Yu-Ming Chen

Metal Organic Frameworks Derived Hierarchical Hollow NiO/Ni/Graphene Composites for Lithium and Sodium Storage

Ni-based metal organic frameworks (Ni-MOFs) with unique hierarchical hollow ball-in-ball nanostructure were synthesized by solvothermal reactions. After successive carbonization and oxidation treatments, hierarchical NiO/Ni nanocrystals covered with a graphene shell were obtained with the hollow ball-in-ball nanostructure intact. The resulting materials exhibited superior performance as the anode in lithium ion batteries (LIBs): they provide high reversible specific capacity (1144 mAh/g), excellent cyclability (nearly no capacity loss after 1000 cycles) and rate performance (805 mAh/g at 15 A/g). In addition, the hierarchical NiO/Ni/Graphene composites demonstrated promising performance as anode materials for sodium-ion batteries (SIBs). Such a superior lithium and sodium storage performance is derived from the well-designed hierarchical hollow ball-in-ball structure of NiO/Ni/Graphene composites, which not only mitigates the volume expansion of NiO during the cycles but also provides a continuous highly conductive graphene matrix to facilitate the fast charge transfer and form a stable SEI layer.

Fabrication of Porous Carbon/TiO2 Composites through Polymerization-Induced Phase Separation and Use As an Anode for Na-Ion Batteries

Polymerization-induced phase separation of nanoparticle-filled solution is demonstrated as a simple approach to control the structure of porous composites. These composites are subsequently demonstrated as the active component for sodium ion battery anode. To synthesize the composites, we dissolved/dispersed titanium oxide (anatase) nanoparticles (for sodium insertion) and poly(hydroxybutyl methacrylate) (PHBMA, porogen) in furfuryl alcohol (carbon precursor) containing a photoacid generator (PAG). UV exposure converts the PAG to a strong acid that catalyzes the furfuryl alcohol polymerization. This polymerization simultaneously decreases the miscibility of the PHBMA and reduces the mobility in the mixture to kinetically trap the phase separation. Carbonization of this polymer composite yields a porous nanocomposite. This nanocomposite exhibits nearly 3-fold greater gravimetric capacity in Na-ion batteries than the same titanium oxide nanoparticles that have been coated with carbon. This improved performance is attributed to the morphology as the carbon content in the composite is five times that of the coated nanoparticles. The porous composite materials exhibit stable cyclic performance. Moreover, the battery performance using materials from this polymerization-induced phase separation method is reproducible (capacity within 10% batch-to-batch). This simple fabrication methodology may be extendable to other systems and provides a facile route to generate reproducible hierarchical porous morphology that can be beneficial in energy storage applications.

Three-Dimensional Bicontinuous Graphene Monolith from Polymer Templates.

The two-dimensional single-layer and few-layered graphene exhibit many attractive properties such as large specific surface area and high charge carrier mobility. However, graphene sheets tend to stack together and form aggregates, which do not possess the desirable properties associated with graphene. Herein, we report a method to fabricate three-dimensional (3D), bicontinuous graphene monolith through a versatile hollow nickel (Ni) template derived from polymer blends. The poly(styrene)/poly(ethylene oxide) were used to fabricate a bicontinuous gyroid template using controlled phase separation. The Ni template was formed by electroless metal depositing on the polymer followed by removing the polymer phase. The resulting hollow Ni structure was highly porous (95.2%). Graphene was then synthesized from this hollow Ni template using chemical vapor deposition and the free-standing bicontinuous graphene monolith was obtained in high-throughput process. Finally, the bicontinuous graphene monolith was used directly as binder-free electrode in supercapacitor applications. The supercapacitor devices exhibited excellent stability.

