Directional and Orderly Arranged Ni0.9Mn0.1(OH)2 Enables the Synthesis of Single-Crystal Ni-Rich Co-Free LiNi0.9Mn0.1O2 with Enhanced Internal Structural Stability.

In this paper, the effect of the structure characteristics of the precursor on the electrochemical properties of a single-crystal cobalt-free high-nickel LiNi0.9Mn0.1O2 cathode is systematically studied. Precursors with different morphologies are synthesized by adjusting the coprecipitation reaction conditions. The results of SEM and XRD show that with the increase in the orderly stacking arrangement of internal primary nanosheets of Ni0.9Mn0.1(OH)2, the exposed active {010} planes at the surface increase. The prepared cathode materials finally inherit the structural features of the precursor, and the single-crystal Co-free Ni-rich LiNi0.9Mn0.1O2 cathode with highly exposed active {010} planes shows a well-ordered crystal structure and low Li+/Ni2+ cation mixing. The characterization results reveal that the high percentage of {010} planes will improve the Li+ transportation kinetics, decrease electrochemical impedance, and significantly alleviate the accumulation of rock-salt phases. Therefore, the material with this structure shows good electrochemical performance.

Cellulose-Assisted Vertically Heterostructured PEO-Based Solid Electrolytes Mitigating Li-Succinonitrile Corrosion for Lithium Metal Batteries.

In the field of solid-state lithium metal batteries (SSLMBs), constructing vertically heterostructured poly(ethylene oxide) (PEO)-based solid electrolytes is an effective method to realize their tight contact with cathodes and Li anodes at the same time. Succinonitrile (SN) has been widely used in PEO-based solid electrolytes to improve the interface contact with cathodes, enhance the ionic conductivities, and obtain a high electrochemical stability window of PEO, but its application is still hindered by its intrinsic instability to Li anodes, which results in corrosion and side interactions with lithium metal. Herein, the cellulose membrane (CM) is introduced creatively into the vertically heterostructured PEO-based solid electrolytes to match the PEO-SN solid electrolytes at the cathode side. With the advantage of the interaction between -OH groups of CM and -C≡N groups in SN, the movement of free SN molecules from cathodes to Li anodes is limited effectively, resulting in a stable and durable SEI layer. In specific, the Li||LiFePO4 battery with the CM-assisted vertically heterostructured PEO-based solid electrolyte by in situ preparation delivers a discharge capacity of around 130 mAh g-1 after 300 cycles and capacity retention of 95% after 500 cycles at 0.5 C. Our work provides a solution to construct PEO-based solid electrolytes feasible to match cathodes and Li anodes effectively by intimate contact with electrodes.

Li-Deficient Materials-Decoration Restrains Oxygen Evolution Achieving Excellent Cycling Stability of Li-Rich Mn-Based Cathode.

With the increasing demand for high energy density and rapid charging performance, Li-rich materials have been the up and coming cathodes for next-generation lithium-ion batteries. However, because of oxygen evolution and structural instability, the commercialization of Li-rich materials is extremely retarded by their poor electrochemical performances. In this work, Li-deficient materials Li0.3NbO2 and (Nb0.62Li0.15)TiO3 are applied to functionalize the surface of Li1.2Mn0.54Ni0.13Co0.13O2, aiming to suppress oxygen evolution and increase structural stability in LIBs. In addition, a fast Li-ion transport channel is beneficial to enhance Li+ diffusion kinetics. The results demonstrate that the electrodes decorated with Li0.3NbO2 and (Nb0.62Li0.15)TiO3 materials exhibit more stable cycling stability after long-term cycling and outstanding rate capability.

Surface LiMn1.4Ni0.5Mo0.1O4 Coating and Bulk Mo Doping of Li-Rich Mn-Based Li1.2Mn0.54Ni0.13Co0.13O2 Cathode with Enhanced Electrochemical Performance for Lithium-Ion Batteries.

To improve the initial Coulombic efficiency, cycling stability, and rate performance of the Li-rich Mn-based Li1.2Mn0.54Ni0.13Co0.13O2 cathode, the combination of LiMn1.4Ni0.5Mo0.1O4 coating with Mo doping has been successfully carried out by the sol-gel method and subsequent dip-dry process. This strategy buffers the electrodes from the corrosion of electrolyte and enhances the lattice parameter, which could inhibit the oxygen release and maintain the structural stability, thus improving the cycle stability and rate capability. After LiMn1.4Ni0.5Mo0.1O4 modification, the initial discharge capacity reaches 272.4 mAh g-1 with a corresponding initial Coulombic efficiency (ICE) of 84.2% at 0.1C (1C = 250 mAh g-1), far higher than those (221.5 mAh g-1 and 68.9%) of the pristine sample. Besides, the capacity retention of the coated sample is enhanced by up to 66.8% after 200 cycles at 0.1C. Especially, the rate capability of the coated sample is 95.2 mAh g-1 at 5C. XRD, SEM, TEM, XPS, and Raman spectroscopy are adopted to characterize the morphologies and structures of the samples. This coating strategy has been demonstrated to be an effective approach to construct high-performance energy storage devices.

