立方相碳化钛在锂空电池中的电化学行为
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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.
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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[25] KALUBARME R S, JADHAV H S, NGO D T, et al. Simple synthesis of highly catalytic carbon-free MnCo2O4@Ni as an oxygen electrode for rechargeable Li-O2 batteries with long-term stability[J]. Scientific Reports, 2015, 5:13266.
[26] PENG S, HU Y, LI L, et al. Controlled synthesis of porous spinel cobaltite core-shell microspheres as high-performance catalysts for rechargeable Li-O2 batteries[J]. Nano Energy, 2015, 13:718-726.
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[29] McCLOSKEY B D, BETHUNE D S, SHELBY R M, et al. Solvents’ critical role in nonaqueous lithium-oxygen battery electrochemistry[J]. Journal of Physical Chemistry Letters, 2011, 2(10):1161-1166.
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[32] SHUI J L, OKASINSKI J S, KENESEI P, et al. Reversibility of anodic lithium in rechargeable lithium-oxygen batteries[J]. Nature Communications, 2013, 4(4):2255.
[33] ASSARY R S, LU J, DU P, et al. The effect of oxygen crossover on the anode of a Li-O2 battery using an ether-solvent: insights from experimental and computational studies[J]. Chemsuschem, 2013, 6(1):51-55.
[34] SU D, DOU S, WANG G. Gold nanocrystals with variable index facets as highly effective cathode catalysts for lithium-oxygen batteries[J]. NPG Asia Materials, 2015, 7(1):e155.
[35] CAO R, LEE J, LIU M, et al. Non-precious catalysts: recent progress in non-precious catalysts for metal-air batteries[J]. Advanced Energy Materials, 2012, 2(7):816-829.
[36] LEE C K, PARK Y J. Polyimide-wrapped carbon nanotube electrodes for long cycle Li-air batteries[J]. Chemical Communications, 2015, 51(7):1210-1213.
[37] ZHANG S S, FOSTER D, READ J. Discharge characteristic of a non-aqueous electrolyte Li/O2 battery[J]. Journal of Power Sources, 2010, 195(4):1235-1240.
[38] BALAISH M, KRAYTSBERG A, EIN-ELI Y. A critical review on lithium-air battery electrolytes[J]. Physical Chemistry Chemical Physics, 2014, 16(7):2801-2822.
[39] CHEN Y, FREUNBERGER S A, PENG Z, et al. Charging a Li-O2 battery using a redox mediator[J]. Nature Chemistry, 2013, 5(6):489-494.
[40] ZHANG T, ZHOU H. A reversible long-life lithium-air battery in ambient air[J]. Nature Communications, 2013, 4(5):1817.
[2] BRUCE P G, FREUNBERGER S A, HARDWICK L J, et al. Li-O2 and Li-S batteries with high energy storage[J]. Nature Materials,2012, 11(1):19-29.
[3] 吴爱明,夏国锋,沈水云,等. 非水体系锂-空气电池研究进展[J]. 物理化学学报, 2016, 32(8):1866-1879. WU A M, XIA G F, SHEN S Y, et al.Recent progress in non-aqueous lithium-air batteries[J]. Acta Physico-Chimica Sinica,2016, 32(8):1866-1879.
[4] LEE J, TAI KIM S, CAO R, et al. Metal-air batteries: Metal-air batteries with high energy density: Li-air versus Zn-air[J]. Advanced Energy Materials, 2011, 1(1):34-50.
[5] GUO Z, ZHOU D, LIU H, et al. Synthesis of ruthenium oxide coated ordered mesoporous carbon nanofiber arrays as a catalyst for lithium oxygen battery[J]. Journal of Power Sources, 2015, 276:181-188.
[6] KIM B G, KIM H J, BACK S, et al. Improved reversibility in lithium-oxygen battery: understanding elementary reactions and surface charge engineering of metal alloy catalyst[J]. Scientific Reports, 2014, 4:4225.
