Characterization of and insight into the electrochemistry of MoS2
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摘要: 结合实验和第一性原理计算,对MoS2首次充放电过程中的第一阶段相变的结构变化进行了研究.研究表明1.1V处的电压平台对应于锂离子嵌入量0.56, 锂离子都是嵌入2H相的八面体空位,与计算出的平台电压值及MoS2的相稳定特性都相吻合.但当锂离子嵌入量超过1.0时, 晶体结构向无定形结构转变,导致后续充电过程中不出现平台特征. 此外,通过对比MoS2和LiCoO2 的嵌入能量项,本文探究了决定正极与负极材料本征电压差的物理机制.}Abstract: By combining experimental methods with first-principles calculations this article reports the determination of the structural characters of MoS2 in the first discharging and charging cycling, where the first stage phase transformation occurs.The significant voltage plateau at 1.1 V is attributed to lithium insertion on octahedral vacancy sites of 2H-Lix MoS2 with lithium concentration (x)up to 0.56, which corresponds with the calculated voltage and phase stability of MoS$_{2}$. However, the ensuing amorphization for $x$ over 1.0 immediately removes the plateau character from the charging curve. Furthermore, we offer a comparison to LiCoO2 to investigate the physical mechanism of the anode and cathode voltaic
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[1]ZHOU X, WAN L J, GUO Y G. Synthesis of MoS$_{2$ nanosheet--graphenenanosheet hybrid materials for stable lithium storage[J]. ChemicalCommunications, 2013, 49(18): 1838.[2] SATHISH M, TOMAI T, HONMA I. Graphene anchored with Fe$_3$O$_4$ nanoparticlesas anode for enhanced Li-ion storage[J]. Journal of Power Sources,2012, 217: 85-91.[3] CHEN S, WANG Y, AHN H, et al. Microwave hydrothermal synthesis of highperformance tin-graphene nanocomposites for lithium ion batteries[J]. Journal of Power Sources, 2012, 216: 22-27.[4] PARK S K, YU S H, WOO S, et al. A facile and green strategy for thesynthesis of MoS$_2$ nanospheres with excellent Li-ion storageproperties [J]. Cryst Eng Comm, 2012, 14(24): 8323.[5] WINTER M, BRODD R J. What are batteries, fuel cells, andsupercapacitors [J]. Chem Rev 2004, 104: 4245-4269.[6] CHANG K, CHEN W. In situ synthesis of MoS$_{2$/graphene nanosheetcomposites with extraordinarily high electrochemical performance forlithium ion batteries [J]. Chemical Communications, 2011, 47(14):4252.[7] BRIVIO J, ALEXANDER D T L, KIS A. Ripples and layers in ultrathinMoS$_{2$ embranes [J]. Nano Letters, 2011, 11(12): 5148-5153.[8] TENNE R, MARGULIS L, GENUT M, et al. Polyhedral and cylindricalstructures of tungsten disulphide [J]. Letters to Nature, 1992, 360:4-6.[9] RAMAKRISHNAMATTE H S S, GOMATHI A, MANNA A K, et al. MoS$_{2$ andWS$_{2$ Analogues of graphene [J]. Angewandte Chemie, 2010,122(24): 4153-4156.[10] WHITTINGHAM M S, GAMBLE JR F R. The lithium intercalates of thetransition metal dichalcogenides [J]. Materials Research Bulletin,1975, 10(5): 363-371.[11] WHITTINGHAM M S. The role of ternary phases in cathode reactions [J].Journal of The Electrochemical Society, 1976, 123(3): 315-320.[12] DINO T, CHRISTIAN P, JAEGERMANN W. Origin of theelectrochemical potential in intercalation electrodes [J]. J PhysChem B, 2004, 108: 6093-6099.[13] WANG Q, LI J. Facilitated lithium storage in MoS$_2$ overlayers supportedon coaxial carbon nanotubes [J]. J Phys Chem C, 2007, 111:1675-1682.[14] DING S, ZHANG D, CHEN J S, et al. Facile synthesis of hierarchicalMoS$_{2$ microspheres composed of few-layered nanosheets and theirlithium storage properties [J]. Nanoscale, 2012, 4(1): 95.[15] KWON J H, AHN H J, JEON M S, et al. The electrochemical properties ofLi/TEGDME/MoS$_{2$ cells using multi-wall carbon nanotubes as aconducting agent [J]. Research on Chemical Intermediates, 2010,36(6/7): 749-759.[16] STEPHENSON T, LI Z, OLSEN B, et al. Lithium ion battery applications ofmolybdenum disulfide (MoS$_{2)$ nanocomposites [J]. Energy {\&Environmental Science, 2014, 7(1): 209.[17] CATHERINE M. ZELENSKI, DORHOUT P K. Template synthesis ofnear-monodisperse [J]. J Am Chem Soc 1998, 120: 734-742.[18] XIANHUI CHEN, FAN R. Low-temperature hydrothermal synthesis oftransition [J]. Chem Mater, 2001, 13: 802 -805.[19] DRESSELHAUS M S, THOMAS I L. Alternative energy technologies [J].Nature, 2001, 414(6861): 332-337.