Zimin Nie

Self-assembled TiO2-Graphene Hybrid Nanostructures for Enhanced Li-ion Insertion

We used anionic sulfate surfactants to assist the stabilization of graphene in aqueous solutions and facilitate the self-assembly of in situ grown nanocrystalline TiO2, rutile and anatase, with graphene. These nanostructured TiO2-graphene hybrid materials were used for investigation of Li-ion insertion properties. The hybrid materials showed significantly enhanced Li-ion insertion/extraction in TiO2. The specific capacity was more than doubled at high charge rates, as compared with the pure TiO2 phase. The improved capacity at high charge-discharge rate may be attributed to increased electrode conductivity in the presence of a percolated graphene network embedded into the metal oxide electrodes.

Sodium ion insertion in hollow carbon nanowires for battery applications.

Hollow carbon nanowires (HCNWs) were prepared through pyrolyzation of a hollow polyaniline nanowire precursor. The HCNWs used as anode material for Na-ion batteries deliver a high reversible capacity of 251 mAh g(-1) and 82.2% capacity retention over 400 charge-discharge cycles between 1.2 and 0.01 V (vs Na(+)/Na) at a constant current of 50 mA g(-1) (0.2 C). Excellent cycling stability is also observed at an even higher charge-discharge rate. A high reversible capacity of 149 mAh g(-1) also can be obtained at a current rate of 500 mA g(-1) (2C). The good Na-ion insertion property is attributed to the short diffusion distance in the HCNWs and the large interlayer distance (0.37 nm) between the graphitic sheets, which agrees with the interlayered distance predicted by theoretical calculations to enable Na-ion insertion in carbon materials.

Hierarchically porous graphene as a lithium-air battery electrode.

The lithium-air battery is one of the most promising technologies among various electrochemical energy storage systems. We demonstrate that a novel air electrode consisting of an unusual hierarchical arrangement of functionalized graphene sheets (with no catalyst) delivers an exceptionally high capacity of 15000 mAh/g in lithium-O(2) batteries which is the highest value ever reported in this field. This excellent performance is attributed to the unique bimodal porous structure of the electrode which consists of microporous channels facilitating rapid O(2) diffusion while the highly connected nanoscale pores provide a high density of reactive sites for Li-O(2) reactions. Further, we show that the defects and functional groups on graphene favor the formation of isolated nanosized Li(2)O(2) particles and help prevent air blocking in the air electrode. The hierarchically ordered porous structure in bulk graphene enables its practical applications by promoting accessibility to most graphene sheets in this structure.

A Soft Approach to Encapsulate Sulfur: Polyaniline Nanotubes for Lithium‐Sulfur Batteries with Long Cycle Life

A novel vulcanized polyaniline nanotube/sulfur composite was prepared successfully via an in situ vulcanization process by heating a mixture of polyaniline nanotube and sulfur at 280 °C. The electrode could retain a discharge capacity of 837 mAh g(-1) after 100 cycles at a 0.1 C rate and manifested 76% capacity retention up to 500 cycles at a 1 C rate.

Ternary self-assembly of ordered metal oxide-graphene nanocomposites for electrochemical energy storage.

Surfactant or polymer directed self-assembly has been widely investigated to prepare nanostructured metal oxides, semiconductors, and polymers, but this approach is mostly limited to two-phase materials, organic/inorganic hybrids, and nanoparticle or polymer-based nanocomposites. Self-assembled nanostructures from more complex, multiscale, and multiphase building blocks have been investigated with limited success. Here, we demonstrate a ternary self-assembly approach using graphene as fundamental building blocks to construct ordered metal oxide-graphene nanocomposites. A new class of layered nanocomposites is formed containing stable, ordered alternating layers of nanocrystalline metal oxides with graphene or graphene stacks. Alternatively, the graphene or graphene stacks can be incorporated into liquid-crystal-templated nanoporous structures to form high surface area, conductive networks. The self-assembly method can also be used to fabricate free-standing, flexible metal oxide-graphene nanocomposite films and electrodes. We have investigated the Li-ion insertion properties of the self-assembled electrodes for energy storage and show that the SnO2-graphene nanocomposite films can achieve near theoretical specific energy density without significant charge/discharge degradation.

Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life

Single crystalline Na4Mn9O18 nanowires were synthesized via pyrolysis of polyacrylate salt precursors prepared by in-situ polymerization of the metal salts and acrylate acid, followed by calcinations at an appropriate temperature to achieve good crystalline structure and uniform nanowire morphology with an average diameter of 50 nm. The Na4Mn9O18 nanowires have shown a high, reversible, and near theoretical sodium ion insertion capacity (128 mA h g-1 at 0.1C), excellent long cyclability (77% capacity retention for 1000 cycles at 0.5 C), along with good rate capability. Good capacity and charge-discharge stability are also observed for full cell experiments using a pyrolyzed carbon as the anode, therefore demonstrating the potential of these materials for sodium-ion batteries for large scale energy storage. Furthermore, this research shows that a good crystallinity and small particles are required to enhance the Na-ion diffusion and increase the stability of the electrode materials for long charge-discharge cycles.

Stabilization of Electrocatalytic Metal Nanoparticles at Metal−Metal Oxide−Graphene Triple Junction Points

Carbon-supported precious metal catalysts are widely used in heterogeneous catalysis and electrocatalysis, and enhancement of catalyst dispersion and stability by controlling the interfacial structure is highly desired. Here we report a new method to deposit metal oxides and metal nanoparticles on graphene and form stable metal-metal oxide-graphene triple junctions for electrocatalysis applications. We first synthesize indium tin oxide (ITO) nanocrystals directly on functionalized graphene sheets, forming an ITO-graphene hybrid. Platinum nanoparticles are then deposited, forming a unique triple-junction structure (Pt-ITO-graphene). Our experimental work and periodic density functional theory (DFT) calculations show that the supported Pt nanoparticles are more stable at the Pt-ITO-graphene triple junctions. Furthermore, DFT calculations suggest that the defects and functional groups on graphene also play an important role in stabilizing the catalysts. These new catalyst materials were tested for oxygen reduction for potential applications in polymer electrolyte membrane fuel cells, and they exhibited greatly enhanced stability and activity.

High‐Performance LiNi0.5Mn1.5O4 Spinel Controlled by Mn3+ Concentration and Site Disorder

The complex correlation between Mn(3+) ions and the disordered phase in the lattice structure of high voltage spinel, and its effect on the charge transport properties, are revealed through a combination of experimental study and computer simulations. Superior cycling stability is achieved in LiNi(0.45)Cr(0.05)Mn(1.5)O(4) with carefully controlled Mn(3+) concentration. At 250th cycle, capacity retention is 99.6% along with excellent rate capabilities.

LiMnPO4 Nanoplate Grown via Solid-State Reaction in Molten Hydrocarbon for Li~Ion Battery Cathode

Electrochemically active LiMnPO(4) nanoplates have been synthesized via a novel, single-step, solid-state reaction in molten hydrocarbon. The olivine-structured LiMnPO(4) nanoplates with a thickness of approximately 50 nm appear porous and were formed as nanocrystals were assembled and grew into nanorods along the [010] direction in the (100) plane. After carbon coating, the prepared LiMnPO(4) cathode demonstrated a flat potential at 4.1 V versus Li with a specific capacity reaching as high as 168 mAh/g under a galvanostatic charging/discharging mode, along with an excellent cyclability.

Optimization of mesoporous carbon structures for lithium–sulfur battery applications

Mesoporous carbon (MC) with tunable pore sizes (22 nm, 12 nm, 7 nm, and 3 nm) and pore volumes (from 1.3 to 4.8 cm3 g−1) containing sulfur in the pores was studied as a mesoporous carbon–sulfur (MCS) composite electrode for lithium–sulfur (Li–S) batteries. Systematic investigation of these MCS composites reveals that MC with a larger pore volume can hold a higher maximum sulfur loading, but overall the battery performance is very similar for different MCS composites at full sulfur-filling conditions (i.e., the condition at which the sulfur loading approaches the maximum limit set by the pore volume of the individual MC and, therefore, the pores of each MC are fully filled by sulfur). For the same MC, partial sulfur-filling (i.e., the condition at which the sulfur loading is lower than the maximum limit and, therefore, the pores are only partially filled with sulfur) leads to an improved initial discharge capacity and cycle stability, probably because of improved electrical and ionic transport during electrochemical reactions. Based on this understanding, an MCS composite electrode using MC with a large pore volume, partial sulfur filling, and a novel surface modification was designed for Li–S batteries. An initial capacity of ∼1390 mA h g−1 (based on sulfur) and a capacity retention of ∼840 mA h g−1 over 100 cycles at a 0.1 C rate were obtained using MC (22 nm, 4.8 cm3 g−1) with 50 wt% sulfur loading and a commercially available Clevios P (poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate) (PEDT/PSS)) coating.