A nitrogen doped carbonized metal–organic framework for high stability room temperature sodium–sulfur batteries

A nanoporous nitrogen doped carbon matrix was prepared by carbonization of metal–organic framework zeolitic imidazolate framework (ZIF-8) precursors. The doped carbon matrix was melt-infiltrated with sulfur to form a carbonized ZIF-8/S composite. The composite material exhibited good performance as the cathode for room-temperature sodium–sulfur battery (Na–S) systems. A reversible specific capacity of around 1000 mA h g−1 could be achieved at a rate of 0.1C; and a reversible specific capacity of 500 mA h g−1 was obtained at a rate of 0.2C after 250 cycles. The good performance of the Na–S battery could be attributed to the synergistic effect from the nanoporosity of the carbon matrix and the high nitrogen-doping content (ca. ∼18 at%). These attributes enhanced the entrapment of the sulfur molecules inside the carbon matrices.

Hierarchical Electrospun and Cooperatively Assembled Nanoporous Ni/NiO/MnOx/Carbon Nanofiber Composites for Lithium Ion Battery Anodes.

A facile method to fabricate hierarchically structured fiber composites is described based on the electrospinning of a dope containing nickel and manganese nitrate salts, citric acid, phenolic resin, and an amphiphilic block copolymer. Carbonization of these fiber mats at 800 °C generates metallic Ni-encapsulated NiO/MnOx/carbon composite fibers with average BET surface area (150 m(2)/g) almost 3 times higher than those reported for nonporous metal oxide nanofibers. The average diameter (∼900 nm) of these fiber composites is nearly invariant of chemical composition and can be easily tuned by the dope concentration and electrospinning conditions. The metallic Ni nanoparticle encapsulation of NiO/MnOx/C fibers leads to enhanced electrical conductivity of the fibers, while the block copolymers template an internal nanoporous morphology and the carbon in these composite fibers helps to accommodate volumetric changes during charging. These attributes can lead to lithium ion battery anodes with decent rate performance and long-term cycle stability, but performance strongly depends on the composition of the composite fibers. The composite fibers produced from a dope where the metal nitrate is 66% Ni generates the anode that exhibits the highest reversible specific capacity at high rate for any composition, even when including the mass of the nonactive carbon and Ni(0) in the calculation of the capacity. On the basis of the active oxides alone, near-theoretical capacity and excellent cycling stability are achieved for this composition. These cooperatively assembled hierarchical composites provide a platform for fundamentally assessing compositional dependencies for electrochemical performance. Moreover, this electrospinning strategy is readily scalable for the fabrication of a wide variety of nanoporous transition metal oxide fibers.

Tuning SEI formation on nanoporous carbon–titania composite sodium ion batteries anodes and performance with subtle processing changes

The morphology of composite materials used in battery electrodes is critical to provide the requisite transport paths for ions and electrons to enable high performance. In this work, we describe a simple and scalable method to fine tune the morphology of carbon/TiO2 composite through polymerization-induced phase separation of a mixture containing commercial TiO2 nanoparticles, poly(hydroxyethyl methacrylate) (PHEMA), and photoacid generator (PAG) dissolved in furfuryl alcohol (FA, monomer). UV exposure converts the PAG to a strong acid that catalyzes the FA polymerization to quickly initiate the polymerization. The morphology is modulated by the molecular weight of PHEMA and FA concentration that impact the miscibility and mobility during phase separation. The polymerized composite is carbonized to yield porous carbon/TiO2 electrodes. The cycling performance is dictated by the morphology that develops during phase separation. Electrochemical impedance spectroscopy (EIS) analysis illustrates that subtle changes in synthetic conditions can dramatically impact the electrical or ion conductance, primarily through modulation in the solid electrolyte interphase (SEI). A careful investigation of the SEI layer on the porous carbon/TiO2 composites demonstrates a clear correlation between the SEI and the surface area of the porous anode as determined by transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). With selection of synthetic conditions to yield a modest surface area composite, sustainable anodes with stable capacity can be fabricated for use in Na ion batteries.

