Li-Chang Yin

Oxygen Bridges between NiO Nanosheets and Graphene for Improvement of Lithium Storage

Graphene has been widely used to dramatically improve the capacity, rate capability, and cycling performance of nearly any electrode material for batteries. However, the binding between graphene and these electrode materials has not been clearly elucidated. Here we report oxygen bridges between graphene with oxygen functional groups and NiO from analysis by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy and confirm the conformation of oxygen bridges by the first-principles calculations. We found that NiO nanosheets (NiO NSs) are bonded strongly to graphene through oxygen bridges. The oxygen bridges mainly originate from the pinning of hydroxyl/epoxy groups from graphene on the Ni atoms of NiO NSs. The calculated adsorption energies (1.37 and 1.84 eV for graphene with hydroxyl and epoxy) of a Ni adatom on oxygenated graphene by binding with oxygen are comparable with that on graphene (1.26 eV). However, the calculated diffusion barriers of the Ni adatom on the oxygenated graphene surface (2.23 and 1.69 eV for graphene with hydroxyl and epoxy) are much larger than that on the graphene (0.19 eV). Therefore, the NiO NS is anchored strongly on the graphene through a C-O-Ni bridge, which allows a high reversible capacity and excellent rate performance. The easy binding/difficult dissociating characteristic of Ni adatoms on the oxygenated graphene facilitates fast electron hopping from graphene to NiO and thus the reversible lithiation and delithiation of NiO. We believe that the understanding of this oxygen bridge between graphene and NiO will lead to the development of other high-performance electrode materials.

A Graphene–Pure‐Sulfur Sandwich Structure for Ultrafast, Long‐Life Lithium–Sulfur Batteries

Lithium-sulfur (Li–S) batteries have high specific capacities and are considered as next-generation batteries for large-scale energy storage and electric vehicles. However, rapid capacity fade and low sulfur utilisation inhibit their use. We designed a unique sandwich structure with pure sulfur between two graphene membranes, which are continuously produced over a large area, as a very simple but effective approach for the fabrication of Li–S batteries with ultrafast charge/discharge rates and long-life. One membrane was used as a graphene current collector (GCC) to replace the conventional aluminium foil current collector, and sulfur was coated onto this membrane as the active material. The other membrane was coated onto a conventional polymer separator (G-separator). This electrode showed a high specific capacity of 1340 mA h g−1 at 300 mA g−1, a Coulombic efficiency approaching 100%, excellent high-rate performance and long cyclic stability. The GCC and G-separator not only effectively reduce the internal resistance of the sulfur cathode but also function as buffer layers to trap/immobilise and reuse the dissolved lithium polysulfides. Furthermore, for the first time, three-dimensional X-ray microtomography was used to investigate sulfur diffusion during electrochemical charge/discharge.

Fibrous Hybrid of Graphene and Sulfur Nanocrystals for High-Performance Lithium–Sulfur Batteries

Graphene-sulfur (G-S) hybrid materials with sulfur nanocrystals anchored on interconnected fibrous graphene are obtained by a facile one-pot strategy using a sulfur/carbon disulfide/alcohol mixed solution. The reduction of graphene oxide and the formation/binding of sulfur nanocrystals were integrated. The G-S hybrids exhibit a highly porous network structure constructed by fibrous graphene, many electrically conducting pathways, and easily tunable sulfur content, which can be cut and pressed into pellets to be directly used as lithium-sulfur battery cathodes without using a metal current-collector, binder, and conductive additive. The porous network and sulfur nanocrystals enable rapid ion transport and short Li(+) diffusion distance, the interconnected fibrous graphene provides highly conductive electron transport pathways, and the oxygen-containing (mainly hydroxyl/epoxide) groups show strong binding with polysulfides, preventing their dissolution into the electrolyte based on first-principles calculations. As a result, the G-S hybrids show a high capacity, an excellent high-rate performance, and a long life over 100 cycles. These results demonstrate the great potential of this unique hybrid structure as cathodes for high-performance lithium-sulfur batteries.

α-Sulfur Crystals as a Visible-Light-Active Photocatalyst

We show that in contrast to conventional compound photocatalysts, α-sulfur crystals of cyclooctasulfur (S(8)) are a visible-light-active elemental photocatalyst. The α-S crystals were found to have the ability not only to generate ·OH radicals but also to split water in a photoelectrochemical process under both UV-vis and visible-light irradiation. Although the absolute activity obtained was low because of the large particle size and poor hydrophilicity of the α-S crystals studied, there is great potential for increasing the activity with the assistance of known strategies such as surface modification, nanoscaling, doping, and coupling with other photocatalysts.

An Amorphous Carbon Nitride Photocatalyst with Greatly Extended Visible-Light-Responsive Range for Photocatalytic Hydrogen Generation

Amorphous carbon nitride (ACN) with a bandgap of 1.90 eV shows an order of magnitude higher photocatalytic activity in hydrogen evolution under visible light than partially crystalline graphitic carbon nitride with a bandgap of 2.82 eV. ACN is photocatalytically active under visible light at a wavelength beyond 600 nm.

