A Chemically Bonded Ultraconformal Layer between the Elastic Solid Electrolyte and Lithium Anode for High‐performance Lithium Metal BatteriesYang, Na; Cui, Yujie; Su, Hang; Peng, Jiaying; Shi, Yongzheng; Niu, Jin; Wang, Feng
doi: 10.1002/anie.202304339pmid: 37158048
Although high ionic conductivities have been achieved in most solid‐state electrolytes used in lithium metal batteries (LMBs), rapid and stable lithium‐ion transport between solid‐state electrolytes and lithium anodes remains a great challenge due to the high interfacial impedances and infinite volume changes of metallic lithium. In this work, a chemical vapor‐phase fluorination approach is developed to establish a lithiophilic surface on rubber‐derived electrolytes, which results in the formation of a resilient, ultrathin, and mechanically integral LiF‐rich layer after electrochemical cycling. The resulting ultraconformal layer chemically connects the electrolyte and lithium anode and maintains dynamic contact during operation, thus facilitating rapid and stable lithium‐ion transport across interfaces, as well as promoting uniform lithium deposition and inhibiting side reactions between electrolyte components and metallic lithium. LMBs containing the novel electrolyte have an ultralong cycling life of 2500 h and deliver a high critical current density of 1.1 mA cm−2 in lithium symmetric cells as well as showing good stability over 300 cycles in a full cell.
Bispalladium(II) Complexes of di‐p‐Pyrirubyrin Derivatives as Promising Near‐Infrared Photoacoustic DyesHurej, Karolina; Oszczęda, Weronika; Opas, Ewelina; Zelewski, Szymon J.; Pawlicki, Miłosz; Białek, Michał J.; Orzeł, Łukasz; Latos‐Grażyński, Lechosław
doi: 10.1002/anie.202303394pmid: 37178418
The insertion of palladium(II) into di‐p‐pyrirubyrin results in mutually convertible bimetallic complexes. Post‐synthetic functionalization of one of them yielded bispalladium(II) dioxo‐di‐p‐pyrirubyrin and, after demetallation, dioxo‐di‐p‐pyrirubyrin, introducing for the first time the α,β′‐pyridin‐2‐one unit into the macrocyclic frame. Bispalladium(II) di‐p‐pyrirubyrin 6, bispalladium(II) dioxo‐di‐p‐pyrirubyrin 9, and dioxo‐di‐p‐pyrirubyrin 10 absorb and emit light around 1000 nm and are characterized by high photostability. Thus, they are promising candidates for near‐infrared photoacoustic dyes, ideally targeting (9) the wavelength of Yb‐based fiber lasers. The incorporation of an α,β′‐pyridine moiety into expanded porphyrins opens a highly interesting area of research due to the attractive optical and coordination properties of the resulting molecules.
High‐throughput Synthesis of Solution‐Processable van der Waals Heterostructures through ElectrochemistryShi, Huanhuan; Li, Mengmeng; Fu, Shuai; Neumann, Christof; Li, Xiaodong; Niu, Wenhui; Lee, Yunji; Bonn, Mischa; Wang, Hai I.; Turchanin, Andrey; Shaygan Nia, Ali; Yang, Sheng; Feng, Xinliang
doi: 10.1002/anie.202303929pmid: 37163208
Two‐dimensional van der Waals heterostructures (2D vdWHs) have recently gained widespread attention because of their abundant and exotic properties, which open up many new possibilities for next‐generation nanoelectronics. However, practical applications remain challenging due to the lack of high‐throughput techniques for fabricating high‐quality vdWHs. Here, we demonstrate a general electrochemical strategy to prepare solution‐processable high‐quality vdWHs, in which electrostatic forces drive the stacking of electrochemically exfoliated individual assemblies with intact structures and clean interfaces into vdWHs with strong interlayer interactions. Thanks to the excellent combination of strong light absorption, interfacial charge transfer, and decent charge transport properties in individual layers, thin‐film photodetectors based on graphene/In2Se3 vdWHs exhibit great promise for near‐infrared (NIR) photodetection, owing to a high responsivity (267 mA W−1), fast rise (72 ms) and decay (426 ms) times under NIR illumination. This approach enables various hybrid systems, including graphene/In2Se3, graphene/MoS2 and graphene/MoSe2 vdWHs, providing a broad avenue for exploring emerging electronic, photonic, and exotic quantum phenomena.
