Carbon Corrosion Induced by Surface Defects Accelerates Degradation of Platinum/Graphene Catalysts in Oxygen Reduction Reaction.

Graphene supported electrocatalysts have demonstrated remarkable catalytic performance for oxygen reduction reaction (ORR). However, their durability and cycling performance are greatly limited by Oswald ripening of platinum (Pt) and graphene support corrosion. Moreover, comprehensive studies on the mechanisms of catalysts degradation under 0.6-1.6 V versus RHE (Reversible Hydrogen Electrode) is still lacking. Herein, degradation mechanisms triggered by different defects on graphene supports are investigated by two cycling protocols. In the start-up/shutdown cycling (1.0-1.6 V vs. RHE), carbon oxidation reaction (COR) leads to shedding or swarm-like aggregation of Pt nanoparticles (NPs). Theoretical simulation results show that the expansion of vacancy defects promotes reaction kinetics of the decisive step in COR, reducing its reaction overpotential. While under the load cycling (0.6-1.0 V vs. RHE), oxygen containing defects lead to an elevated content of Pt in its oxidation state which intensifies Oswald ripening of Pt. The presence of vacancy defects can enhance the transfer of electrons from graphene to the Pt surface, reducing the d-band center of Pt and making it more difficult for the oxidation state of platinum to form in the cycling. This work will provide comprehensive understanding on Pt/Graphene catalysts degradation mechanisms.

Releasing Free Radicals in Precursor Triggers the Formation of Closed Pores in Hard Carbon for Sodium-Ion Batteries.

Increasing closed pore volume in hard carbon is considered to be the most effective way to enhance the electrochemical performance in sodium-ion batteries. However, there is a lack of systematic insights into the formation mechanisms of closed pores at molecular level. In this study, a regulation strategy of closed pores via adjustment of the content of free radicals is reported. Sufficient free radicals are exposed by part delignification of bamboo, which is related to the formation of well-developed carbon layers and rich closed pores. In addition, excessive free radicals from nearly total delignification lead to more reactive sites during pyrolysis, which competes for limited precursor debris to form smaller microcrystals and therefore compact the material. The optimal sample delivers a large closed pore volume of 0.203 cm3 g-1, which leads to a high reversible capacity of 350 mAh g-1 at 20 mA g-1 and enhanced Na+ transfer kinetics. This work provides insights into the formation mechanisms of closed pores at molecular level, enabling rational design of hard carbon pore structures.

Regulating the Pore Structure of Activated Carbon by Pitch for High-Performance Sodium-Ion Storage.

The pore structure of carbon anodes plays a crucial role in enhancing the sodium storage capacity. Designing more confined pores in carbon anodes is accepted as an effective strategy. However, current design strategies for confined pores in carbon anodes fail to achieve both high capacity and initial Coulombic efficiency (ICE) simultaneously. Herein, we develop a strategy for utilizing the repeated impregnation and precarbonization method of liquid pitch to regulate the pore structure of the activated carbon (AC) material. Driven by capillary coalescence, the pitch is impregnated into the pores of AC, which reduces the specific surface area of the material. During the carbonization process, numerous pores with diameters less than 1 nm are formed, resulting in a high capacity and improved ICE of the carbon anode. Moreover, the ordered carbon layers derived from the liquid pitch also enhance the electrical conductivity, thereby improving the rate capability of as-obtained carbon anodes. This enables the fabricated material (XA-4T-1300) to have a high ICE of 91.1% and a capacity of 383.0 mA h g-1 at 30 mA g-1. The capacity retention is 95.5% after 300 cycles at 1 A g-1. This study proposes a practical approach to adjust the microcrystalline and pore structures to enhance the performance of sodium-ion storage in materials.

Whole Landscape of the Origin and Evolution of Gassing in Supercapacitors at a High Voltage.