Nitrogen-doped carbon monolith for alkaline supercapacitors and understanding nitrogen-induced redox transitions

A nitrogen-doped porous carbon monolith was synthesized as a pseudo-capacitive electrode for use in alkaline supercapacitors. Ammonia-assisted carbonization was used to dope the surface with nitrogen heteroatoms in a way that replaced carbon atoms but kept the oxygen content constant. Ammonia treatment expanded the micropore size-distributions and increased the specific surface area from 383 m(2) g(-1) to 679 m(2) g(-1). The nitrogen-containing porous carbon material showed a higher capacitance (246 F g(-1)) in comparison with the nitrogen-free one (186 F g(-1)). Ex situ electrochemical spectroscopy was used to investigate the evolution of the nitrogen-containing functional groups on the surface of the N-doped carbon electrodes in a three-electrode cell. In addition, first-principles calculations were explored regarding the electronic structures of different nitrogen groups to determine their relative redox potentials. We proposed possible redox reaction pathways based on the calculated redox affinity of different groups and surface analysis, which involved the reversible attachment/detachment of hydroxy groups between pyridone and pyridine. The oxidation of nitrogen atoms in pyridine was also suggested as a possible reaction pathway.

Increasing the Visible Light Absorption of Graphitic Carbon Nitride (Melon) Photocatalysts by Homogeneous Self-Modification with Nitrogen Vacancies

A novel reduced melon photocatalyst with a bandgap of 2.03 eV developed here has a widened visible light absorption range and suppressed radiative recombination of photo-excited charge carriers due to the homogeneous self-modification with nitrogen vacancies. As a consequence, the reduced melon shows a much superior photocatalytic activity compared to the pristine melon in generating •OH radicals and degrading the organic pollutant Rhodamine B.

A red anatase TiO2 photocatalyst for solar energy conversion

Narrowing the bandgap of wide-bandgap semiconductor photocatalysts (for instance, anatase TiO2) by introducing suitable heteroatoms has been actively pursued for increasing solar absorption, but usually suffers from a limited thermodynamic/kinetic solubility of substitutional dopants in bulk and/or dopant-induced recombination centres. Here we report a red anatase TiO2 microsphere with a bandgap gradient varying from 1.94 eV on its surface to 3.22 eV in its core by a conceptually different doping approach for harvesting the full spectrum of visible light. This approach uses a pre-doped interstitial boron gradient to weaken nearby Ti-O bonds for the easy substitution of oxygen by nitrogen, and consequently it substantially improves the nitrogen solubility. Furthermore, no nitrogen-related Ti3+ was formed in the red TiO2 due to a charge compensation effect by boron, which inevitably occurs in common nitrogen doped TiO2. The red anatase TiO2 exhibits photoelectrochemical water splitting activity under visible light irradiation. The results obtained may shed light on how to increase high visible light absorbance of wide-bandgap photocatalysts.

Crystal facet-dependent photocatalytic oxidation and reduction reactivity of monoclinic WO3 for solar energy conversion

The reactivity of a photocatalyst is basically influenced by its surface atomic and linked electronic structure. Tuning different crystal facets is becoming an important strategy to optimize the reactivity of a photocatalyst for targeted reactions. Here we report a facile and new route of synthesizing a quasi-cubic-like WO3 crystal with a nearly equal percentage of {002}, {200} and {020} facets, and a rectangular sheet-like WO3 crystal with predominant {002} facet by controlling acidic hydrolysis of crystalline WB. As a result of electronic structure effects induced by crystal facet, the quasi-cubic-like WO3 crystal with a deeper valence band maximum shows a much higher O2 evolution rate in photocatalytic water oxidation than the rectangular sheet-like WO3 crystal. The latter, with an elevated conduction band minimum of 0.3 eV, is able to photoreduce CO2 to generate CH4 in the presence of H2O vapor.

Conductive porous vanadium nitride/graphene composite as chemical anchor of polysulfides for lithium-sulfur batteries

Although the rechargeable lithium–sulfur battery is an advanced energy storage system, its practical implementation has been impeded by many issues, in particular the shuttle effect causing rapid capacity fade and low Coulombic efficiency. Herein, we report a conductive porous vanadium nitride nanoribbon/graphene composite accommodating the catholyte as the cathode of a lithium–sulfur battery. The vanadium nitride/graphene composite provides strong anchoring for polysulfides and fast polysulfide conversion. The anchoring effect of vanadium nitride is confirmed by experimental and theoretical results. Owing to the high conductivity of vanadium nitride, the composite cathode exhibits lower polarization and faster redox reaction kinetics than a reduced graphene oxide cathode, showing good rate and cycling performances. The initial capacity reaches 1,471 mAh g−1 and the capacity after 100 cycles is 1,252 mAh g−1 at 0.2 C, a loss of only 15%, offering a potential for use in high energy lithium–sulfur batteries.