Performance improvement of lithium manganese phosphate by controllable morphology tailoring with acid-engaged nano engineering.

Olivine-type lithium manganese phosphate (LiMnPO4) has been considered as a promising cathode for next-generation Li-ion batteries. Preparation of high-performance LiMnPO4 still remains a great challenge because of its intrinsically low Li-ion/electronic conductivity. In this work, significant performance enhancement of LiMnPO4 has been realized by a controllable acid-engaged morphology tailoring from large spindles into small plates. We find that acidity plays a critical role in altering the morphology of the LiMnPO4 crystals. We also find that size decrease and plate-like morphology are beneficial for the performance improvement of LiMnPO4. Among the plate-like samples, the one with the smallest size shows the best electrochemical performance. After carbon coating, it can deliver high discharge capacities of 104.0 mAh g(-1) at 10 C and 85.0 mAh g(-1) at 20 C. After 200 cycles at 1 C, it can still maintain a high discharge capacity of 106.4 mAh g(-1), showing attractive applications in high-power and high-energy Li-ion batteries.

Reduced graphene oxide-induced recrystallization of NiS nanorods to nanosheets and the improved Na-storage properties.

Preparation of two-dimensional (2D) graphene-like materials is currently an emerging field in materials science since the discovery of single-atom-thick graphene prepared by mechanical cleavage. In this work, we proposed a new method to prepare 2D NiS, where reduced graphene oxide (rGO) was found to induce the recrystallization of NiS from nanorods to nanosheets in a hydrothermal process. The process and mechanism of recrystallization have been clarified by various characterization techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDS) mapping, and X-ray photoelectron spectroscopy (XPS). The characterization of ex situ NiS/rGO products by SEM and EDS mapping indicates that the recrystallization of NiS from nanorods to nanosheets is realized actually through an exfoliation process, while the characterization of in situ NiS/rGO products by SEM, TEM, and EDS mapping reveals the exfoliation process. The XPS result demonstrates that hydrothermally assisted chemical bonding occurs between NiS and rGO, which induces the exfoliation of NiS nanorods into nanosheets. The obtained NiS/rGO composite shows promising Na-storage properties.

Unexpected Low-Temperature Performance of Li-O2 Cells with Inhibited Side Reactions.

In this work, we found that the side reactions of both the Li anode and cathode with the electrolyte can be obviously alleviated at low temperature. This favorable merit enables long cycle life of the Li-O2 cells at low temperature. At 0 °C, the cells can sustain stable cycling of 279 and 1025 cycles at 400 mA g-1 with limited capacities of 1000 and 500 mA h g-1, respectively. Even at -20 °C, the cell can be stably cycled for 83 cycles at 200 mA g-1 with a limited capacity of 500 mA h g-1.

Controlled Growth of Li2O2 by Cocatalysis of Mobile Pd and Co3O4 Nanowire Arrays for High-Performance Li-O2 Batteries.

For Li-O2 batteries, a challenge still remains to achieve high discharge capacity and easy decomposition of the discharge product (Li2O2) simultaneously. In this work, conformal growth of thin-layered Li2O2 on Co3O4 nanowire arrays (Co3O4 NAs) during discharge is realized through the cocatalytic effect of solid/immobile Co3O4 NAs and mobile Pd nanocrystals (Pd NCs), rendering easy decomposition of Li2O2 during recharge. Meanwhile, high discharge capacity is also ensured with unique array-type design of the catalytic cathode despite the surface growth mode of Li2O2. The Li-O2 cells can deliver a high discharge capacity of 5337 mAh g-1 and keep a stable cycling of 258 cycles at a limited capacity of 500 mAh g-1. The achievement of excellent electrochemical performance is attributed to the highly efficient cocatalytic ability of Co3O4 NAs and Pd NCs as well as the desirable array-type architecture of the catalytic electrode free of carbon and binder. The cocatalytic mechanism of Co3O4 NAs and Pd NCs is clarified by systematic electrochemical tests, microstructural analyses, and ζ-potential measurements.

