2021 New's Items

Near-complete depolymerization of polyesters with nano-dispersed enzymes

DelRe C
Jiang Y
Kang P
Kwon J
Hall A
Jayapurna I
Ruan Z
Ma L
Zolkin K
Li T
Scown CD
2021

Successfully interfacing enzymes and biomachinery with polymers affords on-demand modification and/or programmable degradation during the manufacture, utilization and disposal of plastics, but requires controlled biocatalysis in solid matrices with macromolecular substrates1,...

Crystallization of nanoparticles induced by precipitation of trace polymeric additives

Qian Y
Da Silva A
Yu E
Anderson CL
Liu Y
Theis W
Ercius P
Xu T
2021

Orthogonal to guided growth of nanoparticle (NP) crystals using DNA or supramolecules, a trace amount of polymeric impurities (<0.1 wt.%) leads to reproducible, rapid growth of 3D NP crystals in solution and on patterned substrates with high yield. When polymers preferentially precipitate on the NP surfaces, small NP clusters form and serve as nuclei for NP crystal growth in dilute solutions. This precipitation-induced NP crystallization process is applicable for a range of polymers, and the resultant 3-D NP crystals are tunable by varying polymeric additives loading, solvent...

Diversifying Composition Leads to Hierarchical Composites with Design Flexibility and Structural Fidelity

Ma L,
Huang H
Vargo E
Huang J
Anderson CL
Chen T
Kuzmenko I
Ilavsky J
Wang C
Liu Y
Ercius P
2021

Although significant progress has been made in the self-assembly of nanostructures, present successes heavily rely on precision in building block design, composition, and pair interactions. These requirements fundamentally limit our ability to synthesize macroscopic materials where the likelihood of impurity inclusion escalates and, more importantly, to access molecular-to-nanoscopic-to-microscopic-to-macroscopic hierarchies, since the types and compositions of building blocks vary at each stage. Inspired by biological blends and high-entropy alloys, we hypothesize that diversifying...

Orbital Angular Momentum from Self-Assembled Concentric Nanoparticle Rings

Vargo E
Evans KM
Wang Q
Sattler A
Qian Y
Yao J
Xu T
2021

Ring-shaped nanostructures can focus, filter, and manipulate electromagnetic waves, but are challenging to incorporate into devices using standard nanofabrication techniques. Directed self-assembly (DSA) of block copolymers (BCPs) on lithographically patterned templates has successfully been used to fabricate concentric rings and spirals as etching masks. However, this method is limited by BCP phase behavior and material selection. Here, a straightforward approach to generate ring-shaped nanoparticle assemblies in thin films of supramolecular nanocomposites is demonstrated. DSA is...

Synthesis of model sodium sulfide films

McAuliffe RD
Petrova V
McDermott MJ
Tyler JL
Self EC
Persson KA
Liu P
Veith GM
2021

We report the direct deposition of model sodium sulfide films by RF magnetron sputtering from Na2S and Na2S2 deposition targets. Analytical characterization and electrochemical cycling indicate that the deposited films are amorphous with stoichiometries that correspond to Na2S3 and Na2S2 formed from the Na2S and Na2S2 targets,...

Silicon Anodes with Improved Calendar Life Enabled By Multivalent Additives

Zhang Y
Li X
Sivonxay E
Wen J
Persson KA
Vaughey JT
Key B
Dogan F
2021

Silicon is widely recognized as the most promising upgrade for graphite anodes due to its much higher capacity, natural abundance, and ability to be directly applied in the slurry-based, roll-to-roll production lines. However, in addition to the fast capacity decay, silicon anodes also suffer from inferior calendar life in practical applications due to the unstable solid-electrode interface (SEI). Until now, strategies to effectively improve the calendar life by tailored SEIs remain largely unclear, especially in high-Si content, zero-graphite anodes. Here, silicon anodes with...

Selectivity in Yttrium Manganese Oxide Synthesis via Local Chemical Potentials in Hyperdimensional Phase Space

Todd PK
McDermott MJ
Rom CL
Corrao AA
Denney JJ
Dwaraknath SS
Khalifah PG
Persson KA
Neilson JR
2021

In sharp contrast to molecular synthesis, materials synthesis is generally presumed to lack selectivity. The few known methods of designing selectivity in solid-state reactions have limited scope, such as topotactic reactions or strain stabilization. This contribution describes a general approach for searching large chemical spaces to identify selective reactions. This novel approach explains the ability of a nominally “innocent” Na2CO3 precursor to enable the metathesis synthesis of single-phase Y2Mn...

Role of Fluorine in Chemomechanics of Cation-Disordered Rocksalt Cathodes

Chen D
Zhang J
Jiang Z
Wei C
Burns J
Li L
Wang C
Persson KA
Liu Y
Chen G
2021

The role of nanoscale chemomechanical behavior in the macroscopic performance of functional materials is well recognized. For lithium-ion battery cathodes, tremendous effort has been devoted to the development of new chemistry and structure, yet fundamental understanding of the correlation between redox processes and mechanical properties of the novel materials lags behind. In the present study, we prepare large discrete single grains of Li-excess cation-disordered rocksalts (DRX) and investigate their chemomechanical behavior at the particle level, using nanoresolution X-ray...

Quantum chemical calculations of lithium-ion battery electrolyte and interphase species

Spotte-Smith EWC
Blau SM
Xie X
Patel HD
Wen M
Wood B
Dwaraknath S
Perssona KA
2021

Lithium-ion batteries (LIBs) represent the state of the art in high-density energy storage. To further advance LIB technology, a fundamental understanding of the underlying chemical processes is required. In particular, the decomposition of electrolyte species and associated formation of the solid electrolyte interphase (SEI) is critical for LIB performance. However, SEI formation is poorly understood, in part due to insufficient exploration of the vast reactive space. The Lithium-Ion Battery Electrolyte (LIBE) dataset reported here aims to provide accurate first-principles data to...

Quantifying Species Populations in Multivalent Borohydride Electrolytes

Hahn NT
Self J
Han KS
Murugesan V
Mueller KT
Persson KA
Zavadil KR
2021

Multivalent batteries represent an important beyond Li-ion energy storage concept. The prospect of calcium batteries, in particular, has emerged recently due to novel electrolyte demonstrations, especially that of a ground-breaking combination of the borohydride salt Ca(BH4)2 dissolved in tetrahydrofuran. Recent analysis of magnesium and calcium versions of this electrolyte led to the identification of divergent speciation pathways for Mg2+ and Ca2+ despite identical anions and...