Advances in the synthesis and processing of graphene-based materials have presented the opportunity to design novel lithium-ion battery (LIB) anode materials that can meet the power requirements of next-generation power devices. In this work, a poly(methacrylic acid) (PMAA)-induced self-assembly process was used to design super-mesoporous Fe 3 O 4 and reduced-graphene-oxide (Fe 3 O 4 @RGO) anode materials. We demonstrate the relationship between the media pH and Fe 3 O 4 @RGO nanostructure, in terms of dispersion state of PMAA-stabilized Fe 3 O 4 @GO sheets at different surrounding pH values, and porosity of the resulted Fe 3 O 4 @RGO anode. The anode shows a high surface area of 338.8 m 2 g −1 with a large amount of 10–40 nm mesopores, which facilitates the kinetics of Li-ions and electrons, and improves electrode durability. As a result, Fe 3 O 4 @RGO delivers high specific-charge capacities of 740 mA h g −1 to 200 mA h g −1 at various current densities of 0.5 A g −1 to 10 A g −1 , and an excellent capacity-retention capability even after long-term charge–discharge cycles. The PMAA-induced assembly method addresses the issue of poor dispersion of Fe 3 O 4 -coated graphene materials—which is a major impediment in the synthesis process—and provides a facile synthetic pathway for depositing Fe 3 O 4 and other metal oxide nanoparticles on highly porous RGO.
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Synthesis and Li-ion electrode properties of layered MAB phases Ni n+1 ZnB n ( n = 1, 2)
Ternary MAB phases (layered transition metal borides) have recently attracted interest due to their exfoliation potential toward MBenes (analogous to MXenes), which are predicted to have excellent Li-ion battery performance. We have achieved single-phase synthesis of two MAB phases with general composition Ni n+1 ZnB n ( n = 1, 2), the crystal structures of which contain zinc layers sandwiched between thin ( n = 1) and thick ( n = 2) Ni–B slabs. Highly stacked MAB sheets were confirmed by X-ray diffraction and high-resolution scanning electron microscopy for both materials. Exposing Ni n+1 ZnB n to diluted hydrochloric acid led to the creation of crystalline microporous structures for n = 1 and non-porous detached sheets for n = 2. Both morphologies transformed the inactive bulk materials into highly active Li-ion battery anodes with capacities of ∼90 mA h g −1 ( n = 1) and ∼70 mA h g −1 ( n = 2) at a 100 mA g −1 lithiation–delithiation rate. The XPS analysis and BET surface area measurements reveal that the increased surface area and the reversible redox reaction of oxidized nickel species are responsible for this drastic increase of the lithiation–delithiation capacity. This proof of concept opens new avenues for the development of porous MAB, MAB nanosheets, MBenes and their composites for metal-ion battery applications.
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- Award ID(s):
- 1654780
- NSF-PAR ID:
- 10200073
- Date Published:
- Journal Name:
- Journal of Materials Chemistry A
- Volume:
- 8
- Issue:
- 4
- ISSN:
- 2050-7488
- Page Range / eLocation ID:
- 1646 to 1651
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Li2S is one of the most promising cathode materials for Li‐ion batteries because of its high theoretical capacity and compatibility with Li‐metal‐free anode materials. However, the poor conductivity and electrochemical reactivity lead to low initial capacity and severe capacity decay. In this communication, a nitrogen and phosphorus codoped carbon (N,P–C) framework derived from phytic acid doped polyaniline hydrogel is designed to support Li2S nanoparticles as a binder‐free cathode for Li–S battery. The porous 3D architecture of N and P codoped carbon provides continuous electron pathways and hierarchically porous channels for Li ion transport. Phosphorus doping can also suppress the shuttle effect through strong interaction between sulfur and the carbon framework, resulting in high Coulombic efficiency. Meanwhile, P doping in the carbon framework plays an important role in improving the reaction kinetics, as it may help catalyze the redox reactions of sulfur species to reduce electrochemical polarization, and enhance the ionic conductivity of Li2S. As a result, the Li2S/N,P–C composite electrode delivers a stable capacity of 700 mA h g−1with average Coulombic efficiency of 99.4% over 100 cycles at 0.1C and an areal capacity as high as 2 mA h cm−2at 0.5C.
