Bo-Quan Li

Topological Defects in Metal-Free Nanocarbon for Oxygen Electrocatalysis.

A bifunctional graphene catalyst with abundant topological defects is achieved via the carbonization of natural gelatinized sticky rice to probe the underlying oxygen electrocatalytic mechanism. A nitrogen-free configuration with adjacent pentagon and heptagon carbon rings is revealed to exhibit the lowest overpotential for both oxygen reduction and evolution catalysis. The versatile synthetic strategy and novel insights on the activity origin facilitate the development of advanced metal-free carbocatalysts for a wide range of electrocatalytic applications.

Design Principles for Heteroatom‐Doped Nanocarbon to Achieve Strong Anchoring of Polysulfides for Lithium–Sulfur Batteries

Lithium-sulfur (Li-S) batteries have been intensively concerned to fulfill the urgent demands of high capacity energy storage. One of the major unsolved issues is the complex diffusion of lithium polysulfide intermediates, which in combination with the subsequent paradox reactions is known as the shuttle effect. Nanocarbon with homogeneous nonpolar surface served as scaffolding materials in sulfur cathode basically cannot afford a sufficient binding and confining effect to maintain lithium polysulfides within the cathode. Herein, a systematical density functional theory calculation of various heteroatoms-doped nanocarbon materials is conducted to elaborate the mechanism and guide the future screening and rational design of Li-S cathode for better performance. It is proved that the chemical modification using N or O dopant significantly enhances the interaction between the carbon hosts and the polysulfide guests via dipole-dipole electrostatic interaction and thereby effectively prevents shuttle of polysulfides, allowing high capacity and high coulombic efficiency. By contrast, the introduction of B, F, S, P, and Cl monodopants into carbon matrix is unsatisfactory. To achieve the strong-couple effect toward Li2 Sx , the principles for rational design of doped carbon scaffolds in Li-S batteries to achieve a strong electrostatic dipole-dipole interaction are proposed. An implicit volcano plot is obtained to describe the dependence of binding energies on electronegativity of dopants. Moreover, the codoping strategy is predicted to achieve even stronger interfacial interaction to trap lithium polysulfides.

Bifunctional Transition Metal Hydroxysulfides: Room-Temperature Sulfurization and Their Applications in Zn–Air Batteries

Bifunctional electrocatalysis for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) constitutes the bottleneck of various sustainable energy devices and systems like rechargeable metal-air batteries. Emerging catalyst materials are strongly requested toward superior electrocatalytic activities and practical applications. In this study, transition metal hydroxysulfides are presented as bifunctional OER/ORR electrocatalysts for Zn-air batteries. By simply immersing Co-based hydroxide precursor into solution with high-concentration S2- , transition metal hydroxides convert to hydroxysulfides with excellent morphology preservation at room temperature. The as-obtained Co-based metal hydroxysulfides are with high intrinsic reactivity and electrical conductivity. The electron structure of the active sites is adjusted by anion modulation. The potential for 10 mA cm-2 OER current density is 1.588 V versus reversible hydrogen electrode (RHE), and the ORR half-wave potential is 0.721 V versus RHE, with a potential gap of 0.867 V for bifunctional oxygen electrocatalysis. The Co3 FeS1.5 (OH)6 hydroxysulfides are employed in the air electrode for a rechargeable Zn-air battery with a small overpotential of 0.86 V at 20.0 mA cm-2 , a high specific capacity of 898 mAh g-1 , and a long cycling life, which is much better than Pt and Ir-based electrocatalyst in Zn-air batteries.

