MoS2的电化学表征与探究(英)

doi:10.3969/j.issn.1000-5641.2015.03.013

摘要/Abstract

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.}

关键词: 锂离子电池, MoS2结构特性, 电化学性能, 第一性原理计算

Abstract: By combining experimental methods with first-principles calculations this article reports the determination of the structural characters of MoS₂in 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

Key words: lithium-ion batteries, MoS₂, structural characters, electrochemistry, first-principles calculations

中图分类号:

O646.21

张贤惠,陈珍莲,陈晓波. MoS2的电化学表征与探究(英)[J]. 华东师范大学学报(自然科学版), 2015, 2015(3): 105-115.

ZHANG Xian-hui,CHEN Zhen-lian,CHEN Xiao-bo, LI Jun. Characterization of and insight into the electrochemistry of MoS2[J]. Journal of East China Normal University(Natural Sc, 2015, 2015(3): 105-115.

参考文献

[1]ZHOU X, WAN L J, GUO Y G. Synthesis of MoS$_{2$ nanosheet--graphene

nanosheet hybrid materials for stable lithium storage[J]. Chemical

Communications, 2013, 49(18): 1838.
[2] SATHISH M, TOMAI T, HONMA I. Graphene anchored with Fe$_3$O$_4$ nanoparticles

as 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 high

performance 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 the

synthesis of MoS$_2$ nanospheres with excellent Li-ion storage

properties [J]. Cryst Eng Comm, 2012, 14(24): 8323.
[5] WINTER M, BRODD R J. What are batteries, fuel cells, and

supercapacitors [J]. Chem Rev 2004, 104: 4245-4269.
[6] CHANG K, CHEN W. In situ synthesis of MoS$_{2$/graphene nanosheet

composites with extraordinarily high electrochemical performance for

lithium ion batteries [J]. Chemical Communications, 2011, 47(14):

4252.
[7] BRIVIO J, ALEXANDER D T L, KIS A. Ripples and layers in ultrathin

MoS$_{2$ embranes [J]. Nano Letters, 2011, 11(12): 5148-5153.
[8] TENNE R, MARGULIS L, GENUT M, et al. Polyhedral and cylindrical

structures of tungsten disulphide [J]. Letters to Nature, 1992, 360:

4-6.
[9] RAMAKRISHNAMATTE H S S, GOMATHI A, MANNA A K, et al. MoS$_{2$ and

WS$_{2$ Analogues of graphene [J]. Angewandte Chemie, 2010,

122(24): 4153-4156.
[10] WHITTINGHAM M S, GAMBLE JR F R. The lithium intercalates of the

transition 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 the

electrochemical potential in intercalation electrodes [J]. J Phys

Chem B, 2004, 108: 6093-6099.
[13] WANG Q, LI J. Facilitated lithium storage in MoS$_2$ overlayers supported

on 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 hierarchical

MoS$_{2$ microspheres composed of few-layered nanosheets and their

lithium storage properties [J]. Nanoscale, 2012, 4(1): 95.
[15] KWON J H, AHN H J, JEON M S, et al. The electrochemical properties of

Li/TEGDME/MoS$_{2$ cells using multi-wall carbon nanotubes as a

conducting 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 of

molybdenum disulfide (MoS$_{2)$ nanocomposites [J]. Energy {\&

Environmental Science, 2014, 7(1): 209.
[17] CATHERINE M. ZELENSKI, DORHOUT P K. Template synthesis of

near-monodisperse [J]. J Am Chem Soc 1998, 120: 734-742.
[18] XIANHUI CHEN, FAN R. Low-temperature hydrothermal synthesis of

transition [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$_2$/amorphous

carbon composites with high capacity and excellent stability as

anode materials for lithium ion batteries [J]. Journal of Materials

Chemistry, 2011, 21(17): 6251.
[21] YANG L, WANG S, MAO J, et al. Hierarchical MoS$_{2$/polyaniline

nanowires with excellent electrochemical performance for lithium-ion

batteries [J]. Advanced Materials, 2013, 25(8): 1180-1184.
[22] MAP Y, HAERING R R. Structural destabilization induced by lithium

intercalation in MoS$_{2$ andrelated compounds [J]. Canadian

Journal of Physics, 1983, 61: 76-84
[23] DU G, GUO Z, WANG S, et al. Superior stability and high capacity of

restacked molybdenum disulfide as anode material for lithium ion

batteries [J]. Chemical Communications, 2010, 46(7): 1106.
[24] GORDON R A, YANG D, CROZIER E D, et al. Structures of exfoliated single

layers 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 phase

transitions induced by lithium ion intercalation in molybdenum

disulphide [J]. Chinese Science Bulletin, 2013, 58(14): 1632-1641.
[26] CHEN X, HE J, SRIVASTAVA D, et al. Electrochemical cycling

reversibility of LiMoS$_{2$ using first-principles calculations

[J]. Applied Physics Letters, 2012, 100(26): 263901.
[27] JOHN P, KIERON B, ERNZERHOF M. Generalized gradient

approximation made simple [J]. Phys Rev Lett, 1996, 77: 3865-3868.
[28] KRESSE G, HAFNER J. Ab initio molecular-dynamics simulation of the

liquid-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 initio

total-energy calculations using a plane-wave basis set [J]. Physical

Review 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 a

long-range dispersion correction [J]. Journal of Computational

Chemistry, 2006, 27(15): 1787-1799.
[32] CHEN Z, LI J, ZHANG Z. First principles investigation of electronic

structure change and energy transfer by redox in inverse spinel

cathodes LiNiVO$_{4$ and LiCoVO$_{4$ [J]. Journal of Materials

Chemistry, 2012, 22(36): 18968.
[33] NEUGEBAUER J, SCHEFFLER M. Adsorbate-substrate and adsorbate-adsorbate

interactions 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 initio

calculations [J]. Physical Review B, 1995, 51(7): 4014-4022.
[35] ZHANG C, WU H B, GUO Z, et al. Facile synthesis of carbon-coated

MoS$_{2$ 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 disordered

graphene-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-assembled

MoS$_{2$-carbon nanostructures: influence of nanostructuring and

carbon on lithium battery performance [J]. Journal of Materials

Chemistry, 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]. Materials

Research Bulletin, 2009, 44(9): 1811-1815.
[39] FANG X, HUA C, GUO X, et al. Lithium storage in commercial MoS$_{2$ in

different potential ranges [J]. Electrochimica Acta, 2012, 81:

155-160.
[40] LIU C, YU Z, NEFF D, et al. Graphene-based supercapacitor with an

ultrahigh 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 in

open-ended TiS$_{2 $ nano-tubes [J]. Angewandte Chemie, 2003,

115(19): 2197-2201.
[43] JULIEN C M. Lithium intercalated compounds charge transfer and related

properties [J]. Materials Science and Engineering R, 2003, 40:

47-102.
[44] DAHN J R, ZHENG T, LIU Y, et al. Mechanisms for lithium insertion in

carbonaceous materials [J]. Science, 1995, 270(5236): 590-593.