摘要
采用直流电弧等离子体法在甲烷和氩气混合气氛下原位合成碳化钛(TiC)纳米颗粒。X射线衍射、透射电子显微镜等物理表征结果显示TiC纳米颗粒粒径约为40~90 nm的立方体结构。循环伏安(CV)测试表明,TiC纳米颗粒兼具高效的氧还原和氧析出双效催化活性,可有效弥补炭材料氧析出催化活性较弱的缺陷。恒流充放电测试结果表明,相对于普通炭材料(导电炭黑,Super-P),TiC纳米颗粒催化剂可将锂空电池充电过电势降低280mV;在电流密度(i_(sp))为50mA·g~(-1)时,首次放电比容量达1267mAh·g~(-1);即使在较高的电流密度150mA·g~(-1)下,比容量仍保持在778mAh·g~(-1),体现了良好的倍率性能。在电流密度为100mA·g~(-1)、限定比容量为500mAh·g~(-1)下,稳定循环10次。通过XRD、红外、扫描电镜表征可知,在TiC纳米颗粒的双效催化作用下,Li_2O_2的生成与分解具有良好的可逆性,有效避免了大量反应副产物积累的问题,进而提高锂空电池的电化学性能。
Titanium carbide(TiC)nanoparticles were synthesized in situ by direct current(DC)arc-discharge method under the mixture of methane and argon gas atmosphere. The physical characterization including X-ray diffraction(XRD)and transmission electron microscope(TEM)show that TiC nanoparticles have cubic structure with grain sizes of 40-90 nm. Cyclic voltammetry(CV)measurement indicates that TiC nanoparticles are efficient bi-functional catalysts toward both oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)for Li-O_2 batteries, which can effectively compensate for the weak catalytic activity of OER of carbon materials. The results of galvanostatic charge-discharge measurement present that the TiC nanoparticles can reduce the charge-overpotential by 280 mV compared to general carbon materials(Super-P), and the TiC electrode delivers an initial discharge capacity of 1267 mAh·g~(-1) at 50 mA·g~(-1). Even at a high current density of 150 mA·g~(-1), the discharge capacity still maintains 778 mAh·g~(-1), indicating excellent rate performance of lithium-air batteries with TiC nanoparticles as catalysts. The TiC electrode displays 10 cycles at a fixed capacity of 500 mAh·g~(-1) and at a current density of 100 mA·g~(-1).The characterization of XRD, Fourier transform infrared(FT-IR)and scanning electron microscopy(SEM)show that the formation and decomposition of Li_2O_2 have great reversibility under the bi-functional catalysis of TiC nanoparticles, which can significantly alleviate the accumulation of undesired byproducts, and eventually improve the electrochemical performance of Li-air batteries.
引文
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