Synthesis and Application of a Phosphorous-Free and Non-Nitrogen Polymer as an Environmentally Friendly Scale Inhibition and Dispersion Agent in Simulated Cooling Water Systems.

A novel phosphorus-free and non-nitrogen scale inhibition and dispersion agent was synthesized from epoxysuccinic acid (ESA), itaconic acid (IA), and sodium methyl propylene sulfonate (SMAS). It was characterized by infrared spectroscopy (IR), nuclear magnetic resonance (NMR), and elemental analysis, and its molecular weight and distribution were determined by gel permeation chromatography (GPC). Static experimental methods were used to evaluate the scale inhibition against CaCO3, Ca3(PO4)2, and CaSO4. The dispersion ability was evaluated by measuring the dispersive property of iron oxide. By observing the morphology of the CaCO3 scale, the scale inhibition mechanism was discussed. The results showed that when the ratio of raw materials (ESA/IA/SMAS) was 10:10:5, the scale inhibition rate of CaCO3 and CaSO4 reached 100% with the dosages of 20 and 10 mg/L, respectively. In addition, the scale inhibition rate against Ca3(PO4)2 was up to 96.64% with a dosage of 100 mg/L. The property of dispersing iron oxide exhibited the best results with 50 mg/L of the agent. On the 21st day, the biodegradation rate reached 63.33%. This polymer was an environmentally friendly antiscale and dispersant with good scale inhibition and biodegradability.

Structural Design and Synthesis of an SnO2 @C@Co-NC Composite as a High-Performance Anode Material for Lithium-Ion Batteries.

To overcome the drawbacks of the structural instability and poor conductivity of SnO2 -based anode materials, a hollow core-shell-structured SnO2 @C@Co-NC (NC=N-doped carbon) composite was designed and synthesized by employing the heteroatom-doping and multiconfinement strategies. This composite material showed a much-reduced resistance to charge transfer and excellent cycling performance compared to the bare SnO2 nanoparticles and SnO2 @C composites. The doped heteroatoms and heterostructure boost the charge transfer, and the porous structure shortens the Li-ion diffusion pathway. Also, the volume expansion of SnO2 NPs is accommodated by the hollow space and restricted by the multishell heteroatom-doped carbon framework. As a result, this structured anode material delivered a high initial capacity of 1559.1 mA h g-1 at 50 mA g-1 and an initial charge capacity of 627.2 mA h g-1 at 500 mA g-1 . Moreover, the discharge capacity could be maintained at 410.8 mA h g-1 after 500 cycles with an attenuation rate of only 0.069 % per cycle. This multiconfined SnO2 @C@Co-NC structure with superior energy density and durable lifespan is highly promising for the next-generation lithium-ion batteries.

General Synthesis of Transition-Metal Oxide Hollow Nanospheres/Nitrogen-Doped Graphene Hybrids by Metal-Ammine Complex Chemistry for High-Performance Lithium-Ion Batteries.

We present a general and facile synthesis strategy, on the basis of metal-ammine complex chemistry, for synthesizing hollow transition-metal oxides (Co3 O4 , NiO, CuO-Cu2 O, and ZnO)/nitrogen-doped graphene hybrids, potentially applied in high-performance lithium-ion batteries. The oxygen-containing functional groups of graphene oxide play a prerequisite role in the formation of hollow transition-metal oxides on graphene nanosheets, and a significant hollowing process occurs only when forming metal (Co2+ , Ni2+ , Cu2+ , or Zn2+ )-ammine complex ions. Moreover, the hollowing process is well correlated with the complexing capacity between metal ions and NH3 molecules. The significant hollowing process occurs for strong metal-ammine complex ions including Co2+ , Ni2+ , Cu2+ , and Zn2+ ions, and no hollow structures formed for weak and/or noncomplex Mn2+ and Fe3+ ions. Simultaneously, this novel strategy can also achieve the direct doping of nitrogen atoms into the graphene framework. The electrochemical performance of two typical hollow Co3 O4 or NiO/nitrogen-doped graphene hybrids was evaluated by their use as anodic materials. It was demonstrated that these unique nanostructured hybrids, in contrast with the bare counterparts, solid transition-metal oxides/nitrogen-doped graphene hybrids, perform with significantly improved specific capacity, superior rate capability, and excellent capacity retention.

Yolk bishell Mn(x)Co(1-x)Fe2O4 hollow microspheres and their embedded form in carbon for highly reversible lithium storage.

