Se with Se-C bonds encapsulated in a honeycomb 3D porous carbon as an excellent performance cathode for Li-Se batteries
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摘要: 锂-硒电池因其超高的体积能量密度和硒的高电导率而被认为是一种极具有发展前景的锂离子电池。然而，循环过程中电极严重的体积膨胀和多硒化物溶解，以及硒的低负载，阻碍了锂-硒电池应用的发展。解决这三个问题的一种行之有效的方法是将硒限制在具有丰富孔体积的碳基质中，并同时增强硒与碳的界面相互作用。通过将Se浸入酒石酸盐衍生的蜂窝状三维多孔炭中，合成出了一种具有Se―C键的蜂窝状三维多孔炭@硒(HPC@Se)的新型正极材料用于锂-Se电池。得到的蜂窝状三维多孔炭的孔体积可达1.794 cm3g−1，能够均匀包封65%硒。此外，硒与碳之间的强化学键有利于稳定硒，从而进一步缓解其巨大的体积膨胀和多硒化物的溶解，还可促进循环过程中的电荷转移。该HPC@Se正极呈现出极好的循环性能和倍率性能。在0.2 C的电流密度下，经200次循环后，其比容量可保持在561 mAhg−1(为理论比容量的83%)，每次循环的比容量衰减率仅为0.058%。此外，在5 C的高电流密度下，HPC@Se正极还可以达到472.8 mAhg−1的可观容量。Abstract: Li-Se batteries have risen to prominence as promising lithium-ion batteries thanks to their ultrahigh volumetric energy density and the high electrical conductivity of Se. However, the use of Li-Se batteries is limited not only by the large volume expansion and dissolution of polyselenides in the cathodes during cycling, but also the low selenium loading. A highly effective and currently feasible approach to simultaneously tackle these problems is to position the selenium in a carbon matrix with a sufficient pore volume to accommodate the expansion while increasing the interfacial interaction between the selenium and carbon. We have synthesized a novel cathode material (Se@HPC) for Li-Se batteries of a honeycomb 3D porous carbon derived from a tartrate salt, that was impregnated with Se to produce Se-C bonds. The pore volume of the honeycomb 3D porous carbon was as high as 1.794 cm3 g−1, which allowed 65 wt% selenium to be uniformly encapsulated. Moreover, the strong chemical bonds between selenium and carbon stabilize the selenium, thus inhibiting its huge volume expansion and the dissolution of polyselenides, and promoting charge transfer during cycling. As expected, a Se@HCP cathode has excellent cyclability and a good rate performance. After 200 cycles at 0.2 C, its specific capacity remains at 561 mA h g−1, 83% of the theoretical value, and decays by only 0.058% per cycle. It also has a large capacity of 472.8 mA h g−1 under a high current density of 5 C.
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Key words:
- Li-Se batteries /
- Cathodes /
- Honeycomb 3D porous carbon /
- High loading /
- Se―C bonds
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Figure 1. SEM images of (a, b) HPC, (c, d) HPC@Se and (e) Elemental mapping of Se and (f) carbon in HPC@Se composite. Insert in (a) is the digital photograph of honeycomb
Figure 2. TEM images of (a, b) HPC and (c, d) HPC@Se, (e) N2 adsorption-desorption isotherms and (f) pore size distributions of HPC and HPC@Se
Figure 3. (a) Typical XRD spectra, (b) FTIR patterns, (c) Raman patterns of pristine Se, HPC@Se and HPC, (d) TGA of HPC@Se, XPS spectra of Se3d signal (e) and C1s signal (f)
Figure 4. (a) CV curves between 1.0 and 3.0 V (ver. Li/Li+) at a scan rate of 0.1 mV s−1, (b) Galvanostatic charge/discharge profiles for the first 3 cycles at 0.2 C, (c) Cycle capacity at 0.2 C, (d) The rate performance for HPC@Se and (e) Nyquist plots of the HPC@Se and pristine Se
Figure 5. (a, b) Digital photos of pristine Se and HPC@Se electrodes after 200 cycles at 0.2 C in electrolyte. (c) SEM image of HPC@Se after 200 cycles and its elemental mapping of (d) carbon and (e) Se
Figure 6. (a) XRD spectra of pristine Se, Ex-situ XRD spectra of HPC@Se discharged to 1.0 V and charged to 3.0 V, (b) FTIR spectra of HPC@Se discharged to 1.0 V and charged to 3.0 V at 0.2 C
Figure 7. (a) CV profiles of HPC@Se with gradually increasing scan rates from 0.1 to 5 mV s−1, (b) b-value for the oxidation peak and reduction peak, (c) Contribution ratio of capacitance and diffusion behavior at 0.1, 0.5, 1 and 5 mV s−1 scan rates, (d) Summary of the ratio of capacitive-controlled and diffusion-controlled contribution with gradually increasing scan rates for HPC@Se electrode
Table 1. Comparison between HPC@Se (this work) and the published Se/C electrodes
Material Selenium
contentReversible capacity
(mA h g−1)Percentage of theoretical capacity
(678 mA h g−1)Current density
(C, 1C = 678 mA h g−1)Ref. HPC@Se 65 wt% 561/200 cycles 82.7% 0.2 C This work Mic/Se 44.2 wt% 400/500 cycles 59.0% 0.5 C [13] Se@LHPC 52 wt% 450/500 cycles 66.4% 0.5 C [14] Se-HPCF 50 wt% 533/50 cycles 78.6% 0.2 C [15] C/Se 54 wt% 430/250 cycles 63.4% 100 mA g−1 [16] Se@3D MIL-68 (Al)@MWCNTs 56 wt% 453/200 cycles 66.8% 0.2 C [25] Se@HPCNBs 60 wt% 560/100 cycles 82.6% 0.2 C [26] 
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