Bismuth nanoparticles anchored on N-doped graphite felts to give stable and efficient iron-chromium redox flow batteries
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摘要: 铁铬氧化还原液流电池 (ICRFB) 是一种具有成本效益的可规模化储能系统，其利用资源丰富、低成本的铬和铁作为电解液的活性物质。然而，ICRFB存在Cr3+/Cr2+电化学活性低、负极易产生严重的析氢反应 (HER) 等问题。本文报道了一种简单的合成策略，即通过自聚合和湿化学还原方法结合煅烧处理，在氮掺杂石墨毡 (GF) 表面沉积了非晶态铋 (Bi) 纳米颗粒 (NPs)，其作为ICRFB的负极材料时可展示出高效的电化学性能。生成的Bi NPs与H+形成中间体，极大地抑制了HER副反应。此外，Bi的引入和GF表面的N掺杂通过协同作用显著提高了Fe2+/Fe3+和Cr3+/Cr2+的电化学活性，降低了电荷传递电阻，提高了反应传质速率。在不同的电流密度下，经25次循环，库仑效率仍高达97.7%。在60.0 mA cm−2电流密度下，能量效率达到85.8%，超过了许多其他报道的材料。循环100次后容量达到862.7 mAh/L，约为GF的5.3倍。Abstract: Iron-chromium redox flow batteries (ICRFBs) use abundant and inexpensive chromium and iron as the active substances in the electrolyte and have great potential as a cost-effective and large-scale energy storage system. However, they are still plagued by several issues, such as the low electrochemical activity of Cr3+/Cr2+ and the occurrence of the undesired hydrogen evolution reaction (HER). We report the synthesis of amorphous bismuth (Bi) nanoparticles (NPs) immobilized on N-doped graphite felts (GFs) by a combined self-polymerization and wet-chemistry reduction strategy followed by annealing, which are used as the negative electrodes for ICRFBs. The resulting Bi NPs react with H+ to form intermediates and greatly inhibit the parasitic HER. In addition, the combined effect of Bi and N dopants on the surface of GF dramatically increases the electrochemical activity of Fe2+/Fe3+ and Cr3+/Cr2+, reduces the charge transfer resistance, and increases the mass transfer rate compared to plain GF. At the optimum Bi/N ratio of 2, a high coulombic efficiency of up to 97.7% is maintained even for 25 cycles at different current densities, the energy efficiency reaches 85.8% at 60.0 mA cm−2, exceeding many other reported materials, and the capacity reaches 862.7 mAh L−1 after 100 cycles, which is about 5.3 times that of bare GF.
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Key words:
- Iron-chromium flow battery /
- Bi /
- Negative electrode /
- Nitrogen doping /
- Graphite felt
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Figure 2. STEM characterisation of Bi/N-GF. (a) Low magnification bright field (BF)-STEM image. (b) Magnified view of the indicated area in (a), showing nanoparticle decoration of the graphite flake. (c) High magnification HAADF-STEM image of the particles, showing amorphous aggregation of atoms and some loose single atoms. (d) HAADF-STEM image and (e) fast Fourier transform of a nanoparticle, confirming lack of crystallinity. (f) HAADF-STEM image and (g−i) accompanying EDS mapping, confirming Bi aggregate nanoparticles dispersed on the N-doped graphite felt
Figure 3. (a) XRD patterns of GF and Bi/N-GF. (b) Wide-survey and (c) N 1s XPS spectra of GF and Bi/N-GF. (d) Bi 4f XPS spectrum of Bi/N-GF
Figure 4. CV curves of GF, N-GF, Bi-GF and Bi/N-GF derived under (a) 40.0 mV s−1 and voltage range of 0−0.8 V (vs. SCE) at the positive electrode and (b) 6.0 mV s−1 and voltage range from −0.8 to 0 V at the negative electrode. CV curves of GF, Bi/N-GF-0.5, Bi/N-GF-1, and Bi/N-GF-2 obtained under (c) 40.0 mV s−1 and voltage range of 0−0.8 V at the positive electrode and (d) 6.0 mV s−1, −0.8−0 V at the negative electrode. EIS diagrams of GF, N-GF, Bi-GF, and Bi/N-GF measured under (e) 0.35 V at the positive electrode and (f) −0.5 V at the negative electrode. EIS diagrams of GF, Bi/N-GF-0.5, Bi/N-GF-1, and Bi/N-GF-2 acquired under (c) 0.35 V at the positive electrode and (d) −0.5 V at the negative electrode
Figure 5. EEs at different current densities in ICRFB for (a) GF, N-GF, Bi-GF and Bi/N-GF, and (b) GF, Bi/N-GF-0.5, Bi/N-GF-1 and Bi/N-GF-2. EEs of (c) GF, N-GF, Bi-GF and Bi/N-GF and (d) GF, Bi/N-GF-0.5, Bi/N-GF-1 and Bi/N-GF-2 tested at 60.0 mA cm−2 and 100 cycles in ICRFB. Charge–discharge curves at the (e) 2nd and (f) 100th cycle in the voltage range of 0.8 to 1.2 V for GF, N-GF, Bi-GF and Bi/N-GF. Charge–discharge curves at the (g) 2nd and (h) 100th cycle in the voltage range of 0.8 to 1.2 V for GF, Bi/N-GF-0.5, Bi/N-GF-1 and Bi/N-GF-2
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