsulated healing agent that is released upon crack intrusion. Polymerization of the healing agent is triggered by contact with an embedded catalyst. The effects of size and concentration of the catalyst and microcapsules on fracture toughness and healing efficiency are investigated. In all cases, the addition of microcapsules significantly toughens the neat epoxy. Once healed, the self-healing polymer exhibits the ability to recover as much as 90 percent of its virgin fracture toughness.

/pdf/fracture-testing-of-a-self-healing-polymer-composite-2njgdp0rxt.pdf

Eric Brown

Papers

Autonomic healing of polymer composites

In situ poly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Microcapsule induced toughening in a self-healing polymer composite

In situpoly(urea-formaldehyde) microencapsulation of dicyclopentadiene

Fracture testing of a self-healing polymer composite