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null (Ed.)Lithium metal–selenium (Li–Se) batteries offer high volumetric energy but are limited in their cycling life and fast charge characteristics. Here a facile approach is demonstrated to synthesize hierarchically porous hollow carbon spheres that host Se (Se@HHCS) and allow for state-of-the-art electrochemical performance in a standard carbonate electrolyte (1 M LiPF 6 in 1 : 1 EC : DEC). The Se@HHCS electrodes display among the most favorable fast charge and cycling behavior reported. For example, they deliver specific capacities of 442 and 357 mA h g −1 after 1500 and 2000 cycles at 5C and 10C, respectively. At 2C, Se@HHCS delivers 558 mA h g −1 after 500 cycles, with cycling coulombic efficiency of 99.9%. Post-mortem microstructural analysis indicates that the structures remain intact during extended cycling. Per GITT analysis, Se@HHCS possesses significantly higher diffusion coefficients in both lithiation and delithiation processes as compared to the baseline. The superior performance of Se@HHCS is directly linked to its macroscopic and nanoscale pore structure: the hollow carbon sphere morphology as well as the remnant open nanoporosity accommodates the 69% volume expansion of the Li to Li 2 Se transformation, with the nanopores also providing a complementary fast ion diffusion path.more » « less
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Nickel phosphide (Ni 5 P 4 ) nanosheets are synthesized using in situ chemical vapor deposition of P on Ni foam. The thickness of the as-synthesized Ni 5 P 4 film is determined to be ∼5 nm, using atomic force microscopy (AFM). The small thickness shortens the diffusion path of Li ions and results in fast ion transport. In addition, the 2D Ni 5 P 4 nanosheets seamlessly connect to the Ni foam, which facilitates electron transfer between Ni 5 P 4 and the Ni current collector. Therefore, the binder/carbon free-nickel supported Ni 5 P 4 shows fast rate performance as an anode for lithium-ion batteries (LIBs). The specific capacity of 2D Ni 5 P 4 is obtained as 600 mA h g −1 at a cycling rate of 0.1C, approaching the theoretical capacity of 768 mA h g −1 . Even at a rate of 0.5C, the capacity remains as 450 mA h g −1 over 100 cycles. A capacity >100 mA h g −1 is retained at a very high rate of 20C. Ni 5 P 4 also exhibits a low voltage of ∼0.5 V with respect to Li metal, which makes it a suitable negative electrode for LIBs. In operando 31 P NMR and 7 Li NMR are employed to probe the lithiation and de-lithiation mechanisms upon electrochemical cycling.more » « less
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Whilst MXenes (2D carbides and nitrides) have become highly popular in several research fields including the hydrogen evolution reaction (HER), unfortunately they are not competitive HER electrocatalysts in their bulk form (MAX phases). The related MAB (2D‐like bulk borides) phases and the derived 2D MBenes, however, are less studied but show better HER properties. Herein, two highly HER‐active and abundant MAB phases, Ni
n +1ZnBn (n = 1, 2), are studied experimentally and computationally. The pressed pellet electrodes from bulk polycrystalline powders of these phases drive a current density of 10 mA cm−2at impressive overpotentials ofη 10 = −0.171 V (n = 1) andη 10= −0.145 V (n = 2) to efficiently produce hydrogen. Density functional theory (DFT) calculations prove that the most active site is the hollow site on the nickel basal plane, showing a free energy value comparable to that of the hollow site of Pt (111). This study paves the way for further development of bulk and nanoscale MAB phases for clean energy applications.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/c9ta12937e
