The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical ...performance of batteries that use 4 V high-capacity cathodes. We report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) but also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi0.5Co0.2Mn0.3O2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm2 in a carbonate-based electrolyte. This proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.
The solid-electrolyte interphase (SEI) is pivotal in stabilizing lithium metal anodes for rechargeable batteries. However, the SEI is constantly reforming and consuming electrolyte with cycling. The ...rational design of a stable SEI is plagued by the failure to control its structure and stability. Here we report a molecular-level SEI design using a reactive polymer composite, which effectively suppresses electrolyte consumption in the formation and maintenance of the SEI. The SEI layer consists of a polymeric lithium salt, lithium fluoride nanoparticles and graphene oxide sheets, as evidenced by cryo-transmission electron microscopy, atomic force microscopy and surface-sensitive spectroscopies. This structure is different from that of a conventional electrolyte-derived SEI and has excellent passivation properties, homogeneity and mechanical strength. The use of the polymer-inorganic SEI enables high-efficiency Li deposition and stable cycling of 4 V Li|LiNi
Co
Mn
O
cells under lean electrolyte, limited Li excess and high capacity conditions. The same approach was also applied to design stable SEI layers for sodium and zinc anodes.
Exfoliated 2H molybdenum disulfide (MoS2) has unique properties and potential applications in a wide range of fields, but corresponding studies have been hampered by the lack of effective routes to ...it in bulk quantities. This study presents a rapid and efficient route to obtain exfoliated 2H MoS2, which combines fast sonication-assisted lithium intercalation and infrared (IR) laser-induced phase reversion. We found that the complete lithium intercalation of MoS2 with butyllithium could be effected within 1.5 h with the aid of sonication. The 2H to 1T phase transition that occurs during the lithium intercalation could be also reversed by IR laser irradiation with a DVD optical drive.
Producing liquid fuels such as ethanol from CO
, H
O, and renewable electricity offers a route to store sustainable energy. The search for efficient electrocatalysts for the CO
reduction reaction ...relies on tuning the adsorption strength of carbonaceous intermediates. Here, we report a complementary approach in which we utilize hydroxide and oxide doping of a catalyst surface to tune the adsorbed hydrogen on Cu. Density functional theory studies indicate that this doping accelerates water dissociation and changes the hydrogen adsorption energy on Cu. We synthesize and investigate a suite of metal-hydroxide-interface-doped-Cu catalysts, and find that the most efficient, Ce(OH)
-doped-Cu, exhibits an ethanol Faradaic efficiency of 43% and a partial current density of 128 mA cm
. Mechanistic studies, wherein we combine investigation of hydrogen evolution performance with the results of operando Raman spectroscopy, show that adsorbed hydrogen hydrogenates surface *HCCOH, a key intermediate whose fate determines branching to ethanol versus ethylene.
Solid‐state Li metal battery technology is attractive, owing to the high energy density, long lifespans, and better safety. A key obstacle in this technology is the unstable Li/solid‐state ...electrolyte (SSE) interface involving electrolyte reduction by Li. Herein we report a novel approach based on the use of a nanocomposite consisting of organic elastomeric salts (LiO‐(CH2O)n‐Li) and inorganic nanoparticle salts (LiF, ‐NSO2‐Li, Li2O), which serve as an interphase to protect Li10GeP2S12 (LGPS), a highly conductive but reducible SSE. The nanocomposite is formed in situ on Li via the electrochemical decomposition of a liquid electrolyte, thus having excellent chemical and electrochemical stability, affinity for Li and LGPS, and limited interfacial resistance. XPS depth profiling and SEM show that the nanocomposite effectively restrained the reduction of LGPS. Stable Li electrodeposition over 3000 h and a 200 cycle life for a full cell were achieved.
Incorporating a Li salt‐based nanocomposite interphase layer stabilizes the lithium metal/Li10GeP2S12 solid electrolyte interface. This layer consists of organic elastomeric salts and inorganic nanoparticle salts, which offer chemical stability and low resistance. Its use suppresses Li10GeP2S12 reduction and significantly enhanced stability of Li electrodeposition.
Nitrogen-doped graphene-supported single atoms convert CO
to CO, but fail to provide further hydrogenation to methane - a finding attributable to the weak adsorption of CO intermediates. To regulate ...the adsorption energy, here we investigate the metal-supported single atoms to enable CO
hydrogenation. We find a copper-supported iron-single-atom catalyst producing a high-rate methane. Density functional theory calculations and in-situ Raman spectroscopy show that the iron atoms attract surrounding intermediates and carry out hydrogenation to generate methane. The catalyst is realized by assembling iron phthalocyanine on the copper surface, followed by in-situ formation of single iron atoms during electrocatalysis, identified using operando X-ray absorption spectroscopy. The copper-supported iron-single-atom catalyst exhibits a CO
-to-methane Faradaic efficiency of 64% and a partial current density of 128 mA cm
, while the nitrogen-doped graphene-supported one produces only CO. The activity is 32 times higher than a pristine copper under the same conditions of electrolyte and bias.