High-Performance Li-O2 Batteries with Controlled Li2O2 Growth in Graphene/Au-Nanoparticles/Au-Nanosheets Sandwich.

The working of nonaqueous Li-O2 batteries relies on the reversible formation/decomposition of Li2O2 which is electrically insulating and reactive with carbon and electrolyte. Realizing controlled growth of Li2O2 is a prerequisite for high performance of Li-O2 batteries. In this work, a sandwich-structured catalytic cathode is designed: graphene/Au-nanoparticles/Au-nanosheets (G/Au-NP/Au-NS) that enables controlled growth of Li2O2 spatially and structurally. It is found that thin-layer Li2O2 (below 10 nm) can grow conformally on the surface of Au NPs confined in between graphene and Au NSs. This unique crystalline behavior of Li2O2 effectively relieves or defers the electrode deactivation with Li2O2 accumulation and largely reduces the contact of Li2O2 with graphene and electrolyte. As a result, Li-O2 batteries with the G/Au-NP/Au-NS cathode exhibit superior electrochemical performance. A stable cycling of battery can last 300 times at 400 mA g-1 when the capacity is limited at 500 mAh g-1. This work provides a practical design of catalytic cathodes capable of controlling Li2O2 growth.

Understanding Moisture and Carbon Dioxide Involved Interfacial Reactions on Electrochemical Performance of Lithium-Air Batteries Catalyzed by Gold/Manganese-Dioxide.

Lithium-air (Li-air) battery works essentially based on the interfacial reaction of 2Li + O2 ↔ Li2O2 on the catalyst/oxygen-gas/electrolyte triphase interface. Operation of Li-air batteries in ambient air still remains a great challenge despite the recent development, because some side reactions related to moisture (H2O) and carbon dioxide (CO2) will occur on the interface with the formation of some inert byproducts on the surface of the catalyst. In this work, we investigated the effect of H2O and CO2 on the electrochemical performance of Li-air batteries to evaluate the practical operation of the batteries in ambient air. The use of a highly efficient gold/δ-manganese-dioxide (Au/δ-MnO2) catalyst helps to understand the intrinsic mechanism of the effect. We found that H2O has a more detrimental influence than CO2 on the battery performance when operated in ambient air. The battery operated in simulated dry air can sustain a stable cycling up to 200 cycles at 400 mA g(-1) with a relatively low polarization, which is comparable with that operated in pure O2. This work provides a possible method to operate Li-air batteries in ambient air by using optimized catalytic electrodes with a protective layer, for example a hydrophobic membrane.

Nanostructured porous RuO2/MnO2 as a highly efficient catalyst for high-rate Li-O2 batteries.

Despite the recent advancements in Li-O(2) (or Li-air) batteries, great challenges still remain to realize high-rate, long-term cycling. In this work, a binder-free, nanostructured RuO(2)/MnO(2) catalytic cathode was designed to realize the operation of Li-O(2) batteries at high rates. At a current density as high as 3200 mA g(-1) (or ∼1.3 mA cm(-2)), the RuO(2)/MnO(2) catalyzed Li-O(2) batteries with LiI can sustain stable cycling of 170 and 800 times at limited capacities of 1000 and 500 mA h g(-1), respectively, with low charge cutoff potentials of ∼4.0 and <3.8 V, respectively. The underlying mechanism of the high catalytic performance of MnO(2)/RuO(2) was also clarified in this work. It was found that with the catalytic effect of RuO(2), Li(2)O(2) can crystallize into a thin-sheet form and realize a conformal growth on sheet-like δ-MnO(2) at a current density up to 3200 mA g(-1), constructing a sheet-on-sheet structure. This crystallization behavior of Li(2)O(2) not only defers the electrode passivation upon discharge but also renders easy decomposition of Li(2)O(2) upon charge, leading to low polarizations and reduced side reactions. This work provides a unique design of catalytic cathodes capable of controlling Li(2)O(2) growth and sheds light on the design of high-rate, long-life Li-O(2) batteries with potential applications in electric vehicles.

