Xiulei Ji

A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries.

The Li-S battery has been under intense scrutiny for over two decades, as it offers the possibility of high gravimetric capacities and theoretical energy densities ranging up to a factor of five beyond conventional Li-ion systems. Herein, we report the feasibility to approach such capacities by creating highly ordered interwoven composites. The conductive mesoporous carbon framework precisely constrains sulphur nanofiller growth within its channels and generates essential electrical contact to the insulating sulphur. The structure provides access to Li+ ingress/egress for reactivity with the sulphur, and we speculate that the kinetic inhibition to diffusion within the framework and the sorption properties of the carbon aid in trapping the polysulphides formed during redox. Polymer modification of the carbon surface further provides a chemical gradient that retards diffusion of these large anions out of the electrode, thus facilitating more complete reaction. Reversible capacities up to 1,320 mA h g(-1) are attained. The assembly process is simple and broadly applicable, conceptually providing new opportunities for materials scientists for tailored design that can be extended to many different electrode materials.

Advances in Li–S batteries

Rechargeable Li–S batteries have received ever-increasing attention recently due to their high theoretical specific energy density, which is 3 to 5 times higher than that of Li ion batteries based on intercalation reactions. Li–S batteries may represent a next-generation energy storage system, particularly for large scale applications. The obstacles to realize this high energy density mainly include high internal resistance, self-discharge and rapid capacity fading on cycling. These challenges can be met to a large degree by designing novel sulfur electrodes with “smart” nanostructures. This highlight provides an overview of major developments of positive electrodes based on this concept.

Stabilizing lithium–sulphur cathodes using polysulphide reservoirs

The possibility of achieving high-energy, long-life storage batteries has tremendous scientific and technological significance. An example is the Li-S cell, which can offer a 3-5-fold increase in energy density compared with conventional Li-ion cells, at lower cost. Despite significant advances, there are challenges to its wide-scale implementation, which include dissolution of intermediate polysulphide reaction species into the electrolyte. Here we report a new concept to mitigate the problem, which relies on the design principles of drug delivery. Our strategy employs absorption of the intermediate polysulphides by a porous silica embedded within the carbon-sulphur composite that not only absorbs the polysulphides by means of weak binding, but also permits reversible desorption and release. It functions as an internal polysulphide reservoir during the reversible electrochemical process to give rise to long-term stabilization and improved coulombic efficiency. The reservoir mechanism is general and applicable to Li/S cathodes of any nature.

High “C” rate Li-S cathodes: sulfur imbibed bimodal porous carbons

A highly ordered mesoporous carbon with a bimodal pore structure which exhibits a high specific area and large pore volume, was synthesized by a triblock-copolymer-templating approach. This optimized framework served as the scaffold for the preparation of carbon/sulfur (C/S) nanocomposites that serve as novel cathodes for Li-S batteries. They exhibit high discharge capacities and good cycling stability at very high current rates of 1675 mA g−1 (1 C), which can be attributed to the unique bimodal porous structure of the carbon. The small mesopores contain the majority of the sulfur mass and aid in suppressing the diffusion of polysulfide species into the electrolyte, whilst the large interconnected cylindrical pores favour rapid transport of solvated Li+ on charge/discharge. Additional doping with hydrophilic nanoporous silica also aids in capacity retention on cycling.

