Manufacturing molecule-based functional elements directly at device interfaces is a frontier in bottom-up materials engineering. A longstanding challenge in the field is the covalent stabilization of pre-assembled molecular architectures to afford nanodevice components. Here, we employ the controlled supramolecular self-assembly of anthracene derivatives on a hexagonal boron nitride sheet, to generate nanographene wires through photo-crosslinking and thermal annealing. Specifically, we demonstrate µm-long nanowires with an average width of 200 nm, electrical conductivities of 106 S m-1 and breakdown current densities of 1011 A m-2. Joint experiments and simulations reveal that hierarchical self-assembly promotes their formation and functional properties. Our approach demonstrates the feasibility of combined bottom-up supramolecular templating and top-down manufacturing protocols for graphene nanomaterials and interconnects, towards integrated carbon nanodevices.
A high-power P2-Na2/3(Mn1/2Fe1/4Co1/4)O2 (P2-MFC) cathode material is synthesized and investigated for Na-ion batteries. P2 type stacking is observed for a wide range of Na content (0.34 < x < 0.95). Even at 30 C rate a discharge capacity of 130 mAh g−1 is maintained, which is currently the highest rate performance among Na ion intercalation compounds. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
Abstract Despite the potentially higher energy density and improved safety of solid-state batteries (SSBs) relative to Li-ion batteries, failure due to Li-filament penetration of the solid electrolyte and subsequent short circuit remains a critical issue. Herein, we show that Li-filament growth is suppressed in solid-electrolyte pellets with a relative density beyond ~95%. Below this threshold value, however, the battery shorts more easily as the density increases due to faster Li-filament growth within the percolating pores in the pellet. The microstructural properties (e.g., pore size, connectivity, porosity, and tortuosity) of $$75\%{{{{{\rm{L}}}}}}{{{{{{\rm{i}}}}}}}_{2}{{{{{\rm{S}}}}}}-25\%{{{{{{\rm{P}}}}}}}_{2}{{{{{{\rm{S}}}}}}}_{5}$$ 75%Li2S−25%P2S5 with various relative densities are quantified using focused ion beam–scanning electron microscopy tomography and permeability tests. Furthermore, modeling results provide details on the Li-filament growth inside pores ranging from 0.2 to 2 μm in size. Our findings improve the understanding of the failure modes of SSBs and provide guidelines for the design of dendrite-free SSBs.
Despite ongoing efforts aimed at increasing energy density in all-solid-state batteries (ASSBs), the optimal composite cathode morphology, which requires minimal volume change, small void development, and good interfacial contact, remains a significant concern within the community. In this work, we focus on the theoretical investigation of the aforementioned mechanical defects in the composite cathode during electrochemical cycling. It is demonstrated that these mechanical defects are highly dependent on the solid electrolyte (SE) material properties, the external stack pressure, and the cathode active material (CAM) loading. The following conclusions are highlighted in this study: (1) Higher CAM loading (>50 vol %) causes an increase in mechanical defects, including large cathode volume change (>5%), contact loss (50%), and porosity (>1%). (2) High external stack pressure up to 7 MPa reduces mechanical defects while preventing internal fracture in the cathode. (3) Soft SE materials with small Young's modulus (<10 GPa) and low hardness (<2 GPa) can significantly minimize these mechanical defects during cycling. (4) A design strategy is proposed for high CAM loading with minimal mechanical defects when different SE materials are utilized in the composite cathode, including an oxide-type SE, a sulfide-type SE, and a halide-type SE. The research provides specific guidelines to optimize the composite cathode in terms of its mechanical properties. These guidelines broaden the design approach toward improving the performance of ASSBs, by highlighting the importance of considering the mechanical properties of battery materials.
Na Super Ionic Conductor (NASICON) materials are an important class of solid-state electrolytes owing to their high ionic conductivity and superior chemical and electrochemical stability. In this paper, we combine first-principles calculations, experimental synthesis and testing, and natural language-driven text-mined historical data on NASICON ionic conductivity to achieve clear insights into how chemical composition influences the Na-ion conductivity. These insights, together with a high-throughput first-principles analysis of the compositional space over which NASICONs are expected to be stable, lead to the successful synthesis and electrochemical investigation of several new NASICONs solid-state conductors. Among these, a high ionic conductivity of 1.2 mS cm-1 could be achieved at 25 °C. We find that the ionic conductivity increases with average metal size up to a certain value and that the substitution of PO4 polyanions by SiO4 also enhances the ionic conductivity. While optimal ionic conductivity is found near a Na content of 3 per formula unit, the exact optimum depends on other compositional variables. Surprisingly, the Na content enhances the ionic conductivity mostly through its effect on the activation barrier, rather than through the carrier concentration. These deconvoluted design criteria may provide guidelines for the design of optimized NASICON conductors.
Abstract Energy storage with high energy density and low cost has been the subject of a decades-long pursuit. Sodium-ion batteries are well expected because they utilize abundant resources. However, the lack of competent cathodes with both large capacities and long cycle lives prevents the commercialization of sodium-ion batteries. Conventional cathodes with hexagonal-P2-type structures suffer from structural degradations when the sodium content falls below 33%, or when the integral anions participate in gas evolution reactions. Here, we show a “pillar-beam” structure for sodium-ion battery cathodes where a few inert potassium ions uphold the layer-structured framework, while the working sodium ions could diffuse freely. The thus-created unorthodox orthogonal-P2 K 0.4 [Ni 0.2 Mn 0.8 ]O 2 cathode delivers a capacity of 194 mAh/g at 0.1 C, a rate capacity of 84% at 1 C, and an 86% capacity retention after 500 cycles at 1 C. The addition of the potassium ions boosts simultaneously the energy density and the cycle life.
2LiX-GaF3 (X = Cl, Br, I) electrolytes offer favorable features for solid-state batteries: mechanical pliability and high conductivities. However, understanding the origin of fast ion transport in 2LiX-GaF3 has been challenging. The ionic conductivity order of 2LiCl-GaF3 (3.20 mS/cm) > 2LiBr-GaF3 (0.84 mS/cm) > 2LiI-GaF3 (0.03 mS/cm) contradicts binary LiCl (10-12 S/cm) < LiBr (10-10 S/cm) < LiI (10-7 S/cm). Using multinuclear 7Li, 71Ga, 19F solid-state nuclear magnetic resonance and density functional theory simulations, we found that Ga(F,X)n polyanions boost Li+-ion transport by weakening Li+-X- interactions via charge clustering. In 2LiBr-GaF3 and 2LiI-GaF3, Ga-X coordination is reduced with decreased F participation, compared to 2LiCl-GaF3. These insights will inform electrolyte design based on charge clustering, applicable to various ion conductors. This strategy could prove effective for producing highly conductive multivalent cation conductors such as Ca2+ and Mg2+, as charge clustering of carboxylates in proteins is found to decrease their binding to Ca2+ and Mg2+.
Lithium metal batteries using solid electrolytes are considered to be the next-generation lithium batteries due to their enhanced energy density and safety. However, interfacial instabilities between Li-metal and solid electrolytes limit their implementation in practical batteries. Herein, Li-metal batteries using tailored garnet-type Li
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