Although supercapacitors with acetonitrile-based electrolytes (AN-based SCs) have realized high-voltage (3.0 V) applications by manufacturers, gas generation at high voltages is a critical issue. Also, the exact origins and evolution mechanisms of gas generation during SC aging at 3.0 V still lack a whole landscape. In this work, floating tests under realistic working conditions are conducted by 22450-type cylindrical cells with an AN-based commercial electrolyte. Comprehensive insights into the origins and evolution mechanisms of gas species at 2.7 and 3.0 V are acquired, which involves multiple side reactions related to the electrode, current collector, and electrolyte. Both experimental evidence and density functional theory calculations demonstrate that the primary reasons for gas generation are residual water and oxygen-containing functional groups, especially hydroxyl and carboxyl. More importantly, additional types of gas (such as CO2, NH3, and alkenes) can only be detected at a higher voltage of 3.0 V rather than 2.7 V after failure, suggesting that these gas species can be regarded as the failure signatures at 3.0 V. This breakthrough analysis will provide fundamental guidance for failure evaluation and designing AN-based SCs with extended lifetime at 3.0 V.

High-Voltage Redox Mediator of an Organic Electrolyte for Supercapacitors by Lewis Base Electrocatalysis.

Redox electrolytes for supercapacitors (SCs) have recently sparked widespread interest. Due to the redox reactions within electrolytes, they can achieve high capacitance and long cycle stability. However, the energy density of SCs with redox electrolytes is limited by the narrow applied electrochemical window due to the irreversible side reaction of redox mediators at high potential. To overcome this issue, a redox mediator with a high redox potential, tetrachloridehydroquinone (TCHQ), is added to organic electrolytes to obtain a broad electrochemical window. TCHQ is designed to undergo a dehydrogenation reaction catalyzed by N-doped activated carbon to provide capacitance. The pyrrole N atoms have the highest electrocatalytic activity based on the theoretical calculation of reaction overpotential with predicted reaction pathways due to their Lewis basicity. Benefitting from that, TCHQ shows promising reversibility with a larger electrochemical window (up to 2.7 V). As a result, a higher energy density is obtained when compared to commercial SCs. This study proposes a strategy for designing redox mediators and interfaces of SCs with high energy density and a calculation method of dehydrogenation reaction electrocatalysis.

New Insights into the Mechanism of LiDFBOP for Improving the Low-Temperature Performance via the Rational Design of an Interphase on a Graphite Anode.

The high impedance of the solid electrolyte interphase (SEI) is one of the important factors that deteriorate the charge behavior of lithium-ion batteries (LIBs) at low temperatures, which hinders their practical application in portable electronic products and electric vehicles under extreme conditions. Based on this consideration, a LiF-rich SEI film with low impedance, using lithium difluorobis(oxalato)phosphate (LiDFBOP) as an electrolyte additive and a blank electrolyte without commercial additives, is constructed on a graphite surface. The decomposition mechanism of LiDFBOP is further deduced by density functional theory calculations. This additive inhibits the decomposition of the electrolyte and then forms a thin SEI film with more LiF. LiF, possessing high Young's modulus, makes the SEI film dense and stable. At the same time, more LiF/Li2CO3 interfaces are formed to increase the ionic conductivity. Benefiting from the components and the structure of the SEI, the graphite/Li cells exhibit excellent cycling stability (ca. 85.5% initial capacity retention for 200 cycles at 1 C) and an impressive low-temperature performance (ca. 200% capacity for electrolytes without LiDFBOP at -20 °C). This work presents an effective strategy for developing a functional electrolyte to meet the requirement of LIBs with enhanced low-temperature performance.

Critical Role of Surface Defects in the Controllable Deposition of Li2S on Graphene: From Molecule to Crystallite.

Uncontrollable electrochemical deposition of Li2S has negative impacts on the electrochemical performance of lithium-sulfur batteries, but the relationship between the deposition and the surface defects is rarely reported. Herein, ab initio molecular dynamics (AIMD) and density functional theory (DFT) approaches are used to study the Li2S deposition behaviors on pristine and defected graphene substrates, including pyridinic N (PDN) doped and single vacancy (SV), as well as the interfacial characteristics, in that such defects could improve the polarity of the graphene material, which plays a vital role in the cathode. The result shows that due to the constraint of molecular vibration, Li2S molecules tend to form stable adsorption with PDN atoms and SV defects, followed by the nucleation of Li2S clusters on these sites. Moreover, the clusters are more likely to grow near these sites following a spherical pattern, while a lamellar pattern is favorable on pristine graphene substrates. It is also discovered that PDN atoms and SV defects provide atomic-level pathways for the electronic transfer within the Li2S-electrode interface, further improving the electrochemical performance of the Li-S battery. It is found for the first time that surface defects also have strong impacts on the deposition pattern of Li2S and provide electronic pathways simultaneously. Our work demonstrated the interior relationship between the surface defects in carbon substrates and the stability of Li2S precipitates, which is of high significance to understand the electrochemical kinetics and design Li-S battery with long cycle life.