[20] CHANG K, CHEN W X, MA L, et al. Graphene-like MoS$_2$/amorphouscarbon composites with high capacity and excellent stability asanode materials for lithium ion batteries [J]. Journal of MaterialsChemistry, 2011, 21(17): 6251.[21] YANG L, WANG S, MAO J, et al. Hierarchical MoS$_{2$/polyanilinenanowires with excellent electrochemical performance for lithium-ionbatteries [J]. Advanced Materials, 2013, 25(8): 1180-1184.[22] MAP Y, HAERING R R. Structural destabilization induced by lithiumintercalation in MoS$_{2$ andrelated compounds [J]. CanadianJournal of Physics, 1983, 61: 76-84[23] DU G, GUO Z, WANG S, et al. Superior stability and high capacity ofrestacked molybdenum disulfide as anode material for lithium ionbatteries [J]. Chemical Communications, 2010, 46(7): 1106.[24] GORDON R A, YANG D, CROZIER E D, et al. Structures of exfoliated singlelayers of WS$_{2$, MoS$_{2$, and MoSe$_{2$ in aqueous suspension[J]. Physical Review B, 2002, 65(12): 125407.[25] CHEN X, CHEN Z, LI J. Critical electronic structures controlling phasetransitions induced by lithium ion intercalation in molybdenumdisulphide [J]. Chinese Science Bulletin, 2013, 58(14): 1632-1641.[26] CHEN X, HE J, SRIVASTAVA D, et al. Electrochemical cyclingreversibility of LiMoS$_{2$ using first-principles calculations[J]. Applied Physics Letters, 2012, 100(26): 263901.[27] JOHN P, KIERON B, ERNZERHOF M. Generalized gradientapproximation made simple [J]. Phys Rev Lett, 1996, 77: 3865-3868.[28] KRESSE G, HAFNER J. Ab initio molecular-dynamics simulation of theliquid-metal-amorphous-semiconductor transition in germanium [J].Physical Review B, 1994, 49(20): 251-269.[29] KRESSE G, FURTHMULLER J. Efficient iterative schemes for ab initiototal-energy calculations using a plane-wave basis set [J]. PhysicalReview B, 1996, 54(16): 169-186.[30] BLOCHL P E. Projector augmented-wave method [J]. Physical Review B,1994, 50(24): 953-979.[31] GRIMME S. Semiempirical GGA-type density functional constructed with along-range dispersion correction [J]. Journal of ComputationalChemistry, 2006, 27(15): 1787-1799.[32] CHEN Z, LI J, ZHANG Z. First principles investigation of electronicstructure change and energy transfer by redox in inverse spinelcathodes LiNiVO$_{4$ and LiCoVO$_{4$ [J]. Journal of MaterialsChemistry, 2012, 22(36): 18968.[33] NEUGEBAUER J, SCHEFFLER M. Adsorbate-substrate and adsorbate-adsorbateinteractions of Na and K adlayers on Al(111) [J]. Physical Review B,1992, 46(24): 16067-16080.[34] MAKOV G, PAYNE M. Periodic boundary conditions in ab initiocalculations [J]. Physical Review B, 1995, 51(7): 4014-4022.[35] ZHANG C, WU H B, GUO Z, et al. Facile synthesis of carbon-coatedMoS$_{2$ nanorods with enhanced lithium storage properties [J].Electrochemistry Communications, 2012, 20: 7-10.[36] HWANG H, KIM H, CHO J. MoS$_{2$ nanoplates consisting of disorderedgraphene-like layers for high rate lithium battery anode materials[J]. Nano Letters, 2011, 11(11): 4826-4830.[37] DAS S K, MALLAVAJULA R, JAYAPRAKASH N, et al. Self-assembledMoS$_{2$-carbon nanostructures: influence of nanostructuring andcarbon on lithium battery performance [J]. Journal of MaterialsChemistry, 2012, 22(26): 12988.[38] FENG C, MA J, LI H, et al. Synthesis of molybdenum disulfide(MoS$_{2)$ for lithium ion battery applications [J]. MaterialsResearch Bulletin, 2009, 44(9): 1811-1815.[39] FANG X, HUA C, GUO X, et al. Lithium storage in commercial MoS$_{2$ indifferent potential ranges [J]. Electrochimica Acta, 2012, 81:155-160.[40] LIU C, YU Z, NEFF D, et al. Graphene-based supercapacitor with anultrahigh energy density [J]. Nano Letters, 2010, 10(12): 4863-4868.[41] GOODENOUGH J B, KIM Y. Challenges for rechargeable li batteries [J].Chemistry of Materials, 2010, 22(3): 587-603.[42] CHEN J, TAO Z L, SUO L. Lithium intercalation inopen-ended TiS$_{2 $ nano-tubes [J]. Angewandte Chemie, 2003,115(19): 2197-2201.[43] JULIEN C M. Lithium intercalated compounds charge transfer and relatedproperties [J]. Materials Science and Engineering R, 2003, 40:47-102.[44] DAHN J R, ZHENG T, LIU Y, et al. Mechanisms for lithium insertion incarbonaceous materials [J]. Science, 1995, 270(5236): 590-593.
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