Zhanwei Xu

Mesoporous nitrogen-rich carbons derived from protein for ultra-high capacity battery anodes and supercapacitors

In this work we demonstrate that biomass-derived proteins serve as an ideal precursor for synthesizing carbon materials for energy applications. The unique composition and structure of the carbons resulted in very promising electrochemical energy storage performance. We obtained a reversible lithium storage capacity of 1780 mA h g−1, which is among the highest ever reported for any carbon-based electrode. Tested as a supercapacitor, the carbons exhibited a capacitance of 390 F g−1, with an excellent cycle life (7% loss after 10 000 cycles). Such exquisite properties may be attributed to a unique combination of a high specific surface area, partial graphitization and very high bulk nitrogen content. It is a major challenge to derive carbons possessing all three attributes. By templating the structure of mesoporous cellular foam with egg white-derived proteins, we were able to obtain hierarchically mesoporous (pores centered at ∼4 nm and at 20–30 nm) partially graphitized carbons with a surface area of 805.7 m2 g−1 and a bulk N-content of 10.1 wt%. When the best performing sample was heated in Ar to eliminate most of the nitrogen, the Li storage capacity and the specific capacitance dropped to 716 mA h g−1 and 80 F g−1, respectively.

Interconnected carbon nanosheets derived from hemp for ultrafast supercapacitors with high energy.

We created unique interconnected partially graphitic carbon nanosheets (10-30 nm in thickness) with high specific surface area (up to 2287 m(2) g(-1)), significant volume fraction of mesoporosity (up to 58%), and good electrical conductivity (211-226 S m(-1)) from hemp bast fiber. The nanosheets are ideally suited for low (down to 0 °C) through high (100 °C) temperature ionic-liquid-based supercapacitor applications: At 0 °C and a current density of 10 A g(-1), the electrode maintains a remarkable capacitance of 106 F g(-1). At 20, 60, and 100 °C and an extreme current density of 100 A g(-1), there is excellent capacitance retention (72-92%) with the specific capacitances being 113, 144, and 142 F g(-1), respectively. These characteristics favorably place the materials on a Ragone chart providing among the best power-energy characteristics (on an active mass normalized basis) ever reported for an electrochemical capacitor: At a very high power density of 20 kW kg(-1) and 20, 60, and 100 °C, the energy densities are 19, 34, and 40 Wh kg(-1), respectively. Moreover the assembled supercapacitor device yields a maximum energy density of 12 Wh kg(-1), which is higher than that of commercially available supercapacitors. By taking advantage of the complex multilayered structure of a hemp bast fiber precursor, such exquisite carbons were able to be achieved by simple hydrothermal carbonization combined with activation. This novel precursor-synthesis route presents a great potential for facile large-scale production of high-performance carbons for a variety of diverse applications including energy storage.

Carbon Nanosheet Frameworks Derived from Peat Moss as High Performance Sodium Ion Battery Anodes

We demonstrate that peat moss, a wild plant that covers 3% of the earths surface, serves as an ideal precursor to create sodium ion battery (NIB) anodes with some of the most attractive electrochemical properties ever reported for carbonaceous materials. By inheriting the unique cellular structure of peat moss leaves, the resultant materials are composed of three-dimensional macroporous interconnected networks of carbon nanosheets (as thin as 60 nm). The peat moss tissue is highly cross-linked, being rich in lignin and hemicellulose, suppressing the nucleation of equilibrium graphite even at 1100 °C. Rather, the carbons form highly ordered pseudographitic arrays with substantially larger intergraphene spacing (0.388 nm) than graphite (c/2 = 0.3354 nm). XRD analysis demonstrates that this allows for significant Na intercalation to occur even below 0.2 V vs Na/Na(+). By also incorporating a mild (300 °C) air activation step, we introduce hierarchical micro- and mesoporosity that tremendously improves the high rate performance through facile electrolyte access and further reduced Na ion diffusion distances. The optimized structures (carbonization at 1100 °C + activation) result in a stable cycling capacity of 298 mAh g(-1) (after 10 cycles, 50 mA g(-1)), with ∼150 mAh g(-1) of charge accumulating between 0.1 and 0.001 V with negligible voltage hysteresis in that region, nearly 100% cycling Coulombic efficiency, and superb cycling retention and high rate capacity (255 mAh g(-1) at the 210th cycle, stable capacity of 203 mAh g(-1) at 500 mA g(-1)).