[7] SUN B, MUNROE P, WANG G. Ruthenium nanocrystals as cathode catalysts for lithium-oxygen batteries with a superior performance[J]. Scientific Reports, 2013, 3:2247.
[8] CHEN M, JIANG X, YANG H, et al. Performance improvement of air electrode for Li/air batteries by hydrophobicity adjustment[J]. Journal of Materials Chemistry A, 2015, 3(22):11874-11879.
[9] 李鹏,孙彦平. 非水系二次锂-氧电池正极[J]. 化学进展, 2012, 24(12):2457-2471. LI P, SUN Y P. Positive electrodes of non-aqueous rechargeable lithium-oxygen batteries[J]. Progress in Chemistry, 2012, 24(12):2457-2471.
[10] LI Q, CAO R, CHO J, et al. Nanostructured carbon-based cathode catalysts for nonaqueous lithium-oxygen batteries[J]. Physical Chemistry Chemical Physics, 2014, 16(27):13568-13582.
[11] GUO Z, ZHOU D, DONG X, et al. Ordered hierarchical mesoporous/macroporous carbon: a high-performance catalyst for rechargeable Li-O2 batteries[J]. Advanced Materials, 2013, 25(39):5668-5672.
[12] DéBART A, BAO J, ARMSTRONG G, et al. An O2 cathode for rechargeable lithium batteries: the effect of a catalyst[J]. Journal of Power Sources, 2007, 174(2):1177-1182.
[13] THOTIYL M, FREUNBERGER S A, PENG Z, et al. A stable cathode for the aprotic Li-O2 battery[J]. Nature Materials, 2013, 12(11):1050-1056.
[14] KIM J, LEE J, TAK Y. Relationship between carbon corrosion and positive electrode potential in a proton-exchange membrane fuel cell during start/stop operation[J]. Journal of Power Sources, 2009, 192(2):674-678.
[15] PENG Z, FREUNBERGER S A, CHEN Y,et al.A reversible and higher-rate Li-O2battery[J]. Science,2012, 337(6094): 563-566.
[16] PARK I,KIM T,PARK H,et al.Preparation and electrochemical properties of Pt-Ru/Mn3O4/C bifunctional catalysts for lithium-air secondary battery[J].Journal of Nanoscience & Nanotechnology,2016,16(10):10453-10458.
[17] KONINCK M D, MARSAN B. MnxCuxCoO used as bifunctional electrocatalyst in alkaline medium[J]. Electrochimica Acta, 2008, 53(23):7012-7021.
[18] LI C, HAN X, CHENG F, et al. Phase and composition controllable synthesis of cobalt manganese spinel nanoparticles towards efficient oxygen electrocatalysis[J]. Nature Communications, 2015, 6:7345.
[19] QIU F, HE P, JIANG J, et al. Ordered mesoporous TiC-C composites as cathode materials for Li-O2 batteries[J]. Chemical Communications, 2016, 52(13):2713-2716.
[20] 甘小荣,薛方红,黄昊,等. SiC/C纳米复合材料的制备与性能表征[J].材料工程, 2014(2):75-80. GAN X R, XUE F H, HUANG H,et al. Preparation and characterization of SiC/C nano-composites[J]. Journal of Materials Engineering, 2014(2):75-80.
[21] 周远良,赛义德,张黎,等. 树脂基Fe纳米粒子及碳纤维复合吸波平板的制备与性能[J]. 材料工程, 2018,46 (3):41-47. ZHOU Y L, SHAH S, ZHANG L, et al. Preparation and performance of resin-based Fe nanoparticals/carbon fibers microwave absorbing composite plates[J]. Journal of Materials Engineering, 2018,46 (3):41-47.
[22] XU J, XU D, WANG Z, et al. Synthesis of perovskite-based porous La0.75Sr0.25MnO3 nanotubes as a highly efficient electrocatalyst for rechargeable lithium-oxygen batteries[J]. Angewandte Chemie, 2013, 52(14):3887-3890.