Au-nanocrystals-decorated δ-MnO2 as an efficient catalytic cathode for high-performance Li-O2 batteries.

A Li-O2 battery works based on the reversible formation and decomposition of Li2O2, which is insulating and highly reactive. Designing a catalytic cathode capable of controlling Li2O2 growth recently became a challenge to overcome this barrier. In this work, we present a new design of catalytic cathode by growing porous Au/δ-MnO2 electrocatalyst directly on a conductive substrate. We found that Au/δ-MnO2 can catalyze the directed growth of Li2O2 into a thin/small form, only inside porous δ-MnO2, and along the surface of δ-MnO2 sheets. We proposed the catalytic mechanism of Au/δ-MnO2, where Au plays a critical role in catalyzing the nucleation, crystallization and conformal growth of Li2O2 on δ-MnO2 sheets. Li-O2 batteries with an Au/δ-MnO2 catalytic cathode showed excellent electrochemical performance due to this favorable Li2O2 growth habit. The battery yielded a high capacity of 10,600 mA h g(-1) with a low polarization of 0.91 V at 100 mA g(-1). Superior cycling stability could be achieved in both capacity-limited (500 mA h g(-1), 165 times at 400 mA g(-1)) and unlimited (ca. 3000 mA h g(-1), 50 cycles at 800 mA g(-1)) modes.

Electrochemical properties of CoFe3Sb12 as potential anode material for lithium-ion batteries.

A skutterudite-related antimonide, CoFe(3)Sb(12), was prepared with vacuum melting. XRD analysis showed the material contained Sb, FeSb(2), CoSb(2) and CoSb(3) phases. The electrochemical properties of the ball-milled CoFe(3)Sb(12)-10 wt% graphite composite were studied using pure lithium as the reference electrode. A maximal lithium inserting capacity of about 860 mAh/g was obtained in the first cycle. The reversible capacity of the material was about 560 mAh/g in the first cycle and decreased to ca. 320 mAh/g and 250 mAh/g after 10 and 20 cycles respectively. Ex-situ XRD analyses showed that the antimonides in the pristine material were decomposed after the first discharge and that antimony was the active element for lithium to insert into the host material.

Solvothermal synthesis of nanosized CoSb(3) skutterudite.

Nanostructures enhance phonon scattering and improve the figure of merit of thermoelectric materials. Nanosized CoSb(3) skutterudite was synthesized by solvothermal methods using CoCl(2) and SbCl(3) as the precursors. A "two-step" model was suggested for the formation of CoSb(3) based on the X-ray diffraction analysis. The first step is the formation of cobalt diantimonide in the earlier stage during the synthesis process. Diantimonide was then combined with antimony atoms to form the skutterudite structured triantimonide, CoSb(3), in the later stage of the synthesis process as the second step. The synthesized CoSb(3) powders consist of irregular particles with sizes of about 20 nm and sheets of about 80 nm.

Preferential c-axis orientation of ultrathin SnS2 nanoplates on graphene as high-performance anode for Li-ion batteries.

A SnS2/graphene (SnS2/G) hybrid was synthesized by a facile one-step solvothermal route using graphite oxide, sodium sulfide, and SnCl4·5H2O as the starting materials. The formation of SnS2 and the reduction of graphite oxide occur simultaneously. Ultrathin SnS2 nanoplates with a lateral size of 5-10 nm are anchored on graphene nanosheets with a preferential (001) orientation, forming a unique plate-on-sheet structure. The electrochemical tests showed that the nanohybrid exhibits a remarkably enhanced cycling stability and rate capability compared with bare SnS2. The excellent electrochemical properties of SnS2/G could be ascribed to the in situ introduced graphene matrix which offers two-dimensional conductive networks, disperses and immobilizes SnS2 nanoplates, buffers the volume changes during cycling, and directs the growth of SnS2 nanoplates with a favorable orientation.