skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Polypyrrole coated δ-MnO 2 nanosheet arrays as a highly stable lithium-ion-storage anode
Manganese dioxide (MnO 2 ) with a conversion mechanism is regarded as a promising anode material for lithium-ion batteries (LIBs) owing to its high theoretical capacity (∼1223 mA h g −1 ) and environmental benignity as well as low cost. However, it suffers from insufficient rate capability and poor cyclic stability. To circumvent this obstacle, semiconducting polypyrrole coated-δ-MnO 2 nanosheet arrays on nickel foam (denoted as MnO 2 @PPy/NF) are prepared via hydrothermal growth of MnO 2 followed by the electrodeposition of PPy on the anode in LIBs. The electrode with ∼50 nm thick PPy coating exhibits an outstanding overall electrochemical performance. Specifically, a high rate capability is obtained with ∼430 mA h g −1 of discharge capacity at a high current density of 2.67 A g −1 and more than 95% capacity is retained after over 120 cycles at a current rate of 0.86 A g −1 . These high electrochemical performances are attributed to the special structure which shortens the ion diffusion pathway, accelerates charge transfer, and alleviates volume change in the charging/discharging process, suggesting a promising route for designing a conversion-type anode material for LIBs.  more » « less
Award ID(s):
1803256
PAR ID:
10185787
Author(s) / Creator(s):
; ; ; ; ; ;
Date Published:
Journal Name:
Dalton Transactions
Volume:
49
Issue:
23
ISSN:
1477-9226
Page Range / eLocation ID:
7903 to 7913
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Rechargeable lithium–sulfur batteries have emerged as a viable technology for next generation electrochemical energy storage, and the sulfur cathode plays a critical role in determining the device performance. In this study, we prepared functional composites based on polypyrrole-coated MnO 2 nanotubes as a highly efficient sulfur host (sulfur mass loading 63.5%). The hollow interior of the MnO 2 nanotubes not only allowed for accommodation of volumetric changes of sulfur particles during the cycling process, but also confined the diffusion of lithium polysulfides by physical restriction and chemical adsorption, which minimized the loss of polysulfide species. In addition, the polypyrrole outer layer effectively enhanced the electrical conductivity of the cathode to facilitate ion and electron transport. The as-prepared MnO 2 -PPy-S composite delivered an initial specific capacity of 1469 mA h g −1 and maintained an extremely stable cycling performance, with a small capacity decay of merely 0.07% per cycle at 0.2C within 500 cycles, a high average coulombic efficiency of 95.7% and an excellent rate capability at 470 mA h g −1 at the current density of 3C. 
    more » « less
  2. 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
  3. Current commercial batteries are mainly metal based, with metal elements in charge carriers and/or electrode materials, which poses potential economic and environmental concerns due to the heavy use of nonrenewable metals. Thus, metal-free batteries present a unique opportunity as sustainable energy storage devices, though the relevant research is still in its infancy. Herein, we present an all-organic metal-free NH 4 + ion full battery that can operate at a low temperature of 0 °C, by using polypyrrole (PPy) as the cathode, polyaniline (PANI) as the anode, and 19 m ammonium acetate aqueous solution as electrolyte. For the first time, PPy is demonstrated as a high-capacity host material for both NH 4 + and K + storage, when cycled in water in salt electrolytes (WiSEs). When tested in a three-electrode cell containing 25 m NH 4 CH 3 COO electrolyte, PPy exhibits an impressive capacity of 125 mA h g −1 at a specific current of 1 A g −1 and retains 43.61 mA h g −1 at 25 A g −1 . Additionally, a full battery is assembled using the PPy cathode and PANI anode coupled with 19 m NH 4 CH 3 COO WiSE. This battery is found to deliver a capacity of 78.405 mA h g −1 at 25 °C and 49.083 mA h g −1 at 0 °C with a capacity retention of 71.83% after 200 cycles, demonstrating its potential for operations at low temperatures. Additionally, the physiochemical properties of NH 4 + -based WiSEs are examined by Raman and nuclear magnetic resonance (NMR) spectroscopies, to explore their electrochemical behaviors and the fundamental effect of salt concentration on the electrolyte characteristics. This study presents the first non-metal battery with potential for low-temperature applications and opens the door to future metal-free electronics that would generate long-term benefits to the environment. 
    more » « less
  4. Lithium-ion batteries (LIBs) are widely used energy storage devices, and sodium-ion batteries (SIBs) are promising alternatives to LIBs because sodium is of high abundance and low toxicity. However, a dominant obstacle for the advancement of LIBs and SIBs is the lack of high capacity anode materials, especially for SIBs. Here, we propose that three characteristics, namely appropriate pore size, suitable pore distribution, and an entirely planar topology, can help achieve ultrahigh capacity 2D anode materials. Under such guidelines, we constructed a B 7 P 2 monolayer, and investigated its potential as a LIB/SIB anode material by means of density functional theory (DFT) computations. Encouragingly, the B 7 P 2 monolayer possesses all the essential properties of a high-capacity LIB/SIB anode: its high stability ensures the experimental feasibility of synthesis, its metallicity does not change upon Li/Na adsorption and desorption, the Li/Na can well diffuse on the surface, and the open-circuit voltage is in a good range. Most importantly, the B 7 P 2 monolayer has a high storage capacity of 3117 mA h g −1 for both LIBs and SIBs, and this capacity value ranks among the highest for 2D SIB anode materials. This study offers us some good clues to design/discover other anode materials with ultrahigh capacities, and serves us another vivid example that (implicit and hidden) trends/rules in the literature can guide us in the design of functional materials more efficiently. 
    more » « less
  5. Molybdenum disulfide (MoS 2 ) may be a promising alternative for lithium ion batteries (LIBs) because it offers a unique layered crystal structure with a large and tunable distance between layers. This enables the anticipated excellent rate and cycling stability because they can promote the reversible lithium ion intercalation and de-intercalation without huge volume change which consequently prevents the pulverization of active materials during repeated charge and discharge processes. Herein, we prepared hierarchical MoS 2 –carbon (MoS 2 –C) microspheres via a continuous and scalable ultrasonic nebulization assisted route. The structure, composition, and electrochemical properties are investigated in detail. The MoS 2 –C microspheres consist of few-layer MoS 2 nanosheets bridged by carbon, which separates the exfoliated MoS 2 layers and prevents their aggregation and restacking, thus leading to improved kinetic, enhanced conductivity and structural integrity. The novel architecture offers additional merits such as overall large size and high packing density, which promotes their practical applications. The MoS 2 –C microspheres have been demonstrated with excellent electrochemical performances in terms of low resistance, high capacity even at large current density, stable cycling performance, etc. The electrodes exhibited 800 mA h g −1 at 1000 mA g −1 over 170 cycles. At a higher current density of 3200 mA g −1 , a capacity of 730 mA h g −1 can be also maintained. The MoS 2 –C microspheres are practically applicable not only because of the continuous and large scale synthesis via the current strategy, but also the possess a robust and integrated architecture which ensures the excellent electrochemical properties. 
    more » « less