The yolk-shell hollow structure of transition metal oxides has many applications in lithium-ion batteries and catalysis. However, it is still a big challenge to fabricate uniform hollow microspheres with the yolk bishell structure for mixed transition metal oxides and their supported or embedded forms in carbon microspheres with superior lithium storage properties. Here we report a new approach to the synthesis of manganese cobalt iron oxides/carbon (MnxCo1-xFe2O4 (0 ≤ x ≤ 1)) microspheres through carbonization of Mn(2+)Co(2+)Fe(3+)/carbonaceous microspheres in N2, which can be directly applied as high-performance anodes with a long cycle life for lithium storage. Furthermore, uniform hollow microspheres with a MnxCo1-xFe2O4 yolk bishell structure are obtained by annealing the above MnxCo1-xFe2O4/carbon microspheres in air. As demonstrated, these anodes exhibited a high reversible capacity of 498.3 mAh g(-1) even after 500 cycles for Mn0.5Co0.5Fe2O4/carbon microspheres and 774.6 mAh g(-1) over 100 cycles for Mn0.5Co0.5Fe2O4 yolk bishell hollow microspheres at the current density of 200 mA g(-1). The present strategy not only develops a high-performance anode material with long cycle life for lithium-ion batteries but also demonstrates a novel and feasible technique for designed synthesis of transition metal oxides yolk bishell hollow microspheres with various applications.

Enhancing the electrocatalytic property of hollow structured platinum nanoparticles for methanol oxidation through a hybrid construction.

The integration of different components into a hybrid nanosystem for the utilization of the synergistic effects is an effective way to design the electrocatalysts. Herein, we demonstrate a hybrid strategy to enhance the electrocatalytic property of hollow structured Pt nanoparticles for methanol oxidation reaction. This strategy begins with the preparation of bimetallic Ag-Pt nanoparticles with a core-shell construction. Element sulfur is then added to transform the core-shell Ag-Pt nanostructures into hybrid nanodimers consisting of Ag2S nanocrystals and remaining Pt domains with intact hollow interiors (Ag2S-hPt). Finally, Au is deposited at the surface of the Ag2S domain in each hetero-dimer, resulting in the formation of ternary Ag2S-Au-hPt nanocomposites with solid-state interfaces. The ternary nanocomposites exhibit enhanced electrocatalytic property toward methanol oxidation due to the strong electronic coupling between Pt and other domains in the hybrid particles. The concept might be used toward the design and synthesis of other hetero-nanostructures with technological importance.

Mn0.5Co0.5Fe2O4 nanoparticles highly dispersed in porous carbon microspheres as high performance anode materials in Li-ion batteries.

We report the preparation of Mn(0.5)Co(0.5)Fe2O4 (MCFO) nanoparticles highly dispersed within porous carbon microspheres as anodes for Li-ion batteries. In situ growth of MCFO nanoparticles (5-20 nm) on the surface of carbon black (CB) and graphitized carbon black (GCB) nanoparticles was conducted via a hydrothermal method to form MCFO-CB and MCFO-GCB composites, respectively, which were employed as building blocks to assemble MCFO-CB and MCFO-GCB porous microspheres (PM) with a size of 5-30 µm by the spray drying technique using sucrose as a binder, and followed by carbonization in N2 (labeled as MCFO-CB-PM and MCFO-GCB-PM, respectively). Compared with the pure MCFO, MCFO-CB, and MCFO-GCB, both MCFO-CB-PM and MCFO-GCB-PM showed a significantly improved electrochemical performance. This is attributed to their unique porous structure, in which, the abundant pores promote the diffusion of Li-ion and electrolyte solution, the microspherical morphology enhances the electrode-electrolyte contact, and the carbon substrates from CB (and GCB) and sucrose substantially prevent the aggregation of MCFO nanoparticles and buffer the volume change. Particularly, MCFO-GCB-PM exhibits the best rate performance and excellent cycling stability because of the high graphitization degree of GCB. This work opens up an effective route for large scale fabrication of metal oxide/carbon porous microspheres as anode materials for potential applications in the new generation of Li-ion batteries.

Scalable synthesis of interconnected porous silicon/carbon composites by the Rochow reaction as high-performance anodes of lithium ion batteries.

Despite the promising application of porous Si-based anodes in future Li ion batteries, the large-scale synthesis of these materials is still a great challenge. A scalable synthesis of porous Si materials is presented by the Rochow reaction, which is commonly used to produce organosilane monomers for synthesizing organosilane products in chemical industry. Commercial Si microparticles reacted with gas CH3 Cl over various Cu-based catalyst particles to substantially create macropores within the unreacted Si accompanying with carbon deposition to generate porous Si/C composites. Taking advantage of the interconnected porous structure and conductive carbon-coated layer after simple post treatment, these composites as anodes exhibit high reversible capacity and long cycle life. It is expected that by integrating the organosilane synthesis process and controlling reaction conditions, the manufacture of porous Si-based anodes on an industrial scale is highly possible.