Na-Ion Battery Anodes: Materials and Electrochemistry

The intermittent nature of renewable energy sources, such as solar and wind, calls for sustainable electrical energy storage (EES) technologies for stationary applications. Li will be simply too rare for Li-ion batteries (LIBs) to be used for large-scale storage purposes. In contrast, Na-ion batteries (NIBs) are highly promising to meet the demand of grid-level storage because Na is truly earth abundant and ubiquitous around the globe. Furthermore, NIBs share a similar rocking-chair operation mechanism with LIBs, which potentially provides high reversibility and long cycling life. It would be most efficient to transfer knowledge learned on LIBs during the last three decades to the development of NIBs. Following this logic, rapid progress has been made in NIB cathode materials, where layered metal oxides and polyanionic compounds exhibit encouraging results. On the anode side, pure graphite as the standard anode for LIBs can only form NaC64 in NIBs if solvent co-intercalation does not occur due to the unfavorable thermodynamics. In fact, it was the utilization of a carbon anode in LIBs that enabled the commercial successes. Anodes of metal-ion batteries determine key characteristics, such as safety and cycling life; thus, it is indispensable to identify suitable anode materials for NIBs. In this Account, we review recent development on anode materials for NIBs. Due to the limited space, we will mainly discuss carbon-based and alloy-based anodes and highlight progress made in our groups in this field. We first present what is known about the failure mechanism of graphite anode in NIBs. We then go on to discuss studies on hard carbon anodes, alloy-type anodes, and organic anodes. Especially, the multiple functions of natural cellulose that is used as a low-cost carbon precursor for mass production and as a soft substrate for tin anodes are highlighted. The strategies of minimizing the surface area of carbon anodes for improving the first-cycle Coulombic efficiency are also outlined, where graphene oxide was employed as dehydration agent and 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was used to unzip wood fiber. Furthermore, surface modification by atomic layer deposition technology is introduced, where we discover that a thin layer of Al2O3 can function to encapsulate Sn nanoparticles, leading to a much enhanced cycling performance. We also highlight recent work about the phosphorene/graphene anode, which outperformed other anodes in terms of capacity. The aromatic organic anode is also studied as anode with very high initial sodiation capacity. Furthermore, electrochemical intercalation of Na ions into reduced graphene oxide is applied for fabricating transparent conductors, demonstrating the great feasibility of Na ion intercalation for optical applications.

Plasmonic Photoanodes for Solar Water Splitting with Visible Light

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO(2), forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.

Carbon Electrodes for K-Ion Batteries

We for the first time report electrochemical potassium insertion in graphite in a nonaqueous electrolyte, which can exhibit a high reversible capacity of 273 mAh/g. Ex situ XRD studies confirm that KC36, KC24, and KC8 sequentially form upon potassiation, whereas depotassiation recovers graphite through phase transformations in an opposite sequence. Graphite shows moderate rate capability and relatively fast capacity fading. To improve the performance of carbon K-ion anodes, we synthesized a nongraphitic soft carbon that exhibits cyclability and rate capability much superior to that of graphite. This work may open up a new paradigm toward rechargeable K-ion batteries.

Review on recent advances in nitrogen-doped carbons: preparations and applications in supercapacitors

It is of great interest to develop new carbon-based materials as electrodes for supercapacitors because the conventional electrodes of activated carbons in supercapacitors cannot meet the ever-increasing demands for high energy and power densities for electronic devices. Due to their high electronic conductivity and improved hydrophilic properties, together with their easy syntheses and functionalization, N-doped carbons have shown a great potential in energy storage and conversion applications. In this review, after a brief introduction of electrochemical capacitors, we summarize the advances, in the recent six years, in the preparation methods of N-doped carbons for applications in supercapacitors. We also discuss and predict futuristic research trends towards the design and syntheses of N-doped carbons with unique properties for electrochemical energy storage.

Carbon nanofibers derived from cellulose nanofibers as a long-life anode material for rechargeable sodium-ion batteries

A highly reversible anode is indispensable to the future success of sodium-ion batteries (SIBs). Herein, carbon nanofibers (CNFs) derived from cellulose nanofibers are investigated as an anode material for SIBs. The CNFs exhibit very promising electrochemical properties, including a high reversible capacity (255 mA h g−1 at 40 mA g−1), good rate capability (85 mA h g−1 at 2000 mA g−1), and excellent cycling stability (176 mA h g−1 at 200 mA g−1 over 600 cycles).

Pyrolysis of cellulose under ammonia leads to nitrogen-doped nanoporous carbon generated through methane formation.

Here, we present a simple one-step fabrication methodology for nitrogen-doped (N-doped) nanoporous carbon membranes via annealing cellulose filter paper under NH3. We found that nitrogen doping (up to 10.3 at %) occurs during cellulose pyrolysis under NH3 at as low as 550 °C. At 700 °C or above, N-doped carbon further reacts with NH3, resulting in a large surface area (up to 1973.3 m(2)/g). We discovered that the doped nitrogen, in fact, plays an important role in the reaction, leading to carbon gasification. CH4 was experimentally detected by mass spectrometry as a product in the reaction between N-doped carbon and NH3. When compared to conventional activated carbon (1533.6 m(2)/g), the N-doped nanoporous carbon (1326.5 m(2)/g) exhibits more than double the unit area capacitance (90 vs 41 mF/m(2)).