Operando Grazing Incidence Small-Angle X-ray Scattering/X-ray Diffraction of Model Ordered Mesoporous Lithium-Ion Battery Anodes

Emergent lithium-ion (Li+) batteries commonly rely on nanostructuring of the active electrode materials to decrease the Li+ ion diffusion path length and to accommodate the strains associated with the insertion and de-insertion of Li+, but in many cases these nanostructures evolve during electrochemical charging-discharging. This change in the nanostructure can adversely impact performance, and challenges remain regarding how to control these changes from the perspective of morphological design. In order to address these questions, operando grazing-incidence small-angle X-ray scattering and X-ray diffraction (GISAXS/GIXD) were used to assess the structural evolution of a family of model ordered mesoporous NiCo2O4 anode films during battery operation. The pore dimensions were systematically varied and appear to impact the stability of the ordered nanostructure during the cycling. For the anodes with small mesopores (≈9 nm), the ordered nanostructure collapses during the first two charge-discharge cycles, as determined from GISAXS. This collapse is accompanied by irreversible Li-ion insertion within the oxide framework, determined from GIXD and irreversible capacity loss. Conversely, anodes with larger ordered mesopores (17-28 nm) mostly maintained their nanostructure through the first two cycles with reversible Li-ion insertion. During the second cycle, there was a small additional deformation of the mesostructure. This preservation of the ordered structure lead to significant improvement in capacity retention during these first two cycles; however, a gradual loss in the ordered nanostructure from continuing deformation of the ordered structure during additional charge-discharge cycles leads to capacity decay in battery performance. These multiscale operando measurements provide insight into how changes at the atomic scale (lithium insertion and de-insertion) are translated to the nanostructure during battery operation. Moreover, small changes in the nanostructure can build up to significant morphological transformations that adversely impact battery performance through multiple charge-discharge cycles.

Syndiotactic Polystyrene-Based Ionogel Membranes for High Temperature Electrochemical Applications

This work focuses on ionogel membranes for use in Li-ion batteries fabricated from syndiotactic polystyrene (sPS) gels filled with ionic liquids (ILs). The aim is to increase the operating temperature of Li-ion batteries. Thermal stability and safe operation of Li-ion batteries are two key attributes for their success in hybrid vehicles and other high-temperature applications. The volatility of the liquid electrolytes in current lithium-ion battery technology causes thermal runaway leading to fire, explosion, and swelling of the cell. The approach followed in this work combines the thermal stability and ruggedness of sPS and the extremely low volatility of ILs. The performances of lithium metal/graphite half-cells fabricated with ionogel membranes and those with Celgard-3501 membranes are evaluated at both room temperature and at elevated temperatures of 100 °C. Our data show that the cells with ionogel membranes can be operated continuously at 100 °C without failure. In addition, better charge-discharge capacity is obtained due to high ionic conductivity and high electrolyte retention both derived from high porosity of sPS gels and better wetting of sPS by the ILs.

Nanoporous gyroid Ni/NiO/C nanocomposites from block copolymer templates with high capacity and stability for lithium storage

A nanoporous Ni/NiO/C nanocomposite with a gyroid nanostructure was fabricated by using a nanoporous polymer with gyroid nanochannels as a template. The polymer template was obtained from the self-assembly of a degradable block copolymer, polystyrene-b-poly(L-lactide) (PS-PLLA), followed by the hydrolysis of PLLA blocks. Templated electroless plating followed by calcination was performed to create a precisely controlled Ni/NiO gyroid nanostructure. After carbon coating, a well-interconnected nanoporous gyroid Ni/NiO/C nanocomposite can be successfully fabricated. Benefiting from the well-interconnected nanoporous structure with ultrafine transition metal oxide and uniform carbon coating, the gyroid nanoporous Ni/NiO/C nanocomposite electrodes exhibited high specific capacities at various rates (1240 mA h g−1 at 0.2 A g−1, 902 mA h g−1 at 2 A g−1 and 424 mA h g−1 at 10 A g−1) and excellent cyclability (809 mA h g−1 at 1 A g−1 after 1000 cycles, average coulombic efficiency 99.86%). This research demonstrates a universal approach for constructing a nanostructured electrode with explicitly controlled block copolymer phase separation.