[23] CHEN J, HUMMELSH?J J S, THYGESEN K S, et al. The role of transition metal interfaces on the electronic transport in lithium-air batteries[J]. Catalysis Today, 2011, 165(1):2-9.
[24] ZHANG T, IMANISHI N, SHIMONISHI Y, et al. A novel high energy density rechargeable lithium/air battery[J]. Chemical Communications, 2010, 46(10):1661-1663.
[25] KALUBARME R S, JADHAV H S, NGO D T, et al. Simple synthesis of highly catalytic carbon-free MnCo2O4@Ni as an oxygen electrode for rechargeable Li-O2 batteries with long-term stability[J]. Scientific Reports, 2015, 5:13266.
[26] PENG S, HU Y, LI L, et al. Controlled synthesis of porous spinel cobaltite core-shell microspheres as high-performance catalysts for rechargeable Li-O2 batteries[J]. Nano Energy, 2015, 13:718-726.
[27] WANG C, ZHAO Y, LIU J, et al. Highly hierarchical porous structures constructed from NiO nanosheets act as Li ion and O2 pathways in long cycle life, rechargeable Li-O2 batteries[J]. Chemical Communications, 2016, 52(79):11772-11774.
[28] DONG S, CHEN X, ZHANG K, et al. Molybdenum nitride based hybrid cathode for rechargeable lithium-O2 batteries[J]. Chemical Communications, 2011, 47(40):11291-11293.
[29] McCLOSKEY B D, BETHUNE D S, SHELBY R M, et al. Solvents’ critical role in nonaqueous lithium-oxygen battery electrochemistry[J]. Journal of Physical Chemistry Letters, 2011, 2(10):1161-1166.
[30] McCLOSKEY B D, VALERY A, LUNTZ A C, et al. Combining accurate O2 and Li2O2 assays to separate discharge and charge stability limitations in nonaqueous Li-O2 batteries[J]. Journal of Physical Chemistry Letters, 2013, 4(17):2989-2993.
[31] THOTIYL M M O, FREUNBERGER S A, PENG Z, et al. The carbon electrode in nonaqueous Li-O2cells[J]. Journal of the American Chemical Society, 2016, 135(1):494-500.
[32] SHUI J L, OKASINSKI J S, KENESEI P, et al. Reversibility of anodic lithium in rechargeable lithium-oxygen batteries[J]. Nature Communications, 2013, 4(4):2255.
[33] ASSARY R S, LU J, DU P, et al. The effect of oxygen crossover on the anode of a Li-O2 battery using an ether-solvent: insights from experimental and computational studies[J]. Chemsuschem, 2013, 6(1):51-55.
[34] SU D, DOU S, WANG G. Gold nanocrystals with variable index facets as highly effective cathode catalysts for lithium-oxygen batteries[J]. NPG Asia Materials, 2015, 7(1):e155.
[35] CAO R, LEE J, LIU M, et al. Non-precious catalysts: recent progress in non-precious catalysts for metal-air batteries[J]. Advanced Energy Materials, 2012, 2(7):816-829.
[36] LEE C K, PARK Y J. Polyimide-wrapped carbon nanotube electrodes for long cycle Li-air batteries[J]. Chemical Communications, 2015, 51(7):1210-1213.
[37] ZHANG S S, FOSTER D, READ J. Discharge characteristic of a non-aqueous electrolyte Li/O2 battery[J]. Journal of Power Sources, 2010, 195(4):1235-1240.
[38] BALAISH M, KRAYTSBERG A, EIN-ELI Y. A critical review on lithium-air battery electrolytes[J]. Physical Chemistry Chemical Physics, 2014, 16(7):2801-2822.
[39] CHEN Y, FREUNBERGER S A, PENG Z, et al. Charging a Li-O2 battery using a redox mediator[J]. Nature Chemistry, 2013, 5(6):489-494.
[40] ZHANG T, ZHOU H. A reversible long-life lithium-air battery in ambient air[J]. Nature Communications, 2013, 4(5):1817.