Monolithic-structured ternary hydroxides as freestanding bifunctional electrocatalysts for overall water splitting

Efficient oxygen and hydrogen evolution electrocatalysts, based on low-cost and earth-abundant elements, are strongly required for sustainable hydrogen production through water splitting. Herein, we fabricated a monolithic-structured electrode by facilely electrodepositing NiCoFe ternary layered double hydroxides (LDHs) onto 3D conductive scaffolds, providing abundant fully exposed active sites for electrochemical reactions. The moderate Co dopant effectively improved the electrical conductivity of the LDH phase and substantially increased its intrinsic activity. When used for oxygen evolution, the as-obtained monolith LDH electrode exhibited superior kinetics with 275 mV overpotential required to achieve 10 mA cm−2 in 0.10 M KOH, as well as a very low activation energy of 21.0 kJ mol−1. Such a freestanding electrode was also able to catalyze hydrogen evolution efficiently in alkaline media, which further enabled a high-efficiency water electrolyzer delivering 10 mA cm−2 at a very low cell voltage of 1.62 V in 1.0 M KOH. This sheds fresh insight into the principle and process of practical water electrolysis through the rational design of precious-metal-free bifunctional electrodes with a monolithic configuration.

A Quinonoid‐Imine‐Enriched Nanostructured Polymer Mediator for Lithium–Sulfur Batteries

The reversible formation of chemical bonds has potential for tuning multi-electron redox reactions in emerging energy-storage applications, such as lithium-sulfur batteries. The dissolution of polysulfide intermediates, however, results in severe shuttle effect and sluggish electrochemical kinetics. In this study, quinonoid imine is proposed to anchor polysulfides and to facilitate the formation of Li2 S2 /Li2 S through the reversible chemical transition between protonated state (NH+ ) and deprotonated state (N). When serving as the sulfur host, the quinonoid imine-doped graphene affords a very tiny shuttle current of 2.60 × 10-4 mA cm-2 , a rapid redox reaction of polysulfide, and therefore improved sulfur utilization and enhanced rate performance. A high areal specific capacity of 3.72 mAh cm-2 is achieved at 5.50 mA cm-2 on the quinonoid imine-doped graphene based electrode with a high sulfur loading of 3.3 mg cm-2 . This strategy sheds a new light on the organic redox mediators for reversible modulation of electrochemical reactions.

Anionic Regulated NiFe (Oxy)Sulfide Electrocatalysts for Water Oxidation

The construction of active sites with intrinsic oxygen evolution reaction (OER) is of great significance to overcome the limited efficiency of abundant sustainable energy devices such as fuel cells, rechargeable metal-air batteries, and in water splitting. Anionic regulation of electrocatalysts by modulating the electronic structure of active sites significantly promotes OER performance. To prove the concept, NiFeS electrocatalysts are fabricated with gradual variation of atomic ratio of S:O. With the rise of S content, the overpotential for water oxidation exhibits a volcano plot under anionic regulation. The optimized NiFeS-2 electrocatalyst under anionic regulation possesses the lowest OER overpotential of 286 mV at 10 mA cm-2 and the fastest kinetics being 56.3 mV dec-1 to date. The anionic regulation methodology not only serves as an effective strategy to construct superb OER electrocatalysts, but also enlightens a new point of view for the in-depth understanding of electrocatalysis at the electronic and atomic level.

An aqueous preoxidation method for monolithic perovskite electrocatalysts with enhanced water oxidation performance

Aqueous preoxidation strategy for in situ hybridization of oxidative perovskite and reductive conductive frameworks. Perovskite oxides with poor conductivity call for three-dimensional (3D) conductive scaffolds to demonstrate their superb reactivities for oxygen evolution reaction (OER). However, perovskite formation usually requires high-temperature annealing at 600° to 900°C in air, under which most of the used conductive frameworks (for example, carbon and metal current collectors) are reductive and cannot survive. We propose a preoxidization coupled electrodeposition strategy in which Co2+ is preoxidized to Co3+ through cobalt Fenton reaction in aqueous solution, whereas the reductive nickel framework is well maintained during the sequential annealing under nonoxidative atmosphere. The in situ–generated Co3+ is inherited into oxidized perovskites deposited on 3D nickel foam, rendering the monolithic perovskite electrocatalysts with extraordinary OER performance with an ultralow overpotential of 350 mV required for 10 mA cm−2, a very small Tafel slope of 59 mV dec−1, and superb stability in 0.10 M KOH. Therefore, we inaugurate a unique strategy for in situ hybridization of oxidative active phase with reductive framework, affording superb reactivity of perovskite electrocatalyst for efficient water oxidation.

