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摘要: 在锂离子电池（LIBs）和钠离子电池（SIBs）中，设计同时适用的负极材料，使其具有高倍率性能和超长循环寿命是亟需解决的工作。本文采用静电纺丝技术和硫化工程技术成功制备了一种均匀分布在N,S-掺杂炭纳米纤维上的MoO2/MoS2异质结构（MoO2/MoS2@NSC）。其中一维炭骨架作为导电框架可缩短Li+/Na+的扩散途径；炭纳米纤维中N/S杂原子的掺杂引入了丰富的活性位点，显著增强了离子扩散动力学。此外，在MoO2相中通过原位形成的MoS2纳米片强化了异质界面，MoO2和MoS2之间异质界面的构建使得Li+/Na+的快速传输成为实现高效储能的关键。因此，作为LIBs负极材料时，MoO2/MoS2@NSC电极在5.0 A g−1的电流密度下循环2000圈后，仍具有640 mAh g−1的优异放电比容量，每圈的容量衰减率仅为0.002%；在10.0 A g−1的高电流密度下可达到614 mAh g−1的放电比容量。对于SIBs，在2.0 A g−1的电流密度下循环2000圈后其可逆容量仍能达到242 mAh g−1。本工作采用一种新颖的界面调控策略来合理地设计负极材料，从而提高Li+/Na+储存动力学，实现超长寿命的循环性能。Abstract: It is imperative to design suitable anode materials for both lithium-ion (LIBs) and sodium-ion batteries (SIBs) with a high-rate performance and ultralong cycling life. We fabricated a MoO2/MoS2 heterostructure that was then homogeneously distributed in N,S-doped carbon nanofibers (MoO2/MoS2@NSC) by electrospinning and sulfurization. The one-dimensional carbon fiber skeleton serves as a conductive frame to decrease the diffusion pathway of Li+/Na+, while the N/S doping creates abundant active sites and significantly improves the ion diffusion kinetics. Moreover, the deposition of MoS2 nanosheets on the MoO2 bulk phase produces an interface that enables fast Li+/Na+ transport, which is crucial for achieving high efficiency energy storage. Consequently, as the anode for LIBs, MoO2/MoS2@NSC gives an excellent cycling stability of 640 mAh g−1 for 2000 cycles under 5.0 A g−1 with an ultralow average capacity drop of 0.002% per cycle and an exceptional rate capability of 614 mAh g−1 at 10.0 A g−1. In SIBs, it also produces a significantly better electrochemical performance (reversible capacity of 242 mAh g−1 under 2.0 A g−1 for 2000 cycles and 261 mAh g−1 under 5.0 A g−1). This work shows how introducing a novel interface in the anode can produce rapid Li+/Na+ storage kinetics and a long cycling performance.
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Figure 1. (a) XRD patterns of MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ, and MoO2/MoS2@NSC-Ⅲ. (b) TG curves of MoO2/MoS2@NSC-Ⅱ. (c) S 2p high-resolution XPS spectrum of MoO2/MoS2@NSC-Ⅱ. (d) Mo 3d and (e) N 1s high-resolution XPS spectra of MoO2@NSC and MoO2/MoS2@NSC-Ⅱ
Figure 2. SEM and TEM images of (a, d) MoO2/MoS2@NSC-Ⅰ, (b, e) MoO2/MoS2@NSC-Ⅱ, and (c, f) MoO2/MoS2@NSC-Ⅲ. (g) TEM images and (h) EDS elemental mapping images of MoO2/MoS2@NSC-Ⅱ
Figure 3. (a) CV curves of MoO2/MoS2@NSC-Ⅱ at the first three cycles (scan rate: 0.1 mV s−1). (b) The discharge/charge profiles of MoO2/MoS2@NSC-Ⅱ at 0.1 A g−1. (c) The cycling performance of MoO2@NSC, MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ and MoO2/MoS2@NSC-Ⅲ at 2.0 A g−1. (d) Rate capability of MoO2@NSC, MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ, and MoO2/MoS2@NSC-Ⅲ. (e) Long-term cycling performance and Coulombic efficiency of MoO2/MoS2@NSC-Ⅱ at 5.0 A g−1 and 10.0 A g−1
Figure 4. (a) Comparison of rate capability of the MoO2/MoS2@NSC-Ⅱ electrode with some other previously reported MoO2/MoS2-based anodes for LIBs in the literature. (b) b-Value analysis using the relationship between peak currents and scan rates for MoO2/MoS2@NSC-Ⅱ. (c) The detailed capacitive contribution (shaded region) of MoO2/MoS2@NSC-Ⅱ at 0.8 mV s−1. (d) The percentage ratio of capacitive and diffusion-controlled capacities at different scan rates for MoO2/MoS2@NSC-Ⅱ. (e) Plots of the peak current versus the square root of the scan rate of MoO2@NSC, MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ and MoO2/MoS2@NSC-Ⅲ. (f) Nyquist plots of MoO2@NSC and MoO2/MoS2@NSC-Ⅱ in the 100th and 200th cycles under the current density of 5.0 A g−1 (1: MoO2@NSC 100th; 2: MoO2@NSC 200th; 3: MoO2/MoS2@NSC-Ⅱ 100th; 4: MoO2/MoS2@NSC-Ⅱ 200th). (g) The corresponding plots of the real part of impedance (Z’) as a function of the inverse square root of the angular frequency (ω−1/2) in the Warburg region in the 100th and 200th cycles for MoO2@NSC and MoO2/MoS2@NSC-Ⅱ
Figure 5. (a) CV curves of MoO2/MoS2@NSC-Ⅱ at first three cycles (scan rate: 0.1 mV s−1). (b) The discharge/charge profiles of MoO2/MoS2@NSC-Ⅱ at 0.1 A g−1. (c) The cycling performance of MoO2/MoS2@NSC-Ⅱ at 0.1 A g−1. (d) The rate performance of MoO2@NSC, MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ and MoO2/MoS2@NSC-Ⅲ. (e) Long-term cycling performance of MoO2@NSC, MoO2/MoS2@NSC-Ⅰ, MoO2/MoS2@NSC-Ⅱ and MoO2/MoS2@NSC-Ⅲ at 2.0 A g−1. Ex-situ XPS analysis of the MoO2/MoS2@NSC-Ⅱ electrode at fully discharged/charged states: (f) Mo 3d, (g) O 1s and (h) S 2p high-resolution XPS spectra
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