Huigang Zhang

Three-dimensional bicontinuous ultrafast-charge and -discharge bulk battery electrodes

Rapid charge and discharge rates have become an important feature of electrical energy storage devices, but cause dramatic reductions in the energy that can be stored or delivered by most rechargeable batteries (their energy capacity). Supercapacitors do not suffer from this problem, but are restricted to much lower stored energy per mass (energy density) than batteries. A storage technology that combines the rate performance of supercapacitors with the energy density of batteries would significantly advance portable and distributed power technology. Here, we demonstrate very large battery charge and discharge rates with minimal capacity loss by using cathodes made from a self-assembled three-dimensional bicontinuous nanoarchitecture consisting of an electrolytically active material sandwiched between rapid ion and electron transport pathways. Rates of up to 400C and 1,000C for lithium-ion and nickel-metal hydride chemistries, respectively, are achieved (where a 1C rate represents a one-hour complete charge or discharge), enabling fabrication of a lithium-ion battery that can be 90% charged in 2 minutes.

High-power lithium ion microbatteries from interdigitated three-dimensional bicontinuous nanoporous electrodes

High-performance miniature power sources could enable new microelectronic systems. Here we report lithium ion microbatteries having power densities up to 7.4 mW cm(-2) μm(-1), which equals or exceeds that of the best supercapacitors, and which is 2,000 times higher than that of other microbatteries. Our key insight is that the battery microarchitecture can concurrently optimize ion and electron transport for high-power delivery, realized here as a three-dimensional bicontinuous interdigitated microelectrodes. The battery microarchitecture affords trade-offs between power and energy density that result in a high-performance power source, and which is scalable to larger areas.

Three-dimensional metal scaffold supported bicontinuous silicon battery anodes.

Silicon-based lithium ion battery anodes are attracting significant attention because of silicons exceptionally high lithium capacity. However, silicons large volume change during cycling generally leads to anode pulverization unless the silicon is dispersed throughout a matrix in nanoparticulate form. Because pulverization results in a loss of electric connectivity, the reversible capacity of most silicon anodes dramatically decays within a few cycles. Here we report a three-dimensional (3D) bicontinuous silicon anode formed by depositing a layer of silicon on the surface of a colloidal crystal templated porous nickel metal scaffold, which maintains electrical connectivity during cycling due to the scaffold. The porous metal framework serves to both impart electrical conductivity to the anode and accommodate the large volume change of silicon upon lithiation and delithiation. The initial capacity of the bicontinuous silicon anode is 3568 (silicon basis) and 1450 mAh g(-1) (including the metal framework) at 0.05C. After 100 cycles at 0.3C, 85% of the capacity remains. Compared to a foil-supported silicon film, the 3D bicontinuous silicon anode exhibits significantly improved mechanical stability and cycleability.

Mechanically and Chemically Robust Sandwich-Structured C@Si@C Nanotube Array Li-Ion Battery Anodes

Stability and high energy densities are essential qualities for emerging battery electrodes. Because of its high specific capacity, silicon has been considered a promising anode candidate. However, the several-fold volume changes during lithiation and delithiation leads to fractures and continuous formation of an unstable solid-electrolyte interphase (SEI) layer, resulting in rapid capacity decay. Here, we present a carbon-silicon-carbon (C@Si@C) nanotube sandwich structure that addresses the mechanical and chemical stability issues commonly associated with Si anodes. The C@Si@C nanotube array exhibits a capacity of ∼2200 mAh g(-1) (∼750 mAh cm(-3)), which significantly exceeds that of a commercial graphite anode, and a nearly constant Coulombic efficiency of ∼98% over 60 cycles. In addition, the C@Si@C nanotube array gives much better capacity and structure stability compared to the Si nanotubes without carbon coatings, the ZnO@C@Si@C nanorods, a Si thin film on Ni foam, and C@Si and Si@C nanotubes. In situ SEM during cycling shows that the tubes expand both inward and outward upon lithiation, as well as elongate, and then revert back to their initial size and shape after delithiation, suggesting stability during volume changes. The mechanical modeling indicates the overall plastic strain in a nanotube is much less than in a nanorod, which may significantly reduce low-cycle fatigue. The sandwich-structured nanotube design is quite general, and may serve as a guide for many emerging anode and cathode systems.

Fabrication and magnetic properties of hierarchical porous hollow nickel microspheres

Hierarchical porous hollow nickel microspheres with nickel nanoparticles as the in situ formed building units have been fabricated via a novel precursor hydrothermal redox method in alkaline solution of KBH4. The microspheres exhibit enhanced coercivity and remanent magnetization as compared with hollow nickel submicrometer spheres, hollow nickel nanospheres, bulk nickel, and free Ni nanoparticles. Investigations have demonstrated that the enhancement is attributed to the hierarchical porous hollow structure, while the hierarchical structure has little influence on saturation magnetization.

3D Scaffolded Nickel-Tin Li-Ion Anodes with Enhanced Cyclability

A 3D mechanically stable scaffold is shown to accommodate the volume change of a high-specific-capacity nickel-tin nanocomposite during operation as a Li-ion battery anode. The nickel-tin anode is supported by an electrochemically inactive conductive scaffold with an engineered free volume and controlled characteristic dimensions, which engender the electrode with significantly improved cyclability.

Hydrothermal Fabrication of Three‐Dimensional Secondary Battery Anodes

A generalized hydrothermal strategy for fabricating three-dimensional (3D) battery electrodes is presented. The hydrothermal growth deposits electrochemically active nanomaterials uniformly throughout the complex 3D mesostructure of the scaffold. Ni inverse opals coated with SnO2 nanoparticles or Co3O4 nanoplatelets, and SiO2 inverse opals coated with Fe3O4 are fabricated, all of which show attractive properties including good capacity retention and C-rate performances.

Electrochemically tunable thermal conductivity of lithium cobalt oxide

Using time-domain thermoreflectance, the thermal conductivity and elastic properties of a sputter deposited LiCoO2 film, a common lithium-ion cathode material, are measured as a function of the degree of lithiation. Here we report that via in situ measurements during cycling, the thermal conductivity of a LiCoO2 cathode reversibly decreases from ~5.4 to 3.7 W m(-1) K(-1), and its elastic modulus decreases from 325 to 225 GPa, as it is delithiated from Li1.0CoO2 to Li0.6CoO2. The dependence of the thermal conductivity on lithiation appears correlated with the lithiation-dependent phase behaviour. The oxidation-state-dependent thermal conductivity of electrolytically active transition metal oxides provides opportunities for dynamic control of thermal conductivity and is important to understand for thermal management in electrochemical energy storage devices.

Template-assisted three-dimensional nanolithography via geometrically irreversible processing.

An innovative and versatile nanofabrication technique based on template assisted three-dimensional (3D) nanolithography is presented that takes advantage of the irreversibility of conformal growth and conformal etching at locations with negative surface curvatures in 3D templates. Using colloidal crystals as templates, nanoring particles are generated with quantity much higher than conventional methods. Relying on the same principle, metallodielectric photonic crystals with discrete metal elements are fabricated that show strong absorption in the near-IR and transmission at longer wavelengths.

A 500 MHz carbon nanotube transistor oscillator

Operation of a carbon nanotube field effect transistor (FET) oscillator at a record frequency of 500 MHz is described. The FET was fabricated using a large parallel array of single-walled nanotubes grown by chemical vapor deposition on ST-quartz substrates. Matching of the gate capacitance with a series inductor enabled greater than unity net oscillator loop gain to be achieved at 500 MHz.