Graphene-Nickel Cobaltite Nanocomposite Asymmetrical Supercapacitor with Commercial Level Mass Loading

AbstractA high performance asymmetric electrochemical supercapacitor with a mass loading of 10 mg·cm−2 on each planar electrode has been fabricated by using a graphene-nickel cobaltite nanocomposite (GNCC) as a positive electrode and commercial activated carbon (AC) as a negative electrode. Due to the rich number of faradaic reactions on the nickel cobaltite, the GNCC positive electrode shows significantly higher capacitance (618 F·g−1) than graphene-Co3O4 (340 F·g−1) and graphene-NiO (375 F·g−1) nanocomposites synthesized under identical conditions. More importantly, graphene greatly enhances the conductivity of nickel cobaltite and allows the positive electrode to charge/discharge at scan rates similar to commercial AC negative electrodes. This improves both the energy density and power density of the asymmetric cell. The asymmetric cell composed of 10 mg GNCC and 30 mg AC displayed an energy density in the range of 19.5 Wh·kg−1 with an operational voltage of 1.4 V. At high sweep rate, the system is capable of delivering an energy density of 7.6 Wh·kg−1 at a power density of about 5600 W·kg−1. Cycling results demonstrate that the capacitance of the cell increases to 116% of the original value after the first 1600 cycles due to a progressive activation of the electrode, and maintains 102% of the initial value after 10000 cycles.

Colossal pseudocapacitance in a high functionality–high surface area carbon anode doubles the energy of an asymmetric supercapacitor

Here we demonstrate a facile template-free synthesis route to create macroscopically monolithic carbons that are both highly nitrogen rich (4.1–7.6 wt%) and highly microporous (SA up to 1405 m2 g−1, 88 vol% micropores). While such materials, which are derived from common chicken egg whites, are expected to be useful in a variety of applications, they are extremely promising for electrochemical capacitors based on aqueous electrolytes. The Highly Functionalized Activated Carbons (HFACs) demonstrate a specific capacitance of >550 F g−1 at 0.25 A g−1 and >350 F g−1 at 10 A g−1 in their optimized state. These are among the highest values reported in the literature for carbon-based electrodes, including for systems such as templated carbons and doped graphene. We show that HFACs serve as ideal negative electrodes in asymmetric supercapacitors, where historically the specific capacitance of the oxide-based positive electrode was mismatched with the much lower specific capacitance of the opposing AC. An asymmetric cell employing HFACs demonstrates a 2× higher specific energy and a 4× higher volumetric energy density as compared to the one employing a high surface area commercial AC. With 3.5 mg cm−2 of HFAC opposing 5.0 mg cm−2 of NiCo2O4/graphene, specific energies (active mass normalized) of 48 W h kg−1 at 230 W kg−1 and 28 W h kg−1 at 1900 W kg−1 are achieved. The asymmetric cell performance is among the best in the literature for hybrid aqueous systems, and actually rivals cells operating with a much wider voltage window in organic electrolytes.

Supercapacitive carbon nanotube-cobalt molybdate nanocomposites prepared via solvent-free microwave synthesis

Cobalt molybdate (CoMoO4) nanoplatelets with a crystalline-amorphous core-shell structure anchored via multi-walled carbon nanotubes were prepared by a solvent-free microwave synthesis method. The entire procedure took only 15 min. The nanocomposite shows a promising capacitance of 170 F g−1 with a potential window of 0.8 V, degrading by only 6.8% after 1000 cycles.