Merging Styrene and Diene Structures to a Cyclic Diene: Anionic Polymerization of 1‐Vinylcyclohexene (VCH)Hahn, Christoph; Rauschenbach, Moritz; Frey, Holger
doi: 10.1002/anie.202302907pmid: 37186346
We report the first anionic polymerization of 1‐vinylcyclohexene (VCH). This structure may be considered as an intermediate between dienes and styrene. The polymerization of this cyclic 1,2‐disubstituted 1,3‐diene proceeded quantitatively in cyclohexane at 25 °C with sec‐butyllithium as an initiator. The obtained polymers have well‐controlled molecular weights in the range of 5 to 142 kg mol−1, controlled by the molar ratio of monomer and initiator, with narrow molecular weight distributions (Đ<1.07–1.20). In situ 1H NMR kinetic characterization revealed a weak gradient structure for the copolymers of styrene and VCH, (rSty=2.55, rVCH=0.39). P(VCH) obtained in cyclohexane with sec‐BuLi as an initiator showed both 1,4‐ and 3,4‐incorporation mode (ratio: 64 : 36). It was demonstrated that the microstructure of the resulting P(VCH) can be altered by the addition of a modifier (THF), resulting in increasing 3,4‐microstructure (up to 78 %) and elevated glass‐transition temperature up to 89 °C. Thus, the monomer VCH polymerizes carbanionically like a diene, however leading to rigid polymers with high glass transition temperature, which provides interesting options for combination with other dienes to well‐defined polymer architectures and materials.
Regulation of Atomic Fe‐Spin State by Crystal Field and Magnetic Field for Enhanced Oxygen Electrocatalysis in Rechargeable Zinc‐Air BatteriesWang, Yibo; Meng, Pengyu; Yang, Zhaohui; Jiang, Min; Yang, Jian; Li, Huanxin; Zhang, Jiao; Sun, Baode; Fu, Chaopeng
doi: 10.1002/anie.202304229pmid: 37139572
Highly‐active and low‐cost bifunctional electrocatalysts for oxygen reduction and evolution are essential in rechargeable metal‐air batteries, and single atom catalysts with Fe−N−C are promising candidates. However, the activity still needs to be boosted, and the origination of spin‐related oxygen catalytic performance is still uncertain. Herein, an effective strategy to regulate local spin state of Fe−N−C through manipulating crystal field and magnetic field is proposed. The spin state of atomic Fe can be regulated from low spin to intermediate spin and to high spin. The cavitation of dxz and dyz orbitals of high spin FeIII can optimize the O2 adsorption and promote the rate‐determining step (*O2 to *OOH). Benefiting from these merits, the high spin Fe−N−C electrocatalyst displays the highest oxygen electrocatalytic activities. Furthermore, the high spin Fe−N−C‐based rechargeable zinc‐air battery displays a high power density of 170 mW cm−2 and good stability.
Multi‐Step Nucleation of a Crystalline Silicate Framework via a Structurally Precise Prenucleation ClusterJin, Biao; Chen, Ying; Tao, Jinhui; Lachowski, Kacper J.; Bowden, Mark E.; Zhang, Zihao; Pozzo, Lilo D.; Washton, Nancy M.; Mueller, Karl T.; De Yoreo, James J.
doi: 10.1002/anie.202303770pmid: 37145989
Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre‐organized multi‐ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi‐step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small‐angle X‐ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q38 polyanions formed through cross‐linking and polymerization of smaller silicate monomers and other oligomers. These Q38 are stabilized by hydrogen bonds with surrounding H2O and tetramethylammonium ions (TMA+). When Q38 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)x(Q38)⋅n H2O](x−8) clathrate complexes into step edges on the crystals.