Activated Carbon Based Supercapacitors with a Reduced Graphene Oxide Additive: Preparation and Properties.

We have successfully enhanced the performance of commercial supercapacitors that use Japan Kuraray 80F activated carbon and Super-P conductive carbon black as the conductive agent with reduced graphene oxide (rGO) additive. The ratios of conductive carbon black to rGO studied are 3:1, 5:1, 10:1, 15:1 and 1:0. The enhancement is most pronounced at 15:1, and the specific capacitance being 137.5 F g-1, which is a 23.8% improvement over the 1:0 control. The specific capacitance retention is 70.1% after 10000 cycles. The impedance resistance is also reduced to 1.5 Ω, which is 3.3 times lower than the 1:0 control. Additionally, the rGO additive does not alter the favorable pore size distribution of the primary matrix and successfully preserves its small mesoporous structure, which facilitates facile transport of electrolyte.

Self-Assembled 3D Graphene-Based Aerogel with Co3 O4 Nanoparticles as High-Performance Asymmetric Supercapacitor Electrode.

Using graphene oxide and a cobalt salt as precursor, a three-dimensional graphene aerogel with embedded Co3 O4 nanoparticles (3D Co3 O4 -RGO aerogel) is prepared by means of a solvothermal approach and subsequent freeze-drying and thermal reduction. The obtained 3D Co3 O4 -RGO aerogel has a high specific capacitance of 660 F g(-1) at 0.5 A g(-1) and a high rate capability of 65.1 % retention at 50 A g(-1) in a three-electrode system. Furthermore, the material is used as cathode to fabricate an asymmetric supercapacitor utilizing a hierarchical porous carbon (HPC) as anode and 6 M KOH aqueous solution as electrolyte. In a voltage range of 0.0 to 1.5 V, the device exhibits a high energy density of 40.65 Wh kg(-1) and a power density of 340 W kg(-1) and shows a high cycling stability (92.92 % capacitance retention after 2000 cycles). After charging for only 30 s, three CR2032 coin-type asymmetric supercapacitors in series can drive a light-emitting-diode (LED) bulb brightly for 30 min, which remains effective even after 1 h.

Unusual high oxygen reduction performance in all-carbon electrocatalysts.

Carbon-based electrocatalysts are more durable and cost-effective than noble materials for the oxygen reduction reaction (ORR), which is an important process in energy conversion technologies. Heteroatoms are considered responsible for the excellent ORR performance in many carbon-based electrocatalysts. But whether an all-carbon electrocatalyst can effectively reduce oxygen is unknown. We subtly engineered the interfaces between planar graphene sheets and curved carbon nanotubes (G-CNT) and gained a remarkable activity/selectivity for ORR (larger current, and n = 3.86, ~93% hydroxide + ~7% peroxide). This performance is close to that of Pt; and the durability is much better than Pt. We further demonstrate the application of this G-CNT hybrid as an all-carbon cathode catalyst for lithium oxygen batteries.We speculate that the high ORR activity of this G-CNT hybrid stems from the localized charge separation at the interface of the graphene and carbon nanotube, which results from the tunneling electron transfer due to the Fermi level mismatch on the planar and curved sp(2) surfaces. Our result represents a conceptual breakthrough and pioneers the new avenues towards practical all-carbon electrocatalysis.

A graphene-based nanostructure with expanded ion transport channels for high rate Li-ion batteries.

A graphene-based nanostructure with expanded Li(+) transport channels is reported, which is characterized by high capacity and excellent rate performance as an anode material for Li-ion batteries. The expanded structure is obtained by employing linear polymers as the spacers in the stacking process of graphene nanosheets.

Graphene oxide hydrogel at solid/liquid interface.

A strong solid/liquid interfacial interaction is found between porous alumina and graphene oxide (GO) aqueous dispersion, which promotes a fast enrichment of GO on the alumina surface and results in the formation of a GO hydrogel.