The electrocatalytic reduction of carbon dioxide, powered by renewable electricity, to produce valuable fuels and feedstocks provides a sustainable and carbon-neutral approach to the storage of ...energy produced by intermittent renewable sources1. However, the highly selective generation of economically desirable products such as ethylene from the carbon dioxide reduction reaction (CO2RR) remains a challenge2. Tuning the stabilities of intermediates to favour a desired reaction pathway can improve selectivity3-5, and this has recently been explored for the reaction on copper by controlling morphology6, grain boundaries7, facets8, oxidation state9 and dopants10. Unfortunately, the Faradaic efficiency for ethylene is still low in neutral media (60 per cent at a partial current density of 7 milliamperes per square centimetre in the best catalyst reported so far9), resulting in a low energy efficiency. Here we present a molecular tuning strategy-the functionalization of the surface of electrocatalysts with organic molecules-that stabilizes intermediates for more selective CO2RR to ethylene. Using electrochemical, operando/in situ spectroscopic and computational studies, we investigate the influence of a library of molecules, derived by electro-dimerization of arylpyridiniums11, adsorbed on copper. We find that the adhered molecules improve the stabilization of an 'atop-bound' CO intermediate (that is, an intermediate bound to a single copper atom), thereby favouring further reduction to ethylene. As a result of this strategy, we report the CO2RR to ethylene with a Faradaic efficiency of 72 per cent at a partial current density of 230 milliamperes per square centimetre in a liquid-electrolyte flow cell in a neutral medium. We report stable ethylene electrosynthesis for 190 hours in a system based on a membrane-electrode assembly that provides a full-cell energy efficiency of 20 per cent. We anticipate that this may be generalized to enable molecular strategies to complement heterogeneous catalysts by stabilizing intermediates through local molecular tuning.
Atomically dispersed and nitrogen-coordinated single Ni sites (i.e., NiNx moieties) embedded in partially graphitized carbon have emerged as effective catalysts for CO2 electroreduction to CO. ...However, much mystery remains behind the extrinsic and intrinsic factors that govern the overall catalytic CO2 electrolysis performance. Here, we designed a high-performance single Ni site catalyst through elucidating the structural evolution of NiNx sites during thermal activation and other critical external factors (e.g., carbon particle sizes and Ni content) by using Ni–N–C model catalysts derived from nitrogen-doped carbon carbonized from a zeolitic imidazolate framework (ZIF)-8. The N coordination, metal–N bond length, and thermal wrinkling of carbon planes in Ni–N–C catalysts significantly depend on thermal temperatures. Density functional theory (DFT) calculations reveal that the shortening Ni–N bonds in compressively strained NiN4 sites could intrinsically enhance the CO2RR activity and selectivity of the Ni–N–C catalyst. Notably, the NiN3 active sites with optimal local structures formed at higher temperatures (e.g., 1200 °C) are intrinsically more active and CO selective than NiN4, providing a new opportunity to design a highly active catalyst via populating NiN3 sites with increased density. We also studied how morphological factors such as the carbon host particle size and Ni loading alter the final catalyst structure and performance. The implementation of this catalyst in an industrial flow-cell electrolyzer demonstrated an impressive performance for CO generation, achieving a current density of CO up to 726 mA cm−2 with faradaic efficiency of CO above 90%, representing one of the best catalysts for CO2 reduction to CO.
The electrochemical reduction of CO2 has seen many record-setting advances in C2 productivity in recent years. However, the selectivity for ethanol, a globally significant commodity chemical, is ...still low compared to the selectivity for products such as ethylene. Here we introduce diverse binding sites to a Cu catalyst, an approach that destabilizes the ethylene reaction intermediates and thereby promotes ethanol production. We develop a bimetallic Ag/Cu catalyst that implements the proposed design toward an improved ethanol catalyst. It achieves a record Faradaic efficiency of 41% toward ethanol at 250 mA/cm2 and −0.67 V vs RHE, leading to a cathodic-side (half-cell) energy efficiency of 24.7%. The new catalysts exhibit an in situ Raman spectrum, in the region associated with CO stretching, that is much broader than that of pure Cu controls, a finding we account for via the diversity of binding configurations. This physical picture, involving multisite binding, accounts for the enhanced ethanol production for bimetallic catalysts, and presents a framework to design multimetallic catalysts to control reaction paths in CO2 reductions toward desired products.
Li-alloy-based anode materials are very promising for breaking current energy limits of lithium-ion battery technologies. Unfortunately, these materials still suffer from poor solid-electrolyte ...interphase (SEI) stability, resulting in unsatisfied electrochemical performances. The typical SEI formation method, electrochemical decomposition of electrolytes onto the active material surface, lacks a deliberate control of the SEI functions and structures. Here we propose a general method of manipulating the formation process, chemical composition, and morphology of the SEI for Li-alloy anodes, using Si and Ge nanoparticle anodes as the platform. The SEI was fabricated through a covalent anchoring of multiple functional components onto the active material surface, followed by electrochemical decomposition of the functional components and conventional electrolyte. Click reaction, serving as the covalent anchoring approach, allows an accurate control of the SEI composition and structure at the molecular level through tuning the chemical structure and amount of variety of functional components and provides an intimate contact between the SEI and the Li-alloy material surface contributed by the covalent bonding. The optimized Si nanoparticle SEI, functionalized by a unique combination of diverse components and containing a high concentration of organic components attributed to the preanchored functional components, presented a stable composition and durable morphology during cycling and led to an improved first cycle efficiency of Si nanoparticle anodes and its long cycle life in a full cell. This general method displays potential benefits to construct stable SEIs for other Li-alloy anodes.
PDF