A Bifunctional Perovskite Promoter for Polysulfide Regulation toward Stable Lithium–Sulfur Batteries

Lithium-sulfur (LiS) batteries are strongly considered as the next-generation rechargeable cells. However, both the shuttle of lithium polysulfides (LiPSs) and sluggish kinetics in random deposition of lithium sulfides (Li2 S) significantly degrade the capacity, rate performance, and cycling life of LiS cells. Herein, bifunctional Ba0.5 Sr0.5 Co0.8 Fe0.2 O3-δ perovskite nanoparticles (PrNPs) are proposed as a promoter to immobilize LiPSs and guide the deposition of Li2 S in a LiS cell. The oxygen vacancy in PrNPs increases the metal reactivity to anchor LiPSs, and co-existence of lithiophilic (O) and sulfiphilic (Sr) sites in PrNP favor the dual-bonding (LiO and SrS bonds) to anchor LiPSs. The high catalytic nature of PrNP facilitates the kinetics of LiPS redox reaction. The PrNP with intrinsic LiPS affinity serves as nucleation sites for Li2 S deposition and guides its uniform propagation. Therefore, the bifunctional LiPS promoter in LiS cell yields high rate performance and ultralow capacity decay rate of 0.062% (a quarter of pristine LiS cells). The proposed strategy to immobilize LiPSs, promotes the conversion of LiPS, and regulates deposition of Li2 S by an emerging perovskite promoter and is also expected to be applied in other energy conversion and storage devices based on multi-electron redox reactions.

Regulating p -block metals in perovskite nanodots for efficient electrocatalytic water oxidation

Water oxidation represents the core process of many sustainable energy systems, such as fuel cells, rechargeable metal-air batteries, and water splitting. Material surface defects with high-energy hanging bonds possess superb intrinsic reactivity, whose actual performance is limited by the dimension and conductivity of the electrocatalyst. Herein we propose a surface defect-rich perovskite electrocatalyst through a p-block metal regulation concept to achieve high performance for oxygen evolution. As a typical p-metal, Sn4+ dissolves from the solid phase from model SnNiFe perovskite nanodots, resulting in abundant surface defects with superior water oxidation performance. An oxygen pool model and a fusion-evolution mechanism are therefore proposed for the in-depth understanding of p-block metal regulation and the oxygen evolution reaction. The energy chemistry unveiled herein provides insights into water oxidation and helps to tackle critical issues in multi-electron oxygen electrocatalysis.Electrocatalysts that possess high densities of surface defects show great promise for efficient water oxidation. Here the authors demonstrate that regulating the p-block metal content in perovskite nanodots imparts these materials with abundant surface defects and excellent electrocatalytic activity.

Ion–Solvent Complexes Promote Gas Evolution from Electrolytes on a Sodium Metal Anode

Lithium and sodium metal batteries are considered as promising next-generation energy storage devices due to their ultrahigh energy densities. The high reactivity of alkali metal toward organic solvents and salts results in side reactions, which further lead to undesirable electrolyte depletion, cell failure, and evolution of flammable gas. Herein, first-principles calculations and in situ optical microscopy are used to study the mechanism of organic electrolyte decomposition and gas evolution on a sodium metal anode. Once complexed with sodium ions, solvent molecules show a reduced LUMO, which facilitates the electrolyte decomposition and gas evolution. Such a general mechanism is also applicable to lithium and other metal anodes. We uncover the critical role of ion-solvent complexation for the stability of alkali metal anodes, reveal the mechanism of electrolyte gassing, and provide a mechanistic guidance to electrolyte and lithium/sodium anode design for safe rechargeable batteries.