Growth of linked silicon/carbon nanospheres on copper substrate as integrated electrodes for Li-ion batteries.

We report the growth of linked silicon/carbon (Si/C) nanospheres on Cu substrate as an integrated anode for Li-ion batteries. The Si/C nanospheres were synthesized by a catalytic chemical vapor deposition (CCVD) on Cu substrate as current collector using methyltrichlorosilane as precursor, a cheap by-product of the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermal gravimetry, Raman spectroscopy, nitrogen adsorption, inductively coupled plasma optical emission spectrometry, and X-ray photoelectron spectroscopy. It was found that the linked Si/C nanospheres with a diameter of 400-500 nm contain Si, Cu(x)Si, and Cu nanocrystals, which are highly dispersed in the amorphous carbon nanospheres. A CCVD mechanism was tentatively proposed, in which the evaporated Cu atoms play a critical role to catalytically grown Si nanocrystals embedded within linked Si/C nanospheres. The electrochemical measurement shows that these Si/C nanospheres delivered a capacity of 998.9, 713.1, 320.6, and 817.8 mA h g(-1) at 50, 200, 800, and 50 mA g(-1) respectively after 50 cycles, much higher than that of commercial graphite anode. This is because the amorphous carbon, Cu(x)Si, and Cu in the Si/C nanospheres could buffer the volume change of Si nanocrystals during the Li insertion and extraction reactions, thus hindering the cracking or crumbling of the electrode. Furthermore, the incorporation of conductive Cu(x)Si and Cu nanocrystals and the integration of active electrode materials with Cu substrate may improve the electrical conductivity from the current collector to individual Si active particles, resulting in a remarkably enhanced reversible capacity and cycling stability. The work will be helpful in the fabrication of low cost binder-free Si/C anode materials for Li-ion batteries.

Amorphous silicon-carbon nanospheres synthesized by chemical vapor deposition using cheap methyltrichlorosilane as improved anode materials for Li-ion batteries.

We report the preparation and characterization of amorphous silicon-carbon (Si-C) nanospheres as anode materials in Li-ion batteries. These nanospheres were synthesized by a chemical vapor deposition at 900 °C using methyltrichlorosilane (CH3SiCl3) as both the Si and C precursor, which is a cheap byproduct in the organosilane industry. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric analysis, Raman spectroscopy, and X-ray photoelectron spectroscopy. It was found that the synthesized Si-C nanospheres composed of amorphous C (about 60 wt%) and Si (about 40 wt%) had a diameter of 400-600 nm and a surface area of 43.8 m(2) g(-1). Their charge capacities were 483.6, 331.7, 298.6, 180.6, and 344.2 mA h g(-1) at 50, 200, 500, 1000, and 50 mA g(-1) after 50 cycles, higher than that of the commercial graphite anode. The Si-C amorphous structure could absorb a large volume change of Si during Li insertion and extraction reactions and hinder the cracking or crumbling of the electrode, thus resulting in the improved reversible capacity and cycling stability. The work opens a new way to fabricate low cost Si-C anode materials for Li-ion batteries.

Facile solvothermal synthesis of mesoporous manganese ferrite (MnFe2O4) microspheres as anode materials for lithium-ion batteries.

We report the synthesis and characterization of the mesoporous manganese ferrite (MnFe2O4) microspheres as anode materials for Li-ion batteries. MnFe2O4 microspheres were synthesized by a facile solvothermal method using Mn(CH3COO)2 and FeCl3 as metal precursors in the presence of CH3COOK, CH3COOC2H5, and HOCH2CH2OH. The samples were characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, nitrogen adsorption, thermal gravimetric, X-ray photoelectron spectroscopy, temperature programmed reduction, and temperature programmed oxidation. The synthesized mesoporous MnFe2O4 microspheres composed of nanoparticles (10-30 nm) were 100-500 nm in diameter and had surface areas between 60.2 and 86.8 m(2) g(-1), depending on the CH3COOK amounts added in the preparation. After calcined at 600°C, MnFe2O4 was decomposed to Mn2O3 and Fe2O3 mixture. The mesoporous MnFe2O4 microspheres calcined at 400°C showed a capacity of 712.2 mA h g(-1) at 0.2C and 552.2 mA h g(-1) at 0.8C after 50 cycles, and an average capacity fading rate of around 0.28%/cycle and 0.48%/cycle, much better than those of the samples without calcination and calcined at 600°C. The work would be helpful in the fabrication of binary metal oxide anode materials for Li-ion batteries.